Ninth International Workshop“Characterization of Porous Materials: From
Angstroms to Millimeters”
May 19 – May 22, 2024
Workshop Chair: Alexander V. Neimark
Rutgers University, USA
Workshop Vice-Chair: Matthias Thommes
Friedrich-Alexander University Erlangen-Nürnberg, Germany
The Workshop will provide an opportunity to Discussion Topics
review and discuss the state-of-the-art • Molecular Thermodynamics of Fluids in Pores
approaches to characterize porous materials of • Adsorption and Capillary Phenomena
different origin. Lectures by recognized leaders• Intermolecular Interactions in Porousin porous materials science will cover both
Confinements
theoretical principles and methodology of• Computer Simulations and Density Functionalmodernexperimental
techniques.
Oral
Theorypresentations and poster sessions will
• Energetic Heterogeneity of Surfaces
complement invited and keynote lectures.
Proceedings will be published as a special • Fractal Characterization of Disordered Structures• Adsorption Porosimetry of Micro andvolume of the journal “Adsorption”.
Mesoporous Solids
Special sessions will focus on:• Mercury Porosimetry and Liquid Intrusion• Novel Nanoporous Materials and Adsorption
Techniques
Processes for Industrial Applications• Thermoporometry and Calorimetry• Computational Design and Screening of Novel• Chromatographic Characterization of Porous
Adsorbents
Materials• Modeling and Characterization of Hierarchical• High Resolution Microscopy and Image Analysis
Nanostructured Materials• Scattering Techniques for Pore Structure• Adsorption Induced Deformation and Phase
Analysis
Transformations of Porous Frameworks• In-situ Monitoring of Adsorption and Fluid
Flow in Porous Structures• Adsorption and Characterization of
Geosorbents: Shale, Coal, Soil
• Adsorption of Polymers, Proteins, andNanoparticles on Porous Substrates• Relations Between Structural, Transport, andFunctional Properties

International Advisory Committee
Australia
Paul A. Webley, Monash University
Austria• Freddy Kleitz, University of Vienna
Argentina• Karim Sapag, Universidad Nacional de San Luis
Belgium• Joeri Denayer, Vrije Universiteit Brussel
Brazil• Diana Azevedo, Federal University of Ceara. Fortaleza• Fred Tavares, Federal University of Rio de Janeiro
France• Benoit Coasne, University of Grenoble-Alpes, France• Renaud Denoyel, Aix-Marseille University-CNRS• Alain Fuchs, Paris Science and Letters
Germany• Michael Fröba, University of Hamburg• Martin Hartman, Friedrich-Alexander-University Erlangen-Nürnberg• Stefan Kaskel, Technische Universität Dresden
Greece• Theodore Steriotis, NCSR Demokritos• Pantelis N. Trikalitis, University of CreteJapan• Katsumi Kaneko, Shinshu University• Hirotomo Nishihara, Tohoku University
Morocco• Youssef Belmabkhout, Mohammed VI Polytechnic University, Benguerir
Poland• Bogdan Kuchta, Wrocław University of Science and Technology
Portugal• Paulo Mota, Universidade NOVA de Lisboa
Spain• Joaquin Silvestre-Albero, University of Alicante
UK• Stefano Brandani, University of Edinburgh• Marc-Olivier Coppens, University College London• Erich Muller, Imperial College London• Lev Sarkisov, University of Manchester
USA• Teresa Bandosz, City College, New York• Keith Gubbins, North Carolina State University• Peter Ravikovitch, ExxonMobil, Annandale, NJ• Randy Snurr, Northwestern University, Evanston, IL• Krista Walton, Georgia Institute of Technology

2From the Organizers
On behalf of the Organizing Committee, we would like to welcome the advisory committee
members, lecturers, and participants of the 9th International Workshop “Characterizationof Porous Materials: from Angstroms to Millimeters” – CPM-9 in Delray Beach, Florida, USA,on May 19-22, 2024.
CPM-9 is organized in a similar manner as the previous meetings in the CPM series
held in Princeton in 1997, 2000, 2003, 2006, New Brunswick in 2009, and in Delray Beachin 2012, 2015, and 2019. Following our tri-annual schedule, CPM-9 should have been heldin 2021. However, due to the Covid-19 pandemics, we had to postpone CPM-9 until 2024.
Designed to serve a bridge between academics and industrial scientists, CPM Workshops
have gained an international reputation for their high-quality interdisciplinary program,interactive style of presentations, and vivid discussions. With the participants representing
18 countries from five continents, CPM-9 is one of the central international events in thesubject area in 2024.
The CPM-9 program features 9 invited keynote lectures, 37 oral presentations, and70 posters, which address topical problems in the experimental, theoretical, and simulation
methods of characterization of structural, transport, and functional properties of porous
materials of various origins. The range of practical applications include regular, disordered,and hierarchical nanostructured materials used as adsorbents, catalysts, drug carriers, andmembranes, as well as natural nanoporous systems like shale, coal, and other geomaterials.
After the conclusion of the CPM-9 program on Wednesday afternoon, May 22, ourlocal sponsor Anton Paar QuantaTec will host a barbeque lunch and a lab tour of theirfacilities in nearby Boynton Beach.The CPM-9 papers selected through a rigorous peerreview process will be published as a Special Issue of Adsorption, the journal of theInternational Adsorption Society, following a tradition of previous CPM meetings, whose
proceedings were published in the special issues of Advances in Colloid and Interface
Science, vol. 76-77, 1998, and Colloids and Surfaces A, vol.187-188, 2001, vol. 241, 2004,
vol. 300, 2007, vol. 357, 2010, vol. 437, 2013, and vol. 496, 2016, and Microporous andMesoporous Materials, V. 304, 2020.
The submission website will be open and ready for article submission at the
Springer Nature system on May 31, 2024, at https://link.springer.com/journal/10450. To
access the submission portal, please visit the main journal web page and click at “Submit
your manuscript”. To ensure that all manuscripts are correctly identified for inclusion into
the special issue, it is important to select the Special Issue title under the “Details” tab, inthe “Collection” drop-down menu. Note that we intend to publish the full-scale concise
articles of the highest quality; abbreviated versions will not be considered. Please strictly
follow the submission guidelines posted on the journal website. The deadline formanuscript submission is August 31, 2024. Papers accepted for publication will be
continuously published online and the Special Issue web page will gradually be filled. We
expect the CPM-9 Special Issue to be completed around January 2025.
We are looking forward to an exciting and fruitful meeting.
With warm wishes,Alex Neimark, Workshop Chair
Rutgers University
Piscataway, New Jersey

Matthias Thommes, Workshop Co-ChairFriedrich-Alexander University
Erlangen-Nürnberg, Germany3

CPM9 | PROGRAM
Sunday, 19 May, 2024
4:00pm – 6:00pm Registration
6:00pm – 8:00pm Welcome Reception

Monday, May 20, 2024
8:30am – 8:40am Welcome Address
Alex Neimark and Matthias Thommes
8:40am – 9:00am Opening Remarks
Katsumi Kaneko, Shinshu University, Japan

Session 1: Adsorption and Transport
Session Chair: José Paulo Mota
9:00 –
9:30

Keynote: Adsorption and diffusion in nanoporous materials:
the view from the nanoscale
Benoit Coasne
CNRS/Univ. Grenoble Alpes

9:30 –
9:50

Rapid Characterization of Mass Transfer in Fiber Composites
Using a Commercial Volumetric Adsorption Instrument
Kaihang Shi, Florencia Son, Randall Snurr, Omar Farha
University at Buffalo, State University of New York
Shell-Core Structure in Extruded Pellets Characterized Using
the Zero Length Column Technique
Stylianos Kalaitzopoulos, Enzo Mangano, Stefano Brandani
University of Edinburgh

9:50 –
10:10

10:10 –
10:40

Coffee Break4

CPM9 | PROGRAM
Monday, May 20, 2024
Session 2: Experimental Methods I
Session Chair: Teresa Bandosz
10:40 –
11:10

11:10 –
11: 30
11:30 –
11: 50Keynote: Deformation Dynamics of Nanoporous Solids
upon Liquid Imbibition
Juan Sanchez, Patrick Huber
Hamburg University of Technology and Deutsches ElektronenSynchrotron DESY
Topological cluster structure of water confined inhydrophobic pores
Yasuhiro Sugiyama, Ryusuke Futamura, Taku Iiyama
Shinshu University
Quantitative Assessment of Hydrophilicity/Hydrophobicity
in Nanoporous Materials
Carlos Cuadrado Collados, Alexandra Inayat, Ana-Sunčana
Smith, Dorothea Wisser, Jakob Söllner, Jan Paul Grass, Martin
Hartmann, Matthias Thommes, Rustam Durdyyev
FAU Erlangen-Nürnberg, Erlangen, Germany

11:50 –
12:10

Investigating preferential adsorption of N2 from the air in
Zeolite 13X using total neutron scattering
Daniel Bowron, Marta Falkowska
The University of Manchester

12:10 –
12:30

Selectivity in adsorption of responsive metal-organic
frameworks
Irena Senkovska, Leila Abylgazina, Mariia Maliuta, Stefan
Kaskel, Volodymyr Bon
Dresden University of Technology

12:30 –
2:00

Lunch Break5

CPM9 | PROGRAM
Monday, May 20, 2024
Session 3: Molecular Simulations
Session Chair: Guillaume Maurin
2:00 2:30

2:30 –
2:50

2:50 –
3:10

Keynote: Insights into Capillary Condensation and Hysteresis in
Nanoporous Materials from New Simulation Methods
Randall Q. Snurr, Zhao Li, Filip Formalik, Jesse Prelesnik, and J. Ilja
Siepmann
Northwestern University
Anomalous interaction between propylene and Ag cation inzeolites
Hideki Tanaka, Tomoki Ogata, Motomu Sakai, Masahiko Matsukata,
Katsuya Teshima
Shinshu University
Unusual coexisting adsorption and structural transformations
mechanism in Nano-Porous Materials
Bogdan Kuchta
Wroclaw University of Science and Technology, Department ofChemistry

3:10 –
3:30

Understanding the Origins of Reversible and Hysteretic Pathwaysof Adsorption Phase Transitions by Mesocanonical Ensemble
Monte Carlo Simulations
Shivam Parashar, Alexander Neimark
Rutgers University

3:30 –
3:50

Flat-histogram Simulations of Water in MOFs: Advanced Strategies
for Overcoming Sampling Challenges
Daniel Siderius, Harold Hatch, Vincent Shen
National Institute of Standards and Technology

3:50 –
4:10

Mechanism of Vapor Sorption and Sorption-Induced Deformationin Bacterial Spores
Gennady Gor, George Scherer, Howard Stone
Princeton University, NJIT

4:30 –
7:00

Poster Session with Refreshments (Coffee/ Beer/ Horsd’oeuvres)
Session Chairs: Daniel Siderius and Gennady Gor

6

CPM9 | PROGRAM
Tuesday, 21 May, 2024
Session 4: Experimental Methods II
Session Chair: Stefano Brandani
8:00 –
8:30

8:30 –
8:50

8:50 –
9:10

Keynote: Combining multiple functions to achieve processintensification in adsorptive separations
Joeri Denayer, Mohsen Gholami, Ravi Sharma, Matthias Schoukens, Gille
Wittewrongel, Rahul Maity
Vrije Universiteit Brussel
Measurement of multicomponent adsorption isotherms based on atemperature-step approach and mass spectrometry
Nicolas Chanut, Robbe Van Loenhout, Cesar Para Cabrera, Masaya
Sugihara, João Fernandes, Margot Verstreken, Leen Boullart, Rob
AMeloot
KU Leuven
Direct visualization of Al distribution inside zeolite crystals
Yoshihiro Kamimura, Tetsuya Kodaira, Akira Endo
National Institute of Advanced Industrial Science and Technology

9:10 –
9:30

Predicting the pore-structure transport relationship in disorderedalumina using hyperpolarized xenon MRI and NMR
cryodiffusometry
Stefano Marc Collins, Sean Rigby, Huw Williams, Galina Pavlovskaya,
Thomas Meersmann, Arthur Harrison, Christophe Vallée, Thibaud
Chevalier, Dina Lofficial
University of Nottingham and IFP Energies Nouvelles

9:30 –
9:50

Kinetic measurements on monoliths using the Adsorption
Differential Volumetric Apparatus (ADVA)
Enzo Mangano, Riccardo Rea, Mohsen Gholami, Joeri Denayer, Stefano
Brandani
The University of Edinburgh

9:50 –
10:10

Towards “infinite” selectivities in CO2/CH4 and CO2/N2
separations with MgNa-GIS flexible zeolite
Remy Guillet
CNRS - LCS

10:10 –
10:40

Coffee Break7

CPM9 | PROGRAM
Tuesday, May 21, 2024
Session 5: Computational Design of Nanoporous
Materials
Session Chair: Randy Snurr
10:40 – Keynote: Material discovery with physics and AI
Lev Sarkisov
11:10 The University of Manchester, UK
11:10 – Dissemination and updates to the universal standard archive filefor adsorption data
11: 30 Daniel Siderius, Jack Evans, Stefan Kaskel
Fraunhofer IWS & TU Dresden
Applications of 3D Amorphous Carbon Molecular Models for
11:30 –
Adsorption and Mechanical Property Predictions
11: 50 Nicholas Corrente, Elizabeth Hinks, Aastha Kasera, Raleigh Gough, PeterI. Ravikovitch, Alexander Neimark
Rutgers University

11:50 – Computational-aided development of MOF-based Mixed Matrix
12:10 Membranes for molecular separation
Guillaume Maurin
Université Montpellier/CNRS

12:10 – Molecular Simulation of Peptide Retention in Reversed-Phase
12:30 Liquid Chromatography
José Paulo Mota
NOVA School of Science and Technology

12:30 –
2:00

Lunch Break8

CPM9 | PROGRAM
Tuesday, 21 May, 2024
Session 6: Experimental Methods II
2:00 2:30
2:30 –
2:50
2:50 –
3:10

3:10 –
3:30

Keynote: Structural changes in ZIFs upon gas and liquid phaseadsorption
Joaquin Silvestre Albero
University of Alicante
On the characterization of nanoporous carbons with small-angle
scattering
Oskar Paris, Christian Prehal
Montanuniversität Leoben
Use of Ultrasonic Monitoring for In situ Diagnostics of Zeolite and
MOF Crystallization
Martin Hartmann, Hasan Baser, Marcus Fischer, Rebecca Reber, Wilhelm
Schwieger
Erlangen Center for Interface Research and Catalysis, FAU ErlangenNürnberg, Erlangen, Germany
Correlations of NMR Relaxometry Data and Polymer Surface
Chemistry
Alan Allgeier, Murilo Suekuni
University of Kansas

3:30 –
3:50

Advanced Textural and Surface Chemistry Characterization by
Combining Adsorption and Liquid Intrusion with NMR Relaxometry
Carola Schlumberger, Carlos Cuadrado Collados, Jakob Söllner, Lukas
Sandner, Jincheng Xu, Matthias Thommes
Institute of Separation Science and Technology, Friedrich-AlexanderUniversity Erlangen-Nuremberg

3:50 –
4:10

Brain Tissue Modeled as a Porous Medium with parameters
derived from Micro-Iontophoresis Experiments
Charles Nicholson
NYU School of Medicine

4:10 –
4:40

Coffee Break9

CPM9 | PROGRAM
Tuesday, 21 May, 2024
Session 7: Theoretical Methods
Session Chair: Benoit Coasne
4:40 –
5:10

5:10 –
5:30
5:30 –
5:50

Keynote: 3-D Density Functional Theory to Describe
Adsorption of Pure Substances and Their Mixtures on
Crystalline and AMorphous Adsorbents
Frederico Wanderley Tavares
Universidade Federal do Rio de Janeiro
A non-local Density Functional Theory for water adsorbed
in nanoporous materials.
Antoine Barthes, David Grégoire, Christelle Miqueu
Université de Pau et des Pays de l'Adour
Coupling between poroelasticity and the density functional
theory for the estimation of adsorption-induced swelling in
nanoporous materials
David GREGOIRE, Youssef Khaldouni, Laurent Perrier, Thomas
Bernet, Christelle Miqueu
Universite de Pau et de Pays de l’Adour, E2S UPPA, CNRS, LFCR,
Anglet, France

5:50 –
6:10

Framework-dependent kinetics of adsorption-induced
structural transition in flexible metal-organic frameworks
Shotaro Hiraide, Yuta Sakanaka, Iori Sugawara, Hajime Uematsu,
Shogo Kawaguchi, Minoru Miyahara, Satoshi Watanabe
Kyoto University

6:10 –
6:30

Impact of a kerogen network on the behavior of confinedhydrocarbon liquids
Bennett D Marshall, Dmitry N. Lapshin, Erich A. Muller, Peter I.
Ravikovitch
Imperial College London

8:00

Conference Dinner10

CPM9 | PROGRAM
Wednesday, 22 May, 2024
Session 8: Experimental Methods III
Session Chair: Oskar Paris
8:30 –
9:00

Keynote: Structure characterization-mediated designing of novel
carbon-based nanostructured materials
Katsumi Kaneko
Research Initiative for Supra-Materials, Shinshu University

9:00 –
9:20

Designing Macroporous-Mesoporous Adsorbents for Sustainability
Freddy Kleitz, Aaron Brewer, Changxia Li, Patrick Guggenberger,
Justyna Florek
University of Vienna, Austria
Tuneable mesoporous silica materials for gas storage applications
via nanoconfined clathrate formation
Pegie Cool
University of Antwerp
Effect of surface chemical heterogeneity of carbon textiles on theirdetoxification activity against CWA surrogate
Marc Florent, Paola S Pauletto, Teresa J Bandosz
CCNY

9:20 –
9:40
9:40 –
10:00

10:00 – Adsorption separation of CO2 from CH4/CO2 mixture by Low Silica
10:20 X zeolite and Recovering of Adsorption Heat for Further
Applications
Akihiko MATSUMOTO, Keiichi Hasegawa, Yuji Hasegawa
Toyohashi University of Technology

10:20 –
10:50

Coffee Break11

CPM9 | PROGRAM
Wednesday, 22 May, 2024
Session 9: Nanomaterials for Adsorption Applications
Session Chair: Martin Hartmann
10:35 –
11:20

Keynote: Separation Performance of Zeolitic-ImidazolateFramework-Based Membranes
Michael Tsapatsis
John Hopkins University

11:20 –
11:40

Unique characterization data of graphene mesosponge
Hirotomo Nishihara
Tohoku University

11:4012:00

Formation and Characterization of ZIF-8 Supraparticles and Their
Packings with Hierarchical Porosity
Satoshi Watanabe, Atsushi Fujiwara, Minoru Miyahara, Nicolas Vogel,Shotaro Hiraide
Department of Chemical Engineering, Kyoto University
Functional porous physisorbent materials from phosphorite
waste: Advanced characterizations and applications
Ali Mohammed YIMER, Ayalew Hussen ASSEN, Youssef BELMABKHOUT
Mohammed VI Polytechnic University

12:00 –
12:20
12:20 –
12:40

Porous silica-coated magnetic nanoparticles for moleculardiagnostics of virus infection
Adriana Zelenakova
Pavol Jozef Šafarik University in Košice

12:40 –
1:00

CPM9 Closing:Concluding Remarks
Keith Gubbins
North Carolina State University, USA
Closing Ceremony
Alex Neimark and Matthias Thommes

1:30

Barbecue lunch and company tour of Anton-Paar
QuantaTec in nearby Boynton Beach(Transportation Provided)12

CPM9 | POSTER PRESENTATION

13

1. Temperature-Dependent V-Type Isotherm Models: Applied to Water Vapor
Adsorption on Metal-Organic Frameworks
Cristian Cardenas
IFP Energies Nouvelles
2. Facile Characterization of Pore Accessibility in Metal-Organic
Framework/Polymer Composites
Trenton Tovar
U.S. Army, DEVCOM Chemical Biological Center
3. Characterization of hydroxyl groups in zeolite defects using advanced
temperature-programmed desorption
Shunsuke Shimizu, Hirotomo Nishihara, Ryota Osuga, Takeharu Yoshii
Institute of Multidisciplinary Research for Advanced Materials, Tohoku
University
4. High sensitivity analysis of nitrogen in carbon materials using
temperature-programmed desorption up to 2100 °C
Takeharu Yoshii, Ginga Nishikawa, Hirotomo Nishihara
Tohoku University
5. Explorations of the Molecules-to-Materials Continuum
Robert Szilagyi
The University of British Columbia - Okanagan
6. Characterization of Mycelium-Based Leather Using Sorption-UltrasonicExperiments
Gunel Nabiyeva, Ashoka Karunarathne, Christopher Rasmussen, Naila Assem,
Jonathan Bauer, Alexei Khalizov, Gennady Gor
Dept. of Chemical and Materials Engineering, New Jersey Institute ofTechnology, Newark, NJ, USA
7. Validation of pore size distribution from a new GCMC kernel based on a slitpore model with carbon surface heterogeneity
Kazuyuki Nakai
MicrotracBEL Corp.
8. Kinetics of Adsorption-Induced Deformation in Microporous Materials
Andrei Kolesnikov, Gennady Gor
Department of Chemical and Materials Engineering, New Jersey Institute ofTechnology
9. Sorption-Ultrasonic Characterization of Water-Filled Xerogels
Ashoka Karunarathne, Alexei Khalizov, Gennady Gor, Gudrun Reichenauer,
Stephan Braxmeier
New Jersey Institute of Technology
10. Assessment of the Specific Surface Area by Small-Angle X-ray Scattering
Andreas Keilbach, Armin Moser, Heike Ehmann
Anton Paar GmbH14

11. Extruding diffusion constants from your extrudates: PFG-NMR andchromatography
Sean Mclntyre, Daryl Williams, Paola Sáenz-Cavazos, Paul IACOMI
12. Impact of Crystal Structure on Methanol Vapor Adsorption in MFI-Type
Zeolites: Equilibrium Isotherms and Kinetic Insights
Coset Abreu Jauregui, Francisco Murilo Tavares de Luna, Igor de Mesquita
Figueredo, Joaquín Silvestre-Albero, Leandro Martins
University of Alicante
13. Quantification of Copolymer Microstructure from Liquid Chromatographyusing a Statistical Interaction Model
Christopher Rasmussen, Yefim Brun
Bolt Threads Inc.
14. Estimation of porous media transport properties solely based on mercury
intrusion porosimetry
David Grégoire, Gilles Pijaudier-Cabot, Fadi Khaddour, Lionel Ecay, Sara Khalil
Universite de Pau et de Pays de l’Adour, E2S UPPA, CNRS, LFCR, Anglet, France
15. The influence of confinement effects on the thermophysical properties of 4methoxyazobenzene
Timm Kraus, Michael Fröba
Universität Hamburg
16. PyCOSMOS: A Python Tool for Compartmentalization of Unit Cells of MetalOrganic Frameworks
Shivam Parashar, Alexander Neimark
Rutgers University, New Jersey, USA
17. Modelling Kerogen Flexibility in Response to Hydrocarbon Adsorption using
Hybrid Molecular Dynamics/Monte Carlo
Shivam Parashar, Alexander Neimark, Peter I. Ravikovitch
Rutgers University, New Jersey, USA
18. Characterization of Nanoporous Carbons Using Generative Models
Lucas J. Santos, Elvis do A. Soares, Amaro Gomes Barreto Jr., Frederico
Wanderley Tavares
Universidade Federal do Rio de Janeiro
19. A Novel Method for Obtaining Carbon Molecular Sieves for N2/O2
Separation
Koki Urita, Kaito Marubayashi, Miyu Hamasaki, Hideki Tanaka, Takashi Ishida,
Yasuyuki Yamane, Jin Miyawaki, HIroo Notohara, Isamu Moriguchi
Nagasaki University
20. INFRAsorp & MULTIport Rapid surface analysis by optical calorimetry
Stefan Kaskel, Felix Spranger
Fraunhofer IWS; TU Dresden
21. Unique dissolution/precipitation phenomena in microspace induced byphysisorption
Takeru Yokoyama, Taku Iiyama, Ryusuke Futamura, Takahiro Ueda, Yuka
15

Matsuda
Faculty of Science, Shinshu University 3-1-1 Asahi, Matsumoto, Nagano 3908621, Japan
22. Reference Isotherms for Water Vapor Sorption on Nanoporous Carbon:
Results of an Interlaboratory Study
Huong Giang Nguyen, Blaza Toman, Roger van Zee, Matthias Thommes
National Institute of Standards and Technology
23. Small-angle neutron scattering reveals high-density adsorbed hydrogen incarbon micropores at low pressures and supercritical temperature
Sebastian Stock, Malina Seyffertitz, Nikolaos Kostoglou, Max Valentin Rauscher,
Bruno Demé, Christian Mitterer, Oskar Paris
Montanuniversität Leoben, Chair of Physics
24. Scalable Continuous Flow Hydrogenation Using Structured Catalyst Reactor
Andrea Adamo, James Mannino, John Holcombe, Lorenzo Milani, Steve Stark,
Vladimiros Nikolakis
W.L. Gore & Associates Inc.
25. Solid-State Hydrogen Storage: Advancements in Nanoporous Materials andNeutron Scattering Techniques
Haihua Wang, Mi Tian, Oana Ghita, Valeska Ting, Xiayi Hu
University of Exeter
26. Microscopic understanding of stability and adsorption/separation of CO2
from flue gas by MOFs in real industrial conditions
M. Wahiduzzama, P. Lyu, N. Heymans, N. Garcia-Moncada, G. Mouchaham, M.
Daturi, G. De Weireld, C. Serre, Sabine Devautour-Vinot, G. Maurin
ICGM CNRS/ENSCM/UM
27. Understanding wetting and drying of nanoporous media through opticaland dilatometry experiments
Juan Sanchez, Laura Gallardo, Yannick Tetzner, Patrick Huber
Hamburg University of Technology
28. CH4/H2O Competitive adsorption in Nano porous materials under clathrate
hydrate formation conditions
JYOTI SHANKER PANDEY, Joaquin Silvestre Albero
DTU CHEMICAL ENGINEERING
29. Acoustic Response of Fluid Adsorption in Nanoporous Materials
Loriane Didier, Alan Sam, Rodolfo Venegas, Benoit Coasne
CNRS/Univ. Grenoble Alpes
30. Supercritical fluid activation and in-situ adsorption-microcalorimetricsystem to directly measure the gas adsorption amount, heat and kinetic
data
Wentao Jiang, liuliu long, Yue-Biao Zhang
ShanghaiTech University
31. Evaluation of a Commercial Chabazite-Type Zeolite Aging in the Industrial
Process of Dehydration of Natural Gas CO2-Enriched
16

Kalil Kashefi, Marcos Anacleto da Silva, Vera M.M. Salim, Frederico W. Tavares,
NEUMAN SOLANGE DE RESENDE, Amaro G. Barreto
Universidade Federal do Rio de Janeiro, EQ
32. Reference Isotherms using Reference Materials
Roger van Zee, Blaza Toman, Huong Giang Nguyen, Matthias Thommes
NIST
33. Converting Waste Tire to Activated Carbon Adsorbent Materials for Landfill
Gas Purification
Brandyn Nutter, Amirjavad Ahmadian Hosseini, Laura Rojas, Masoud Jahandar
LashakiFlorida Atlantic University
34. Improving the robustness and reproducibility of gas adsorption isotherm
measurements on nanoporous materials
Darren Broom
Hiden Isochema Ltd
35. Densification and Validation of Binderless MOF Monoliths Based On
Temperature-Pressure Swing Hydrogen Storage and Delivery Conditions
Ruthradharshini Murugavel, Ali Rownaghi, Fateme Rezaei
Department of Chemical & Biochemical Engineering, Missouri University of
Science and Technology
36. Self-template Synthesis of Nanoporous Carbons from π-conjugated Ionic
Liquids with Molecular Nanocarbon Functionalities
Ryusuke Futamura, Toshinori Seki, Kento Nakamura, Ryuta Sekiguchi, Taku
IiyamaShinshu University
37. Investigating the effect of the extra-framework cation on propane /propylene adsorption in LTA zeolites
Claessens Benjamin, Emily Bloch, Gabriel Trierweiler-Conçalves, Gerald
Chaplais, Jean Daou, Jean-Louis Paillaud, Mohammed-El Amine Benchaabane,
Sandrine Bourrelly
Aix-Marseille University, CNRS
38. Carbon Dioxide Capture in NaOH-Impregnated Activated Carbon
Prapatsorn Borisut, Atichat Wongkoblap, Chaiyot Tangsathitkulchai, Aroonsri
Nuchitprasitchai, Krittamet Phothong
Suranaree University of Technology
39. Metal Organic Framework Hollow Fibers for CO2 adsorption and Chemical
Warfare Agent Degradation
John Landers
Apollodyne
40. Hydrophobic metal-organic frameworks with new fluorinated ligands
Vladimír Zeleňák, Dávid Princík, Adriána Zeleňáková
Faculty of Natural Science, Pavol Jozef Safarin University in Kosice, Slovakia
1741. Development of novel porous geopolymer monoliths based on Moroccan oil
shale for effective removal of heavy metals (Zn (II), Cu (II), Pb (II)) fromwastewater.
said mansouri, SANAE SBI, JONES ALAMI, HASSAN HANNACHE, YOUSSEF
TAMRAOUIMohammed VI Polytechnic University, Benguerir
42. Sorption of SF6 and SO2 on Modified Zeolites Materials
Katarzyna Zarębska, Mikihiro Nomura, Megumi Irie, Jakub Szczurowski
Faculty of Environmental Engineering, Geomatics and Renewable Energy,
Kielce University of Technology, 25-314 Kielce, Poland
43. Trapped in the CO2 Loop: A Study of Carbon/MOF Composites for Direct Air
Capture (DAC)
Jakub Szczurowski, Adrian Lubecki, Katarzyna Zarębska, Patryk Bartulik
Faculty of Environmental Engineering, Geomatics and Renewable Energy,
Kielce University of Technology, 25-314 Kielce, Poland
44. Applications of MOFs for the chemical warfare agents (CWAs) simulant
adsorption
Emily Bloch, Guillaume Maurin, Lotfi Boudjema, Sandrine Bourrelly
Aix-Marseille University - CNRS MADIREL
45. 3D-printed hybrid zeolite structures constructed by a phase inversion
process
Ben Sutens, Marleen Rombouts, Steven Mullens, Yoran De Vos
VITO
46. Novel nanoporous composites for hydrogen storage
Alex Pennetier, Jean-Philippe Torré, Laurent Perrier, Christelle Miqueu
Université de Pau et des Pays de l'Adour
47. In situ pXRD monitoring of compliant MOFs under combined mechanicaland gas pressure
Paul IACOMI, Pascal Yot, Christian Serre, Frederico Alabarse, Sujing Wang,
Guillaume Maurin
48. Impact of Carbon Content in Single-Wall Carbon Nanotube-Titanium
Dioxide Composites Interfacial Modulation and Catalytic Behavior
Coset Abreu Jauregui, Antonio Sepúlveda-Escribano, Joaquín Silvestre-Albero
University of Alicante
49. Tailoring the Adsorption Properties of Hierarchical Porous Silicas for HighCapacity Water Sorbents
Pasquale Fulvio, JiaJi Lin, Krista Walton
Georgia Institute of Technology
50. Quantifying Structural Rigidity in Metal–Organic Frameworks with
Increased Linker Dimensionality
18

Courtney Smoljan, Omar Farha, Randall Snurr
Northwestern University
51. Carbon Dioxide Capture from Flue Gas using 13X binder free Zeolite: effectof the presence of Sulfur Dioxide
Celio Cavalcante, Diana Azevedo, Enrique Vilarrasa-Garcia, Eurico Torres,
Moises Bastos-Neto, Rafaelle Santiago
Universidade Federal do Ceara
52. A Comparative Study of Physical and Chemical Modification for Improved
CO2 Capture in Fixed-Bed Adsorption
Suravit Naksusuk
School of Chemical Engineering, Suranaree University of Technology
53. Analyzing the Performance of Propylamine-Grafted Mesoporous Silica for
Direct Air Capture Applications
Amirjavad Ahmadian Hosseini, Laura Rojas, Masoud Jahandar Lashaki
Florida Atlantic University
54. Triamine-Grafted Mesoporous Silica Materials for CO2 Capture from theAtmosphere
Laura Rojas, Amirjavad Ahmadian Hosseini, Masoud Jahandar Lashaki
Florida Atlantic University
55. Molecular mechanisms of water intrusion and extrusion in hydrophobic
nanopores
Abdelraheem Abdella, Kolattukudy P. Santo, Alexander Neimark
Rutgers, The State University of New Jersey
56. Molecular simulation of separation of C60 and coronene in silica nanopores
Rustam Durdyyev, György Hantal, Ana-Sunčana Smith
PULS Group, Friedrich-Alexander-Universität Erlangen-Nürnberg, Institute for
Theoretical Physics, Interdisciplinary Center for Nanostructured Films
57. Composite Boron Nitride-based Immobilized Nanohydride Toward SelfAccelerated Reversible Hydrogen Storage
Maxwell Tsipoaka, Fateme Rezaei
Missouri University of Science and Technology
58. The Effect of Carbon Nanotube Diameter on Hydration of Critical Material
Ions from E-waste
Qing Shao, Zachary Baker
University of Kentucky
59. Mechanical Properties of Gases Adsorbed in Micropores from theFluctuation Theory
Santiago Flores Roman, Alina Emelianova, Gennady Gor
New Jersey Institute of Technology
60. Molecular Simulation of Adsorption of Sarin and Simulants on Metal–
Organic Frameworks
Elizaveta Basharova, Alina Emelianova, Allen Reed, Gennady Gor, Andrei
19

Kolesnikov
New Jersey Institute of Technology
61. A unified approach for bridging the gap between cDFT and equation ofstate for confined fluids
Amaro Gomes Barreto Jr., Dárley Carrijo de Melo, Felipe Rocha Pinto, Frederico
Wanderley Tavares, Vítor Sermoud
Universidade Federal do Rio de Janeiro
62. Hydrogen storage: predicting at room temperature in a series of activatedcarbons
José Carlos Alexandre de Oliveira, Daniel V. Gonçalves, Sebastião M. P. Lucena
Universidade Federal do Ceara
63. Study of Crystallization Pressure by Molecular Simulation
Bilal MAHMOUD HAWCHAR, Laurent brochard, Florian osselin, Jean-Michel
Pereira, Matthieu Vandamme, tulio honorio
64. Incorporating material flexibility effects into adsorption modeling using
non-local Density Functional Theory
Christelle Miqueu, Raphael Labeyrie
Université de Pau et des Pays de l'Adour
65. Modeling Adsorption of Simple Fluids and Alkanes on 3D Nanoporous
Carbons
Nicholas Corrente, Elizabeth Hinks, Aastha Kasera, Raleigh Gough, Peter I.
Ravikovitch, Alexander Neimark
Rutgers University, New Jersey, USA
66. SAFT-DFT Studies of Nanoporous Carbon Deformation Induced byMulticomponent Adsorption
Nicholas Corrente, Elizabeth Hinks, Aastha Kasera, Alexander Neimark
Rutgers University, New Jersey, USA
67. Development and application of an advanced percolation model for pore
network characterization by physical adsorption
Jakob Söllner, Alexander Neimark, Matthias Thommes
Institute of Separation Science and Technology, Friedrich-Alexander
Universität Erlangen-Nürnberg

20

CPM9 | REPORT OF ABSTRACTSMONDAY, MAY 20, 2024

Adsorption and diffusion in nanoporous materials: the view fromthe nanoscale21

Benoit Coasne1
1

Univ. Grenoble Alpes, CNRS, LIPhy, 38000 Grenoble, France

Email for correspondence: benoit.coasne@univ-grenoble-alpes.fr
Nanoporous materials (pore size 1–100 nm) are at the heart of numerous important applications:adsorption (e.g. gas sensing, chromatography), energy (e.g. hydrogen storage, fuel cells andbatteries), environment (e.g. phase separation, water treatment, nuclear waste storage), etc. Amongthese materials, nanoporous solids which have pores ≲ nm (e.g. active carbons, zeolites), areparticularly interesting as ultraconfinement in their porosity leads to novel adsorption and transportphenomena. Thorough understanding of these effects and the underlying molecular mechanisms iscritically needed to better characterize nanoporous solids. In this talk, I will present how statisticalphysics allows developing models for adsorption and transport in these extremely confining
materials [1,2]. We will see how simple thermodynamic modeling allows rationalizing adsorption byconsidering reminiscent capillarity at vanishing lengthscales. Then, we will show how transport insubnanoporous media can be described without having to rely on macroscopic concepts such ashydrodynamics [3,4,5]. In particular, using parameters and coefficients available to experiments, wewill see how transport coefficients can be rigorously upscaled using simple models such as freevolume theories, etc. I will also briefly illustrate how the confinement of fluids in metallic nanoporous
materials departs from what is observed for insulating materials [6].
Figure 1. Propagator Gs(r,t) [prob. that a molecule istranslated by a quantity r over a time t] for a LennardJones fluid confined in a nanoporous carbon (FromRef. [5]).

References:
1 B. Coasne et al., Chem. Soc. Rev. 42, 4141 (2013).
2 I. Deroche et al., Nature Comm. 10, 4642 (2019).
3 K. Falk et al., Nature Comm. 6, 6949 (2015)
4 T. Lee et al., Nature Comm. 7, 11890 (2016)
5 C. Bousige et al., Nature Comm. 12, 1043 (2021).
6 A. Schlaich et al., Nature Materials 21, 237 (2022).

Rapid Characterization of Mass Transfer in Fiber Composites
using a Commercial Volumetric Adsorption Instrument
22

Kaihang Shi,*†,1,2 Florencia A. Son, †,3 Randall Q. Snurr,*1and Omar K. Farha*1,3
1 Department of Chemical and Biological Engineering, Northwestern University, Evanston, Illinois,60208, United States

2 Department of Chemical and Biological Engineering, University at Buffalo, The State University of

New York, Buffalo, New York, 14260, United States

3 Department of Chemistry and International Institute for Nanotechnology, Northwestern

University, Evanston, Illinois, 60208, United States†Equal contribution from both authors
Emails for correspondence: kaihangs@buffalo.edu; snurr@northwestern.edu;
ofarha@northwestern.edu

MOF/fiber composites have shown much promise as protective equipment for the capture andremediation of chemical warfare agents. However, the practical application of these composites
requires an understanding of their mass transport properties, as both mass transfer resistance as thesurface and diffusion within the materials can impact the efficacy of these materials. Experimental
characterization of molecular transport typically requires specialized and expensive facilities, suchas confocal Raman microscopy or infrared Raman microscopy, which – although they provide
beneficial insights – suffer from limited accessibility, inhibiting the development of new applicationsof porous materials.
In this talk, we present a new Fickian diffusion model to quantitatively characterize the surface
permeation and in-pore diffusion of molecules in MOF/fiber composites having cylindrical shapes.
The new diffusion model takes input data from a commercial volumetric adsorption instrument,
which is readily accessible in most laboratories compared to other specialized facilities for studying
molecular diffusion. Using this newly developed method, we were able to study the mass transport ofn-hexane and 2-chloroethyl ethyl sulfide (CEES) in composite fibers of MOF-808 and functionalizedpolymers of intrinsic microporosity. We found that transport in these materials is dominated bysurface barriers, and diffusion within the bulk of the composite materials is fast in comparison. These
preliminary insights and the model introduced in this work lay the groundwork for the design ofnext-generation composite materials for practical applications.
References:
1. F.A. Son†, K. Shi†, R.Q. Snurr, O.K. Farha, Mass Transport of n-Hexane and 2-Chloroethyl Ethyl
Sulfide in Fiber Composites of MOF-808 and Amidoxime-Functionalized Polymers of Intrinsic
Microporosity, in preparation.
Acknowledgements:
O.K.F. and R.Q.S. gratefully acknowledge support from the Defense Threat Reduction Agency(HDTRA1-19-1- 0007). F.A.S. is supported by the Department of Defense (DoD) through the National
Defense Science & Engineering Graduate (NDSEG) Fellowship Program and the Ryan Fellowship
through the International Institute for Nanotechnology at Northwestern University. K.S. gratefully
acknowledges the start-up support from the University at Buffalo.

23

Shell-Core Structure in Extruded Pellets Characterized Using theZero Length Column Technique
Stylianos Kalaitzopoulos1, Enzo Mangano1, Stefano Brandani1
1School of Engineering, Institute for Materials and Processes, University of Edinburgh, The King’s
Buildings, Edinburgh, EH9 3FB, UK
Emails for correspondence: e.mangano@ed.ac.uk, s.kalaitzopoulos@sms.ed.ac.uk,
s.brandani@ed.ac.uk

The presence of shell-core structures in some extruded pellets is a well-known phenomenon [1], but
it is very difficult to quantify the thickness of the external layer and its impact on mass trans- port
kinetics. We present a methodology to characterize mass transport in extruded pellets that shows
for the first time the ability to distinguish uniform structures from shell-core structures. The
measurements are carried out with the zero length column (ZLC) technique [2] including both fullequilibration and partial loading experiments [3]. Two commercial extruded materials from UOP, a
Honeywell company, and UTSA-16 extrudates from SINTEF were used in this study. The two zeolitematerials are shown to behave significantly differently when normal paraffins are used as the probe
molecules. HISIV 3000 (silicalite) pellets show ZLC responses that are perfectly consistent withmacropore diffusion control, while 5A pellets show a distinct “surface resistance” in addition to theinternal diffusion process. The MOF pellets also show a distinct surface resistance, which can bedetected using the ZLC and a suitable probe molecule.
The slower mass transport in the external shell is shown to be a macropore diffusion process byperforming tests with different carrier gases. A detailed shell-core model is developed to analyze theresponses in greater detail and determine the thickness of the external skin by the simultaneous
regression of multiple experiments (different flowrates and partial loading runs) in the whole pellet
and a fragment. This allows to determine quantitatively the thickness of the external layer, which isonly a few microns thick.
The use of the ZLC provides a very efficient method to detect skin effects on pellets which are an
important feature for quality control for manufactures. It also provides the ability to determine theeffect of the skin resistance, allowing to estimate physical parameters that can be used to describe
more accurately mass transport in adsorption and catalytic processes.
References:1.
Roberts CW. Molecular sieves for industrial separation and adsorption applications. In:
Townsend RP, editor. The properties and applications of zeolites, London; The Chemical Society 1980
p. 103– 120.
2.
Eic M. and Ruthven DM, A new experimental technique for measurement of intracrystalline
difusivity. Zeolites 8 (1988) 40–45. https://doi.org/10.1016/S0144-2449(88)80028-9.
3.
Brandani S. and Mangano E. The Zero Length Column Technique to Measure Adsorption
Equilibrium and Kinetics: Lessons Learnt from 30 Years of Experience. Adsorption, 27 (2021) 319–
351. https://doi.org/10.1007/s10450-020-00273-w

24

Deformation Dynamics of Nanoporous Solids upon Liquid
Imbibition
Juan Sanchez1; Patrick Huber2
1
2

Hamburg University of Technology

Hamburg University of Technology and Deutsches Elektronen-Synchrotron DESY
Emails for correspondence: patrick.huber@tuhh.de, juan.sanchez@tuhh.de

Capillarity-driven transport in nanoporous solids is ubiquitous in nature and is of increasing importance for the functionality of modern liquid-infused engineering materials. During imbibition,highly curved menisci are driven by negative Laplace pressures of several hundred atmospheres,
exerting an enormous contractile load on an increasing portion of the porous matrix. Due to thechallenge of simultaneously monitoring imbibition and deformation with high spatial resolution, theresulting coupling of solid elasticity to liquid capillarity has remained largely unexplored. Here, we
study water imbibition in mesoporous silica using optical imaging, gravimetry, and high-resolution
dilatometry. In contrast to an expected Laplace pressure-induced contraction, we find a square-rootof-time expansion and an additional abrupt length increase when the menisci reach the top surface.
The final expansion is absent when we stop the imbibition front inside the porous medium in a
dynamic imbibition-evaporation equilibrium, as is typical for water transport and transpiration inplants. These peculiar deformation behaviors are validated by single-nanopore molecular dynamics
simulations and described by a continuum model that highlights the importance of expansive surface
stresses at the pore walls (Bangham effect) and the buildup or release of contractile Laplacepressures as nanoscale menisci collectively advance, arrest, or disappear. Our model predicts thatthese observations are valid not only for water imbibition in silica, but for any imbibition process in
nanopores, regardless of the liquid/solid combination. This also suggests that simple deformation
measurements can be used to quantify surface stresses and Laplace pressures or transport in a wide
variety of natural and artificial porous media.

25Topological cluster structure of water confined in hydrophobicpores
Yasuhiro Sugiyama1, Ryusuke Futamura2 and Taku Iiyama2,3
1 Graduate School of Medicine, Science and Technology, Shinshu University, 3-1-1 Asahi,

Matsumoto, Nagano, 390-8621 Japan

2 Faculty of Science, Shinshu University, Japan

3 Research Initiative for Supra-Materials, Shinshu University, Japan
Emails for correspondence: 23hs302c@shinshu-u.ac.jp, tiiyama@shinshu-u.ac.jp,
ryu_f@shinshu-u.ac.jp

The behavior of water confined in nanospaces is significantly different from that of bulk water. Water
adsorption on activated carbon with hydrophobic surface shows a characteristic type V isotherm.
Water fills the pores with strong intermolecular interactions and forms clusters inside the pores. We
have been studied the adsorption mechanism from the experiments, X-ray diffraction (XRD) [1] andsmall-angle X-ray scattering (SAXS) [2]. The XRD gives
direct information about the intermolecular structure ofconfined water. The confined water has an ice-likestructure even at room temperature and exhibits acontinuous solid-liquid phase transition phenomenon withtemperature. The SAXS reveals the molecular assemblystate, such as the size of the water clusters, and thedifferences in the shape and size of the clusters cause
adsorption hysteresis.
In this study, we show the anomalous temperaturedependence of the water density confined in hydrophobic
sub-nanometer spaces from in situ XRD measurements [3],and computational analysis, hybrid reverse Monte Carlosimulation (HRMC) and the persistent homology method.
The persistent homology method provides geometricintermolecular structural information about disorderedmaterials, such as amorphous and liquid materials. In subnanometer spaces, the density of confined water is very sparse compared to that of bulk ice even atroom temperature, suggesting that the spatially distorted ice-like hydrogen bonding network would
be formed in the nanospaces.
References:
1.T. Iiyama, K. Nishikawa, T. Otowa, K. Kaneko, J. Phys. Chem., 99, (1995) 10075.
2.T. Iiyama, Y. Kobayashi, K. Kaneko, S. Ozeki, Colloid and Surface A, 241, (2004) 207.
3.Y. Sugiyama, R. Futamura, T. Iiyama, Chem. Lett., 51, 760 (2022)
Acknowledgements:
This work was supported by JSPS KAKENHI (Grant Number 21K04977).

26

Quantitative Assessment of Hydrophilicity/Hydrophobicity in
Nanoporous Materials
Carlos Cuadrado Collados, a Christoph Huber, b Jakob Söllner, a Jan-Paul Grass,c Alexandra Inayat,cRustam Durdyyev,d Ana-Sunčana Smith,d Dorothea Wisser,b Martin Hartmann,b Matthias
Thommesa*
a Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Institution of Separation Science andTechnology Egerlandstr. 3, 91058 Erlangen, Germanyb Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen Center for Interface

Research and Catalysis (ECRC), Egerlandstr. 3, 91058 Erlangen, Germanyc Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Institute of Chemical Reaction

Engineering (CRT) Egerlandstr. 3, 91058 Erlangen, Germany
d PULS Group, Friedrich-Alexander-Universität Erlangen-Nürnberg, Institute for Theoretical
Physics, Centre for Computational Advanced Materials and Processes, IZNF, Cauerstraße 4, 91058
Erlangen, Germany

Email for correspondence: Matthias.Thommes@fau.de
We have developed a comprehensive strategy for assessing the surface chemistry of nanoporous
materials by combining advanced adsorption studies, novel liquid intrusion techniques and solidstate NMR spectroscopy. The methodology was established on a well-defined system of model
materials, the highly ordered mesoporous silica SBA-15, both pristine and functionalized withdifferent amounts of trimethylsilyl (TMS) groups. The surface density of trimethylsilyl groups, wasdetermined by quantitative 1H solid-state NMR spectroscopy under Magic Angle Spinning (MAS). 1H
two-dimensional single quantum double quantum MAS NMR spectra reveal an intimate mixture of
TMS and residual silanol groups on the surface. A full textural characterization of the materials was
obtained by high-resolution argon at 87 K adsorption, coupled with the application of dedicatedmethods based on non-local-density functional theory. We further present a methodology todetermine the effective contact angle of water adsorbed on the pore surfaces, which constitutes a
powerful parameter for the characterization of the surface chemistry inside porous materials. The
surface chemistry was found to vary from hydrophilic to a hydrophobic as the TMS functionalization
content was increased, leading to contact angles from 0 ° (complete wetting) to 120 ° (non-wetting).
For wetting and partial wetting surfaces, the contact angle was determined from the water sorption
isotherms by applying the modified Kelvin equation on the desorption branch of the observed
hysteresis loop, reflecting the thermodynamic liquid-vapour transition. On non-wetting surfaces, weinvestigated the pore filling of water by the application of a novel liquid water intrusion/extrusion
experiment, applying the Washburn equation on the water intrusion branch which reflects thethermodynamic equilibrium vapor-liquid transition for a non-wetting fluid. Molecular simulations
provide density profiles of water on pristine and TMS-grafted silica surfaces, which agree with theobtained experimental data.
The methodology presented here can in principle be used for assessing thehydrophilicity/hydrophobicity of a wide range of nanoporous materials for optimizing theirproperties towards applications in chromatographic separation or heterogeneous catalysis.

27

Investigating preferential adsorption of N2 from the air in
Zeolite 13X using total neutron scattering
Marta Falkowska1,2 and Daniel T. Bowron2
1 Dept. of Chem. Eng., The University of Manchester, Oxford Road, Manchester, M13 9PL, UK
2 ISIS Neutron and Muon Source, Science and Technology Facilities Council, Harwell Campus, OX11

0QX, Didcot, UK
Email for correspondence: marta.falkowska@manchester.ac.uk
Medical oxygen concentrators (MOCs) utilise pressure swing adsorption to produce oxygen with
~88–92 vol% purity from ambient air. In this process a nitrogen-selective zeolite, most commonlymolecular sieve 13X, is first used to adsorb nitrogen from an inlet stream of air at higher pressure(approx. 4 bar), and then subsequent adsorbent regeneration is achieved by passing the air throughthe sieve at lower pressure (below 1 bar).1 By operating in fast adsorption-desorption cycles, themachines can produce a continuous stream of oxygen used in oxygen-therapies often prescribed forpatients with deprived breathing capabilities.2
It has been suggested that the preferential adsorption of nitrogen from the air when compared tooxygen on the 13X molecular sieves is caused by the difference in the quadrupole moment of these
two molecules, and the fact that for nitrogen it is three times higher than for oxygen.3 Consequently,
the affinity of nitrogen molecules to the electrostatic field of the zeolite is greater than for oxygen,and results in their enhanced adsorption from the air. Even higher adsorption of nitrogen can beachieved when the Na+ ions present in the zeolite 13X framework are exchanged for Ca2+ or Li+.1,4
To gain deeper insights, we conducted total neutron scattering experiments (TNS) to directly probe
the molecular arrangement of adsorbates within zeolite 13X under varying pressure conditions. TNS
has been proven to be an exceptional experimental tool for gaining insight into the local environmentof liquids (e.g. water, benzene)5,6 and gases (e.g. nitrogen, oxygen, methane) contained within poresof porous media such as MCM-41, and without making crystallographic assumptions.7,8 Our researchcontributes to the molecular-level understanding of nitrogen adsorption from synthetic air in zeolite
13X (with Na+ and Ca2+), a critical step in the conscious design of gas-separating solutions. The focus
on TNS provides a novel perspective on the behaviour of gases (N2, O2, CO2 and N2/O2 mix) withinzeolite 13X pores, offering valuable experimental insights for the enhancement of gas separation
processes in healthcare applications.
References:
1. Ackley, Adsorption 2019, 25, 1437.
2. Pan et al., J. Nanomater. 2017, 7, 195.
3. Buckingham et al., JACS 1968, 90, 3104.
4. E.g. Wu et al., Eg. Ind. Eng. Chem. Res. 2016, 55, 4676.; Richards et al., J. Porous Mat. 1995, 2,
43.
5. Mancinelli et al., J. Phys. Chem. B 2009, 113, 50, 16169.
6. Falkowska et al., Angewandte Chemie International Edition Engl., 2018, 57, 4565.
7. Soper et al., Chem. Phys. Lett. 2017, 683, 529.
8. Soper et al., J. Chem. Phys. 2021, 154, 184503.
Acknowledgements:
The authors would like to thank Gemma Draper and Mark Kibble for their help in preparing theexperimental setup at ISIS. The authors would also like to acknowledge the ISIS neutron and muonsource for awarding the beam time RB2200307.

28

Selectivity in adsorption of responsive metal-organic frameworks
Irena Senkovska1, Volodymyr Bon1, Leila Abylgazina1, Mariia Maliuta1, and Stefan Kaskel1
1Inorganic Chemistry I, Dresden University of Technology, Bergstr. 66, 01069 Dresden, Germany

Emails for correspondence: irena.senkovska@tu-dresden.de, volodymyr.bon@tu-dresden.deFlexible metal-organic frameworks (MOFs) that show reversible guest-induced phase transitions
between closed and open pore phases have enormous potential for highly selective, energy-efficient
separations, because they can selectively respond to external stimuli, adapting their pore size
triggered by adsorption-induced gating or breathing.
The flexible framework DUT-8 is the focus of the present contribution. It consists of paddle wheels,
2,6-naphthalenedicarboxylate linkers, and 1,4-diazabicyclo(2.2.2)octane pillars forming a primitive
cubic net. The composition of the metal node, crystal size, morphology, and conformation are used toeffectively tune the responsivity of DUT-8.
The macrosized crystals of DUT-8 show selective guest responsivity associated with a pronounced
cell volume change (~250%) upon gate opening. For DUT-8(Ni), an adsorption-induced transition
from a closed-pore (cp) to an open-pore (op) phase can be triggered by nitrogen, carbon dioxide, orhydrocarbons at their standard boiling points, as well as by the majority of solvent vapors and CO2 athigh pressure at room temperature. Nanocrystals of DUT-8 are rigid instead and show reversible
uptake of gasses after desolvation. This is a behavior typical for conventional microporous solids.
The mechanism behind gate opening relies on the hinge energetics of the network nodes, balancing
strain energy (favoring the open form) and linker-linker interactions (stabilizing the closed form).
The guest molecules’ interactions with the pore interior counteract these linker-linker interactions
and induce gate opening. For gas separation, selective pore opening can induce colossal selectivity,
which is a crucial aspect of energy-efficient separation processes.
DUT-8(Ni) is able to discriminate between CO2 and CH4 in the mixture of these gases at room
temperature.1 It is also able to isotopolog-selective switching, demonstrating D2 over H2 selective
responsivity.2
The macrocrystals of DUT-8(Zn) show selective reopening in the presence of dichloromethane (DCM)
over alcohols, wherever the crystal downsizing to micron size unexpectedly reverses the gate opening
selectivity, causing DUT-8(Zn) to open its nanosized pores for alcohols but suppressing the
responsivity towards DCM.3
References:
1. M. Sin, N. Kavoosi, M. Rauche, J. Pallmann, S. Paasch, I. Senkovska, S. Kaskel, E. Brunner, Langmuir
2019, 35, 3162.
2. L. Bondorf, J. L. Fiorio, V. Bon, L. D. Zhang, M. Maliuta, S. Ehrling, I. Senkovska, J. D. Evans, J. O. Joswig,
S. Kaskel, T. Heine, M. Hirscher, Sci. Adv. 2022, 8, eabn7035.
3. L. Abylgazina, I. Senkovska, R. Engemann, N. Bönisch, T.E. Gorelik, Ch. Bachetzky, U. Kaiser, E.
Brunner, and S.Kaskel, under revision.
Acknowledgements:
The authors gratefully acknowledge the financial
Forschungsgemeinschaft) under contracts FOR 2433.

29

supportfrom

DFG(DeutscheInsights into Capillary Condensation and Hysteresis in
Nanoporous Materials from New Simulation Methods
Randall Q. Snurr1, Zhao Li1, Filip Formalik1, Jesse Prelesnik2, and J. Ilja Siepmann2
1 Department of Chemical & Biological Engineering, Northwestern University, Evanston, IL 60208,

USA

2 Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA

Email for correspondence: snurr@northwestern.edu

Capillary condensation and the related phenomenon of adsorption hysteresis can impact
applications of porous materials such as gas storage, separations, and adsorption cooling. To better
understand these phenomena, we have calculated the adsorption isotherms for methane, ethane,
propane, and n-hexane from atomistic grand canonical Monte Carlo (GCMC) simulations in a metalorganic framework having both micropores and mesopores [1]. At low temperatures, the calculated
isotherms exhibit sharp steps accompanied by hysteresis. As a complementary simulation method,
canonical (NVT) ensemble simulations with Widom test particle insertions are demonstrated toprovide additional information about these systems. The NVT+Widom simulations provide the fullvan der Waals loop associated with the sharp steps and hysteresis, including the locations of the
spinodal points and points within the metastable and unstable regions that are inaccessible to GCMC
simulations. The simulations provide molecular-level insight into pore filling and equilibria between
high- and low-density states within individual pores. The effect of framework flexibility on
adsorption hysteresis was also investigated for methane in IRMOF-1 [1].
We have also the adsorption and desorption isotherms for argon at 87 K in 1873 MOFs from the CoRE
MOF database [2] and for short n-alkanes in selected MOFs. Analysis of the molecular configurations
showed at least two different mechanisms and origins of hysteresis: one involving a transition in the
pores similar to a liquid-to-solid transition and one more similar to a gas-to-liquid transition. The
validity of an empirical relationship for the critical pore diameter for hysteresis was also tested using
the calculated argon desorption isotherms. The simulations reveal some structures where isotherms
exhibit two steps in the adsorption branch and only one step in the desorption branch. Hysteresis
loops with a different number of adsorption and desorption steps are quite rare in the literature. To
better understand why hysteresis is observed in the GCMC simulations, the concept of the transition
probability, which describes the probability of observing a step in the adsorption isotherm at a given
pressure in a GCMC simulation, is introduced. We used three different methods to calculate thetransition probabilities, and we validated that the three methods yielded similar results. The
transition probability can be used as a method to quantify and test the convergence of GCMC
simulations in the metastable region of an adsorption process.
References:
1. Z. Li, J. Turner, R.Q. Snurr, Computational investigation of hysteresis and phase equilibria of nalkanes in a metal-organic framework with both micropores and mesopores,” Comms. Chemistry, 6(2023) 90.
2. Y.G. Chung, E. Haldoupis, B.J. Bucior, M. Haranczyk, S. Lee, H. Zhang, K.D. Vogiatzis, M. Milisavljevic,
S. Ling, J.S. Camp, B. Slater, J.I. Siepmann, D.S. Sholl, R.Q. Snurr, Advances, updates, and analytics forthe computation-ready, experimental metal-organic framework database: CoRE MOF 2019, J. Chem.
Eng. Data, 64 (2019) 5985−5998.
Acknowledgements:
This work was supported by the U.S. Department of Energy, Office of Basic EnergyvSciences, Divisionof Chemical Sciences, Geosciences and Biosciences under Award No. DE-SC0023454.

30

Anomalous interaction between propylene and Ag cation inzeolites
Hideki Tanaka,1,* Tomoki Ogata,2 Motomu Sakai,3 Masahiko Matsukata,4 Katsuya Teshima1,2
1 Research Initiative for Supra-Materials (RISM), Shinshu University, Japan
2 Department of Materials Chemistry, Faculty of Engineering, Shinshu University, Japan
3Research Organization for Nano & Life Innovation, Waseda University, Japan
4Department of Applied Chemistry and Advanced Research Institute for Science and Engineering,

Waseda University, Japan
Email for correspondence: htanaka@shinshu-u.ac.jp
Recently, Ag-exchanged zeolite X (Ag-X) membrane was found to be promising for
propylene/propane separation [1]; however, the separation mechanism providing the high C3H6
selectivity is still unclear. To elucidate this mechanism, it is essential to identify the positions of theAg cations in the zeolite X framework, and to clarify the adsorption behavior of C3H6 on Ag-X bymolecular modeling. In this study, in situ synchrotron X-ray powder diffraction of Ag-X wasmeasured, and the positions of Ag cations were identified by the Rietveld and MEM analyses, andthen the obtained structure was used to understand the adsorption mechanism of C3H6 by ab initio
molecular dynamics (MD) simulation.
In situ XRPD measurements were carried out
at SPring-8 (BL02B2). The Rietveld analysis(RIETAN-FP) of the obtained XRPD pattern was
successfully performed (Rwp = 7.7, S = 1.5) (Fig.
1), and the fractional coordinates (I−VI sites) andoccupancies of Ag cations were identified. In
addition, the electron distribution of the Ag
cation was observed at each site by the MEM
analysis (Dysnomia) (Fig. 1), which shows thevalidity of the Rietveld analysis. The only Ag
cation sites that should contribute to C3H6
adsorption are the IV, V, and VI sites. The ratio of
Ag cations in these sites to total Ag cations was
0.53. On the other hand, the number of adsorbed
C3H6 molecules per Ag cation was estimated to be
ca. 0.55 from the low relative pressure region of the C3H6 adsorption isotherm (313 K). In otherwords, if we assume that one C3H6 molecule is adsorbed per Ag cation, the ratio of Ag cations that cancontribute to C3H6 adsorption is 0.55, which is in good agreement with the result from the Rietveld
analysis.
Ab initio MD simulation based on the Ag-X structure from the Rietveld method showed that the
12-membered ring channels of Ag-X were blocked by the adsorbed C3H6 molecules on Ag cations andthe C3H6 molecules diffused by hopping between the Ag cations. This blocking should prevent the
diffusion of propane inside Ag-X, which does not have a specific interaction with the Ag cation andcontribute to the high C3H6 selectivity of the Ag-X membrane. The most interesting finding revealedby this ab initio MD simulation is that the Ag cations exhibit extremely specific motion, resembling
the role of a “pump” that releases and diffuses the adsorbed C3H6.

References:1.

M. Sakai et al., ACS Appl. Mater. interfaces 12 (2020) 24086–24092; 11 (2019) 4145−4151.

31

Unusual coexisting adsorption and structural transformations
mechanism in Nano-Porous Materials
Bogdan Kuchta1,2, Bartosz Mazur1, Lucyna Firlej1,3, 1,3Malgorzata Stankiewicz1,3
1Department of Micro, Nano, and Bioprocess Engineering, Faculty of Chemistry, Wroclaw Universityof Science and Technology, 50-370 Wroclaw, Poland
2 MADIREL, CNRS, Aix-Marseille University, 13397 Marseille, France
3Laboratoire Charles Coulomb, University of Montpellier-CNRS, 34095 Montpellier, France

Email for correspondence: Bogdan.kuchta@pwr.edu.pl

The phase behavior of confined fluids adsorbed in nanopores differs significantly from their bulk
counterparts and depends on the chemical and structural properties of the confining structures. In
general, phase transitions in nanoconfined fluids are reflected in stepwise adsorption isotherms witha pronounced hysteresis. Here, we show experimental evidence and an in-silico interpretation of thereversible stepwise adsorption isotherm which is observed when methane is adsorbed in the rigid,
crystalline metal−organic framework IRMOF-1 (MOF-5) [1]. In a very narrow range of pressures, theadsorbed fluid undergoes a structural and highly cooperative reconstruction and transition between
low-density and high-density nanophases, as a result of the competition between thefluid−framework and fluid−fluid interactions. This mechanism evolves with temperature: below 110
K, a reversible stepwise isotherm is observed, which is a result of the bimodal distribution of thecoexisting nanophases. This temperature may be considered as a critical temperature of methane
confined to nanopores of IRMOF-1. Above 110 K, as the entropy contribution increases, the isotherm
shape transforms to a common continuous S-shaped form [2] that is characteristic to a gradualdensification of the adsorbed phase as the pressure increases. The other IRMOF structures have been
also modeled and the results compared to the IRMOF-1 case. The density distribution shows
symmetric structures which structural properties evolve in a function of uptake and temperature [3].

References:
1. B. Mazur, F. Formalik, K. Roztocki, V. Bon, S. Kaskel, Alexander V. Neimark, Lucyna Firlej, andBogdan Kuchta, Quasicontinuous Cooperative Adsorption Mechanism in Crystalline Nanoporous
Materials, J. Phys. Chem. Lett. 2022, 13, 6961−6965
2. D. Fairen-Jimenez, N. A. Seaton, T. Dü ren, Unusual Adsorption Behavior on Metal-Organic
Frameworks. Langmuir 2010, 26 (18), 14694−14699.
3. Kuchta, B.; Dundar, E.; Formalik, F.; Llewellyn, P. L.; Firlej, L. Adsorption-Induced Structural Phase
Transformation in Nanopores. Angewandte Chemie - International Edition 2017, 56 (51),16243−16246.
Acknowledgements:
Supported by the National Science Centre (NCN), Poland (grant: 2022/45/B/ST8/02028).

Understanding the Origins of Reversible and Hysteretic Pathwaysof Adsorption Phase Transitions by Mesocanonical Ensemble
Monte Carlo Simulations
Shivam Parashar1, Alexander Neimark 1
1

Department of Chemical and Biochemical Engineering, Rutgers, The State University of New
Jersey,Piscataway, New Jersey 08854, United States
Emails for correspondence: sp1709@soe.rutgers.edu, aneimark@rutgers.edu

Phase transformations in adsorbed fluids frequently involve metastable states and hysteretictransitions. This phase behavior is revealed in adsorption experiments with mesoporous materials
and most prominently in Grand Canonical Monte Carlo (GCMC) simulations, which are mostcommonly used to calculate adsorption isotherms. GCMC simulation typically produces a hysteretic
adsorption-desorption isotherm with stepwise transitions. Due to the difference in experimental andsimulation conditions (range of fluctuations and time of observation), the positions of experimentallyobserved and simulated transitions may differ significantly. Also, the hysteretic GCMC isotherm does
not allow for determination of the position of true equilibrium between the coexisting phases.
Alternative methods, such as the canonical ensemble, address this limitation fixing the number ofparticles and measuring the chemical potential using the Widom insertion method. Canonicalensemble generates a Van der Waals type isotherm that traces stable, metastable, and unstablestates. However, calculation of chemical potential is computationally expensive, especially at higher
fluid densities, due to a difficulty of inserting probe particles.
Mesocanonical ensemble 1, 2, 3 provides an efficient method of MC simulations (MCEMC), called thegauge cell method, for calculating the chemical potential, sampling of metastable and labile statesand producing a continuous Van der Waals type phase diagram of nanoconfined fluids. This method
involves coupling the sample cell with a finite volume reservoir (gauge cell), which restricts thedensity fluctuations and stabilizes the adsorbed phase. The MCEMC method allows for calculating thepositions of true phase equilibrium and the nucleation barriers, which control the hysteretic phasetransitions. In this work, we implemented the MCEMC method in the open source software RASPA
and demonstrated its capabilities and efficiency for studies adsorption on practical MOFs, like
IRMOF-1, ZIF-412, UiO-66, Cu-BTC, IRMOF-74-V, VII, and IX. The calculated adsorption isotherms aretested against the experiments and compared with the results of grand canonical, transition matrix,
canonical ensemble MC simulations.

References:
1. Neimark, A. V.; Vishnyakov, A., Gauge cell method for simulation studies of phase transitions in
confined systems. Physical Review E 2000, 62 (4), 4611-4622.
2.
Vishnyakov, A.; Neimark, A. V., Studies of Liquid−Vapor Equilibria, Criticality, and Spinodal Transitions in Nanopores by the Gauge Cell Monte Carlo Simulation Method. The Journal of Physical
Chemistry B 2001, 105 (29), 7009-7020.
3.
A.V. Neimark and A. Vishnyakov, - A Simulation Method for the Calculation of Chemical Potentials in Small, Inhomogeneous, and Dense Systems, Journal of Chemical Physics, 2005, V. 122,
234108.
Acknolegments: This work is supported by the NSF CBET grant 1834339.

33

Flat-histogram Simulations of Water in MOFs: Advanced
Strategies for Overcoming Sampling Challenges
Daniel W. Siderius1, Harold W. Hatch1, and Vincent K. Shen1
1 Chemical Sciences Division, National Institute of Standards and Technology, 100 Bureau Dr,

Gaithersburg, MD, 20899, USA
Email for correspondence: daniel.siderius@nist.gov
Adsorption of water by porous materials has recently reemerged as an area of interest due to its
possible application as a platform for harvesting water from humid air. Combined with the widespread
application of computational screening of adsorbent materials for various applications, molecularsimulations of water in confinement are once again an area of ongoing investigation. However, the key
challenge of water simulations in porous materials remains unchanged: due to strong water-waterhydrogen bonding, adsorption of water occurs primarily at high relative humidity or low temperatureand typically over a narrow pressure range [1], akin to Type V isotherms in the standard IUPAC
classification scheme. Hydrogen bonding networks also encourage coalescence of water in pores
rather than monolayer formation [2,3]. These challenges are exacerbated in hydrophobic metalorganic frameworks (MOFs) with cage-like pores, where adsorption occurs non-sequentially, but via
abrupt steps in which one cage (cavity) fills with a single cluster of water in each step [1]. Thesesimulation challenges are manifested by slow equilibration, inefficient sampling, and large
uncertainties in ensemble averages [1]. The introduction of so-called superhydrophobic materials only
amplifies these simulation challenges. Recent work has explored strategies to overcome the sampling
challenges by using energy look-up tables, insertion (deletion) biases, and continuous-fractional
component Monte Carlo [1].
We approach the problematic sampling of water adsorption in hydrophobic materials through asimilar suite of simulation tools, starting with flat-histogram Monte Carlo (MC) and adding advanced
MC moves, and then parallel simulations, all focuses on improving the efficiency with which thestatistical phase space is sampled. In particular, we introduce configurational-bias MC operations thatare tuned for adsorption in crystalline materials and specialized MC moves that address the proclivityof water to form clusters. We implement flat-histogram MC using Wang-Landau and Transition-matrix
biases, which additionally allows us to examine water cluster formation via the macrostate probability
distribution, such as through identification of free-energy barriers between individual clusters.
However, the water-clustering effect necessitates the introduction of new analysis tools for converting
the macrostate probability distribution to ensemble averages including the adsorption isotherm.
These advanced strategies are implemented using the FEASST Monte Carlo toolkit [4], which provides
modularity and is accessible to other researchers. The end effect is to both present simulation results
for specific materials that highlight the challenges of water adsorption and use these prototype
systems to suggest specific strategies for other researchers that simulate water adsorption.
References:
1. Zhang and Snurr, J Chem Phys C, 121:24000 (2017);
2. Striolo, Gubbins, Chialvo, and Cummings, Mol Phys 102:243 (2004);
3. Sarkisov, Centineo, and Brandani, Carbon 118:127 (2017);
4. Hatch, Mahynski, and Shen, J Res NIST, 123:123004 (2018).

34

Mechanism of Vapor Sorption and Sorption-Induced
Deformation in Bacterial Spores
Gennady Y. Gor1,2, George W. Scherer3, Howard A. Stone1
1 Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ, USA
2 Dept. of Chemical and Materials Engineering, New Jersey Institute of Technology, Newark, NJ, USA
3 Department of Civil and Environmental Engineering, Princeton University, Princeton, NJ, USA

Email for correspondence: ggor@princeton.edu
Bacterial spores have outstanding properties from the materials science perspective, which allow
them to survive extreme environmental conditions. Recent work by Harrellson et al. [1] studied themechanical properties of Bacillus Subtilis spores, and unique evolution of these properties with thechange of humidity. The experimental measurements were interpreted assuming that the spores
behave as water-filled porous solids, subjected to hydration forces. Here we revisit theirexperimental data using literature data on vapor sorption on spores and ideas from polymer physics.
We demonstrate that upon the change of humidity the spores behave like hydrogels with respect totheir swelling, elasticity, and relaxation times. This picture is consistent with the knowledge of thematerials comprising the bacterial cell walls – cross-linked peptidoglycan. Our results provide aninterpretation of the mechanics of bacterial spores and can help in developing novel synthetic
materials mimicking the mechanical properties of the spores.
References:
1. Harrellson, S.G., DeLay, M.S., Chen, X., Cavusoglu, A.H., Dworkin, J., Stone, H.A. and Sahin, O.,
Hydration solids, Nature, 619, (2023) 500-505.
Acknowledgements:
G.Y.G. thanks NSF CBET-1944495 grant for the support.

35

CPM9 | REPORT OF ABSTRACTSTUESDAY, MAY 21, 2024

36

Combining multiple functions to achieve process intensificationin adsorptive separations
Mohsen Gholami1; Ravi Sharma1; Matthias Schoukens1; Gille Wittewrongel1; Rahul Maity1; Joeri
Denayer1
1Dept. of Chem. Eng., Vrije Universiteit Brussels, BE
Email for correspondence: joeri.denayer@vub.be

There is a tendency in chemical industry to electrify thermal chemical processes in order to reducecarbon footprint 1. Therefore, electrification of Thermal Swing Adsorption processes is also of interest. Alternative heating methods such as Joule heating (Electrical Swing Adsorption - ESA) [2],Microwave heating (Microwave Swing Adsorption - MSA) [3] and Magnetic Induction heating (Magnetic Induction Swing adsorption –MISA) [4] have been considered by various researchers to heatand regenerate the adsorbent bed. These methods have a number of advantages, such as the direct,
contactless and localized heating of the bed, resulting in reduced heat losses; high heating rates andan on/off behavior, offering perspectives for improved process control and reduced cycle time.
Nevertheless, these electrified regeneration methods require materials that are compatible with therespective heating method. Joule heating requires an electrically conductive path, microwave heating requires dielectric properties for the adsorbent material and induction heating requires an adsorbent with magnetic properties. Obviously, common porous solids don’t have all of these properties.
Therefore, composite materials have to be developed such that the resulting hybrid adsorbent becomes susceptible to the applied heating method. Such materials can be shaped as beads, extrudates,
3D-printed materials or monoliths. This does not only affect the separation performance, but also theheating behavior.
In this paper, a number of approaches to prepare hybrid materials for electrified Temperature Swing
Adsorption processes will be discussed, from literature and our own work. Examples in the field ofcarbon capture, direct air capture and solvent recovery will be given.
References:
1. M. Bonheure, L. Vandewalle, G. Marin and K. Van Geem, Dream or reality? Electrification of thechemical process industries, Chemical Engineering Progress, 117(3). (2021) 37-42.
2. R.P.P.L. Ribeiro, C.A. Grande, A.E. Rodrigues, Electric Swing Adsorption for Gas Separation and
Purification:
A
Review,
Sep.
Sci.
Technol.
49(2014)
1985–2002.
3. Reuß, J., Bathen, D., & Schmidt-Traub, H. (2002). Desorption by microwaves: Mechanisms of multicomponent mixtures. Chemical Engineering and Technology, 25(4), 381–384.
https://doi.org/10.1002/15214125(200204)25:4<381::AID-CEAT381>3.0.CO;2-0
4. Gholami, M., Verougstraete, B., Vanoudenhoven, R., Baron, G. V., Van Assche, T., & Denayer, J. F.
M. (2021). Induction heating as an alternative electrified heating method for carbon capture process.
Chemical Engineering Journal, 431.
Acknowledgements:
The authors would like to acknowledge VLAIO for the financial support (HBC.2019.0109).

37

Measurement of multicomponent adsorption isotherms based ona temperature-step approach and mass spectrometry
Nicolas Chanut1, Robbe Van Loenhout1, Cesar Parra Cabrera1, Masaya Sugihara1, João Fernandes1,
Margot Verstreken1, Leen Boullart1, Rob Ameloot1
1 Center for Membrane Separations, Adsorption, Catalysis, and Spectroscopy (cMACS), KU Leuven,

Celestijnenlaan 200F, 3001 Leuven, Belgium
Email for correspondence: nicolas.chanut@kuleuven.be

Equilibrium single-component measurements are routinely performed using volumetric orgravimetric techniques. However, because industrial processes deal with mixtures and different
molecules compete for the same adsorption sites, single-component isotherms are of limited use indesigning a separation process. Researchers have long tried to predict mixture adsorption based on
single-component isotherms (e.g., ideal adsorbed solution theory), but non-ideal behavior remains
challenging to forecast without actual mixture adsorption experiments. Unfortunately, measuringmulticomponent adsorption is complex and time consuming. A range of methods has beendeveloped, yet none combines ease of operation, straightforward data analysis, and fastmeasurements. Breakthrough methods, by far the most common approach, illustrate this trade off.
While it provides robust multicomponent adsorption data, each data point requires a few hours to
one day due to the relatively large adsorbent mass (> 100 mg)
and the reactivation of the adsorbent between eachmeasurement, making this approach time-consuming for thecollection of full multicomponent isotherms.
In this presentation, we will present a new methodology for the
rapid measurement of reliable multicomponent adsorption
isotherms. Instead of a concentration change in the atmospheresurrounding the adsorbent, a sudden temperature change of theadsorbent is used to induce full desorption after equilibration at
every partial pressure. The desorbed fraction is quantified
downstream using a mass spectrometer, by integration of thesignal in excess of its baseline. Because of the use of downstream
MS analysis, the method can be readily extended tomulticomponent measurements (Figure 1).
Compared to breakthrough measurements the temperature-step approach is much faster. The
temperature-step approach uses much smaller adsorbent quantities (< 100 µg), which considerably
decreases the equilibration time. Moreover, since at each step all guest molecules are thermallydesorbed, no separate re-activation step of the adsorbent is necessary in between measurements.
Our results show a data acquisition time of < 10 min per point on a multicomponent isotherm andstraightforward data analysis (i.e., integration of the MS signal).
The methodology has first been validated for the measurement of single-component isotherms. The
high sensitivity of a triple-quadrupole MS allows for the quantification of small amounts of preadsorbed species (e.g., 1 nmol or 60 ng for 1-propanol). A full isotherm of 1-propanol on ZIF-8 (using
a 57µg sample) was compared to results obtained by Quartz Crystal Microbalance and volumetry
measurements, showing a good agreement between the different methods. Results ofmulticomponent adsorption measurements on industrially relevant adsorbents and theirinterpretation will be further detailed in the presentation.

38

Direct visualization of Al distribution inside zeolite crystals
Yoshihiro Kamimura1, Tetsuya Kodaira1 and Akira Endo1
1 National Institute of Adavance Industrial Science and Technology (AIST), Central 5,

1-1-1 Higashi,Tsukuba, Ibaraki 305-8565, Japan
Email for correspondence: endo-akira@aist.go.jp

Zeolites are porous material widely used as a catalyst, adsorbent in many industrial fields.
Zeolite framework consist of mainly Si, Al and O, and it is important to control the position of Al at
the atomic level. In addition, the size of zeolite particles are generally micron order, and the
distribution of elements at that scale is expected to significantly affect the properties of zeolites. In
this study, we aim to characterize zeolites in more detail by combining the visualization of atomic
distribution at sub-micron scale by scanning electron microscopy and the evaluation of zeolite pore
structure by a gas adsorption method. SEM is widely used as a tool to observe surfaces andmicroscopic shapes and sizes. Retarding methods have made it possible to observe the topmost
surface structure of a sample with a resolution of about 1 nm using low acceleration voltages lessthan 1kV [1]. In addition, it has become possible to obtain information on the internal structure ofparticles by forming a smooth cross-section using Ar ions [2], and to directly observe thecompositional distribution inside the sample by combining this technique with the EDS method. In
this study, visualization of aluminum distribution inside the zeolites was performed by applying
high-resolution FE-SEM and EDS mapping. Commercially available and synthesized zeolites withvarious Si/Al were selected as target material and Al-distribution inside zeolite particles werevisualized. As shown in Figure 1, the Al distribution inside the zeolite particle is clearly observed.
Furthermore, high-resolution Ar physisorption measurements were conducted to correlate with thedetailed pore textural assessment. The origin of this Al-distribution will be discussed in thepresentation.

Figure 1. (a) Top-surface and (b) cross-sectional surface FE-SEM images for protonated-form pristinezeolite Y (Si/Al = 2.75). Cross-sectional surface (c) FE-SEM and (d) EDS mapping images for samezeolite Y sample at different viewing position. (e) Argon physisorption isotherms at 87.3K.
References:
1. A.Endo, M. Yamada, S. Kataoka, T. Sano, Y. Inagi, A. Miyaki, Direct observation of surface structureof mesoporous silica with low acceleration voltage FE-SEM. Colloids Surf. A Physicochem. Eng. Asp.
2010, 357, 11–16.
Acknowledgements:
Moonshot Project entitled as the “Development of Recovery and Removal Techniques of Dilute
Reactive Nitrogen to Realize Nitrogen Circulating Society” from the New Energy and Industrial
Technology Development Organization (NEDO) funding agency, Japan.

39

Predicting the pore-structure transport relationship indisordered alumina using hyperpolarized xenon MRI and NMR
cryodiffusometry
S. M. Collins1,2, H. Williams2, G. E. Pavlovskaya2, T. Meersmann2, A. Harrison2, C. Vallée1, T.
Chevalier1, D. Lofficial1 and S. P. Rigby2
1 IFP Energies Nouvelles, Rond-point de l’échangeur de Solaize, BP 3, 69360 Solaize, France
2 University of Nottingham, Nottingham, United Kingdom

Email for correspondence: enysmc@nottingham.ac.uk
The characterization of porous aluminas has been a long-standing problem due to their complex,
disordered porous structures, with structural features ranging from the nanometre to the millimetre
scale. There is a need to understand how the pore structure influences mass transport, to guide newcatalyst designs and optimize catalytic processes. However, the complex, hierarchical nature of pellet
structure often means that a so-called “brute force” approach is beyond the reach of current
computing power, and methods enabling selection of the key structural features to incorporate intoa model are necessary. In this work, the combination of hyperpolarized (hp) 129Xe MRI and NMR
cryodiffusometry, has been used to probe the structural-transport relationship of bimodal
amorphous gamma alumina support pellets, with different degrees of controlled macroporosity toassess the key void space features determining tortuosity.
NMR cryodiffusometry experiments, using water or cyclohexane as the probe fluid, were performed
using both boundary and scanning, and both melting and freezing curves. These experiments were
coupled with complementary DSC thermoporometry to corroborate the cryoporometry results, and
FIB-SEM experiments to aid the interpretation of the NMR data. A novel hp 129Xe NMR/I technique
has been developed to allow the probing of the spatial distribution of rates of gas uptake acrossindividual catalyst pellets, and this to be related to pore structure and, also, catalytic performance.
The self-diffusivity of water as a function of molten fraction has been measured using NMR
cryodiffusometry1, and, thence, the relative importance of different aspects of the void space, andvarious bins within the pore size distribution, to mass transport rates has been investigated. Pore
structure models have been fitted to the tortuosity versus molten fraction plots, to infer the basic
geometrical character. Hp 129Xe MRI allows for the study of low-density, gas-phase mass-transport,such that diffusion can be measured in the Knudsen diffusional regime, instead of the purely
molecular regime, more closely mimicking the transport processes that would occur in gas-phasecatalytic reactions2. Whilst NMR cryodiffusometry measures the average self-diffusion coefficient ofliquid water over 10s of microns, the hp xenon experiments measures the impact of long-scale
structural features on pellet mass transfer. Through the combination of these two techniques,
structural and diffusional heterogeneities at different length scales can be measured, and theiroverall contribution to the observed catalytic activity evaluated.
References:
1. E. Perkins et al., Determination of the percolation properties and pore connectivity formesoporous solids using NMR cryodiffusometry, Chemical Engineering Science, 63 (2008) 1929–
1940
2. G. Pavlovskaya et al., NMR Imaging of Low Pressure, Gas-Phase Transport in Packed Beds Using
Hyperpolarized Xenon-129 AIChE, 61 (2015), 4013–4019
Acknowledgements:
I would like to thank IFP Energies nouvelles for sponsoring this research.

40

Kinetic measurements on monoliths using the Adsorption
Differential Volumetric Apparatus (ADVA)
Riccardo Rea1, Mohsen Gholami2, Joeri Denayer 2, Stefano Brandani1, Enzo Mangano1
1 University of Edinburgh, Edinburgh, United Kingdom
2 Vrije Universiteit Brussels, Brussels, Belgium

Email for correspondence: E.Mangano@ed.ac.uk
In recent years, the ever increasing development of manufacturing techniques has allowed thesynthesis of a wide range of structured adsorbents designed to address some of the shortcomings ofconventional pelletised materials. Channel shapes and flow patterns are engineered to minimisepressure drop, improve adsorption/desorption kinetics and maximise accessibility to the active
material. The main challenges in the field of monoliths are commonly associated with the synthesis
and production process while it is often neglected that testing and characterise these structured
materials is equally challenging. Monoliths are produced in a variety of shapes and sizes and thisprevents the use of most conventional and commercial adsorption techniques. Most of these systems(microbalances and commercial volumetric apparatuses, for example) are generally designed tominimise dead volumes, sample units normally house relatively small quantities of powders orpelletised materials and accessibility to the uptake cells is often very limited. This means that in manycases monoliths need to be broken down to smaller pieces or fragments to be tested in the mostcommon apparatuses, providing only partial insights on the performance of the formed material.
The Adsorption Differential Volumetric Apparatus (ADVA) is a novel volumetric system designedwith two symmetric branches (sample and reference) and relies on a differential pressure transducer
across the sample and reference side for increased accuracy. This allows the system to provide highly
accurate equilibrium and kinetic measurements in the entire pressure range using very small sample
masses (<100 mg). The system has a modular design that allows to adapt the uptake cell to samples
of different sizes and shapes, making it ideal for the characterization of structured adsorbents.
In this work, we present gas transport measurements of CO2 and N2 at different pressure levels on anumber of monoliths. Samples include zeolite-based adsorbents with different pores sizes extruded
as monoliths of different wall sizes manufactured at Vrije Universiteit Brussels.
The measurements provide insights on the process performance of the material as well as the
manufacturing process.
References:
1.

J. Wang, E. Mangano, S. Brandani, F. Brandani, P. Pullumbi, A novel adsorption differential
volumetric apparatus to measure mass transfer in nanoporous materials, Separation and
Purification Technology, Volume 283, 2022.

41

Towards “infinite”selectivities in CO2/CH4 and CO2/N2
separations with MgNa-GIS flexible zeolite
J. Al Atrach, Y. Xiong1, E. B. Clatworthy1, V. Valtchev1,* and R. Guillet-Nicolas1,*
1

Normandie Université, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie (LCS),
14000 Caen, France.
Email for correspondence: remy.guillet@ensicaen.fr

Thanks to their perfectly tailored framework topologies, small-pore zeolites have received muchattention in the last years for separation of small gases with high added values.[1]. However, finding
the best zeolites for such task is not easy since many parameters have to be synergistically screened.
In this context, we present a comprehensive study mixing DFT calculations and molecular dynamics
simulations to isolate the best formulations for CO2 separation. This first step led to the templatefree synthesis of stable Na-GIS followed by partially ion-exchange with Mg2+ cations. The parent NaGIS and partially-exchanged NaMg-GISs were thoroughly characterized using state-of-the-art
techniques, and studied for their applicability for CO2 adsorption and CO2/N2/CH4 separation
through single component adsorption at both low and high pressures and dynamic breakthroughcurve analysis methods. In all cases, deep investigations were conducted using advanced and highprecision sorptiometry to understand the effect of the network dimensionality, flexibility andaccessibility on the resulting adsorption behaviour and heat of adsorption values with purecomponent and gas mixtures. Finally, simplified fast cycling experiments consisting of five complete
dynamic cycles were conducted to evaluate the potential of this material in pseudo realistic flow
setups. Our findings revealed that NaMg-GIS zeolite exhibits highly promising potential for efficient
CO2 separation, outperforming the parent Na-GIS and reference zeolites in both CO2/CH4 and CO2/N2
binary systems. Of particular importance, NaMg-GIS demonstrated an “infinite” selectivity for CO2 in
the CO2/CH4 separation at both 25 and 50°C.

Fig. CO2 breakthrough (a, c) anddesorption curves (b, d) at 25 and 50 °C
obtained from competitive dynamic
adsorption experiments, CO2/N2/He,
5/25/70 (a,b) and CO2/CH4/He, 20/30/50(c,d).

References:1.
M. Dusselier & M. E. Davis,
Chemical Reviews 2018, 118 (11), 52655329.

42

Material discovery with physics and AI
Lev Sarkisov1
The University of Manchester, UK

1

Email for correspondence: lev.sarkisov@manchester.ac.uk

Imagine a computer dreaming up a porous material with mathematically optimized properties for a
specific application. In this presentation, I will share some ideas on how to practically realize thisconcept.
The exponential growth of available and hypothesized porous materials, including Metal-Organic
Frameworks (MOFs), has necessitated a fundamental shift in our approach to selecting porous
materials for specific applications. Computational screening methods have emerged as a necessary
step to identify the most promising candidates before committing to costly experimental efforts.
Machine learning (ML) methods can significantly accelerate computational screening protocols. A
typical application of ML models involves training them to predict material properties from features
such as surface area or more complex characteristics, thus partially reducing the need for timeconsuming molecular simulations. Essentially, the ML model facilitates the process of sifting throughmillions of materials to identify promising ones.
A new emerging idea is to discard direct screening approaches and instead develop methods thatenable a computer to "hallucinate" new structures, guiding them towards a pre-specified objectivefunction. This approach is not tied to any specific material database and, we speculate, could be amuch more efficient way to search for materials. Implementing this idea, however, requires
overcoming several challenges associated with material representation, interpretability of themodel, and the physical realism of generated structures. Nonetheless, it may also create thepossibility of discovering entirely new materials with unprecedented properties and novel
adsorption phenomena.

43

Dissemination and updates to the universal standard archive filefor adsorption data
Stefan Kaskel1,4, Daniel Siderius2, and Jack Evans3
1 Dept. of Chem. & Food Chem., TU Dresden, Bergstr. 66, 01059 Dresden, Germany

2 National Institute of Standards & Technology, 100 Bureau Dr, MS 8320, Gaithersburg 20899-8320

Maryland, USA

3 Centre for Advanced Nanomaterials and Department of Chemistry, The University of Adelaide,

Adelaide, SA 5000 Australia

4 Fraunhofer IWS, Winterbergstr. 28, 01277 Dresden, Germany

Email for correspondence: stefan.kaskel@tu-dresden.de

Porous materials have shown remarkable effectiveness in energy and environmental applications.
However, the current method of presenting adsorption isotherms through graphs and figures falls
short in terms of reproducibility, reuse, and data sharing. It is crucial to promote open science in thefield of porous materials for future researchers [1].
Since 2021, we have developed a novel
standard adsorption information file(AIF), taking inspiration from the widelyused crystallographic information file(CIF) [2]. The AIF is a versatile and easily
expandable archive file format that isboth human and machine-readable. We
are continuously enhancing the format tomeet the requirements of researchers.
This initiative marks the first steps
toward an open adsorption data format,
simplifying the exchange of adsorption
data among laboratories, journals,
databases, and the scientific community. The adoption of this format is gaining momentum, driven
by the support of IUPAC (https://iupac.org/project/2021-016-1-024/).
The standardized reporting of adsorption isotherms will enable the application of advanced AI
methods (machine learning etc.) to develop innovative processes for separation and environmental
technologies and accelerate the finding of high performance porous materials for such operations.
References:
1. Wilkinson, M. et al. The FAIR Guiding Principles for scientific data management and stewardship.
Sci. Data 3 (2016) 160018.
2. Evans, J. D. et al. A Universal Standard Archive File for Adsorption Data. Langmuir 37 (2021) 42224226.
Acknowledgements:
We thank IUPAC funding project 2021-016-1-024.

44

Applications of 3D Amorphous Carbon Molecular Models for
Adsorption and Mechanical Property Predictions
Nicholas J. Correntea, Elizabeth L. Hinksa, Aastha Kaseraa, Raleigh Gougha, Peter I. Ravikovitchb, andAlexander V. Neimarkaa Department of Chemical and Biochemical Engineering, Rutgers, The State University of New

Jersey,Piscataway, New Jersey 08854, United Statesb ExxonMobil Technology and Engineering Company, Annandale, NJ, 08801, United States
We explore the capabilities of 3D molecular models of amorphous nanoporous carbons forreproducing the morphological and adsorption properties of practical activated carbons. The 3Dmodels are generated using a reactive forcefield in molecular dynamics (MD) simulations to anneal
and quench structures by mimicking the procedures used for production of practical carbons. Thisapproach allows for the formation of corrugated and defective 3D framework built by graphenesheets. The generated structures possess tunable pore size distributions, pore volumes, and surface
areas. We characterize these models by Monte Carlo (MC) simulations using standard molecular
probes (CO2, N2, and Ar) and show that they replicate the structural properties of practical carbons.
We demonstrate how the 3D models quantitatively predict adsorption of simple fluids and alkanes
at experimentally relevant conditions. [1, 2] We utilize a hybrid MC/MD simulation scheme to explore
how the structures deform in response to fluid adsorption. [2] The suggested method provides athorough understanding of the effect of pore morphology and flexibility on the adsorption dynamics.
This work is supported by the NSF CBET grant 1834339 and ExxonMobil.

Hybrid MC/MD simulation scheme.
References:[1] N.J. Corrente, E.L. Hinks, A. Kasera, R. Gough, P.I. Ravikovitch, A.V. Neimark, Modeling adsorptionof simple fluids and hydrocarbons on nanoporous carbons, Carbon 197 (2022) 526-533. DOI:
10.1016/j.carbon.2022.06.071[2] F. Vallejos-Burgos, C. de Tomas, N.J. Corrente, K. Urita, S. Wang, C. Urita, I. Moriguchi, I. SuarezMartinez, N. Marks, M. Krohn, R. Kukobat, A.V. Neimark, Y. Gogotsi, K. Kaneko, 3D Nanostructure
Prediction of Porous Carbons Via Gas Adsorption, Carbon 215 (2023), 118431. DOI:
10.1016/j.carbon.2023.118431[3] N.J. Corrente, E.L. Hinks, A. Kasera, R. Gough, P.I. Ravikovitch, A.V. Neimark, Adsorption-Induced
Deformation of Nanoporous Carbons with Mixtures: A Hybrid MC/MD Approach. In preparation

45

Computational-aided development of MOF-based Mixed Matrix
Membranes for molecular separation
Guillaume Maurin1
1

Université Montpellier/CNRS

Email for correspondence: guillaume.maurin1@umontpellier.fr

Mixed matrix membranes (MMMs) incorporating MOFs into polymeric matrices show promisingproperties for several key gas separation processes. Understanding of the MOF/polymer interface
and gas transport through the MMMs is of utmost importance. Here, we selected a series of MOFs asfillers in conjunction with both rigid and flexible polymers and we deployed our in-housecomputational strategy to construct MOF/Polymer atomistic models and assess their
thermodynamic and dynamic adsorption properties. This computational screening revealed that thedistinct characteristic of polymer backbones and MOF surfaces results in different interfacial pore
structuring. We evidenced that not only size but also shape of the interfacial pore region has eminent
effects on the gas transport properties of the MMMs with respect to a selected range of molecules.
This conclusion is an important step toward the rational design of MMMs with the optimal interfacial
pore size/shape to achieve the best performance for molecular separation. This computational
strategy has been also applied recently to explore the shaping of MOFs with the selection of theappropriate polymers of crucial importance in diverse industrial applications including CO2 capture.

46

Molecular Simulation of Peptide Retention in Reversed-Phase
Liquid Chromatography
José Paulo Mota1
1

NOVA School of Science and Technology

Email for correspondence: pmota@fct.unl.pt
Reversed-phase high-performance liquid chromatography (HPLC) is a fundamental tool for the purification and analysis of peptides. Peptides are separated on a hydrophobic stationary phase andeluted with a gradient of increasing organic solvent concentration. The nonpolar stationary phases
are most often spherical porous silica particles that have been surface derivatized with hydrocarbon
chains 1. The conditions of reversed-phase chromatography require a nonpolar stationary phase, but
this condition can be met by many different ligands. In fact, there are commercially available columnsof at least C1, C2, C4, Cg, C18, phenyl, and cyano functionalities, where the carbon num- bers refer tothe length of a fully saturated hydrocarbon chain. The most popular stationary phase for this purpose
is an octadecyl carbon chain (C18)-bonded silica [2].
Here, we employ advanced molecular simulation techniques to explore the effect of surface densityof the bonded stationary phase chains and mobile phase composition on the retention coefficients of
peptides over C18-bonded silica. Chromatographic retention involves a process of solute transferfrom a mobile phase into or onto a stationary phase. The association of the solute with the stationary
phase can involve partitioning, adsorption, or both. In either case, transfer is characterized by anexchange of the environment at the surface of the solute molecule: solute is initially surrounded byneighboring mobile phase molecules and is finally surrounded, fully or partially, by neighboring
molecules of the stationary phase. Our aim here is to consider how the standard-state chemical
potentials may be predicted from the molecular structures of the peptide chain and solvents andexternal thermodynamic variables (silica surface derivatized with hydrocarbon chains.).
References:
1. J. G. Dorsey, K. A. Dill, Chem. Rev. 89, 331 (1989).
2. C. A. Browne, H. P. J. Bennett, S. Solomon, Anal. Biochem. 124, 201 (1982)

47

Structural changes in ZIFs upon gas and liquid phase adsorption
Joaquin Silvestre-Albero1, A. Missyul,2 A. Martín-Calvo,3 S. Calero,3 Judit Farrando-Perez1
1 Advanced Materials Laboratory, Inorganic Chemistry Department - University Materials Institute,
University of Alicante, Spain
2ALBA synchrotron light source, Cerdanyola del Valles, Spain
3 Department of Physical, Chemical and Natural Systems, Universidad Pablo de Olavide, Seville,
Spain
Email for correspondence: joaquin.silvestre@ua.es
Chemical contamination in water and air streams requires the design of novel adsorbents able toretain/concentrate these pollutants selectively and with a high adsorption capacity. Activatedcarbons, zeolites, silicas, and metal-organic frameworks are among the most frequently usedadsorbents to this end. Utilizing MOFs for this purpose offers a significant advantage in terms ofcustomization, as the pore structure and surface chemistry of these materials can be tailored tomatch specific applications, rendering them as highly versatile tools for adsorption processes. Amongthem, ZIFs, a sub-class of MOFs, are characterized by a high specific surface area, a flexible and ultrahydrophobic pore structure and a high chemical and thermal stability [1]. These properties and thesimpleness of the synthesis protocols make them ideal adsorbents for gas and liquid-phaseadsorption processes. Compared to conventional adsorbents, ZIFs can suffer structural changes uponadsorption. Gate-opening, phase transition, breathing, etc., have been widely reported in theliterature for ZIFs upon an external stimulus [2,3]. Despite their relevance for the adsorption
performance and the selectivity of the process, structural changes in liquid-phase adsorption
processes are less described. Based on these premises, the aim of this study is to identify potential
structural changes in ZIFs upon liquid-phase adsorption, preferentially for aromatic contaminants,
and to perform a comparative analysis with similar structural phenomena upon gas adsorption. This
comparison will be achieved through the integration of adsorption studies, chemical and structuralcharacterization techniques, modeling, as well as synchrotron-based measurements conducted priorand post-adsorption.

References:
1. R.P. Lively, M.E. Dose, J.A. Thompson, B.A. McCool, R.R. Chance, W.J. Koros, Chem. Commun., 47(2011) 8667-8669.
2. M.E. Casco, Y.Q. Cheng, L.L. Daemen, D. Fairen-Jimenez, E.V. Ramos-Fernandez, A.J. Ramirez-Cuesta,
J. Silvestre-Albero, Chem. Commun., 52 (2016) 3639.
3. J. Gandara-Loe, A. Missyul, F. Fauth, L.L. Daemen, Y.Q. Cheng, A. Ramirez-Cuesta, P.I. Ravikovitch,
J. Silvestre-Albero, J. Mater. Chem. A, 7 (2019) 14552-14558.
Acknowledgements:
The authors acknowledge financial support from the MINECO (Projects PID2019-108453GB-C21 and
PCI2020- 111968/ERANET-M/3D-Photocat) and European Union: Horizon Europe (project MOSTH2; Grant agreement no. 101058547).

48

On the characterization of nanoporous carbons with small-angle
scattering
Oskar Paris1, and Christian Prehal2
1 Chair of Physics, Department Physics, Mechanics and Electrical Engineering, Montanuniversität

Leoben, Franz-Josef-Strasse 19, 8700 Leoben, Austria
2 Department of Chemistry and Physics of Materials, Paris Lodron University of Salzburg, Jakob-

Haringer-Strasse 2a, 5020 Salzburg, Austria
Email for correspondence: Oskar.paris@unileoben.ac.at
Small-angle scattering of X-rays (SAXS) has long been used to characterize nanoporous materials. An
advantage is that SAXS is sensitive to both, open and closed pores, and can thus delivercomplementary information to gas sorption analysis (GSA). While integral parameters such as the
specific pore volume or the specific surface area can readily be obtained from both methods usingclassical approaches, pore size distributions (PSDs) derived from the two techniques - even whencomparing fully open pore systems - are usually hardly comparable on a quantitative level. Apartfrom the inherent difficulty of defining a “smooth” surface for, e.g., micropores with sub-nanometer
pore sizes, also the shape and pore arrangement influences the results of a PSD determination. Here
we show an attempt to make PSDs derived from SAXS and GSA data from a series of microporous
activated carbons directly comparable [1]. To this end, a real space model of the pore structure iscreated from the SAXS data using the concept of Gaussian random fields. From these data, “sizedistributions”, e.g., the distribution of normal distances from points on the surface to the opposite
surface of a pore can easily be calculated. This distribution however deviates considerably from the
PSD obtained from GSA data using a mixed quenched solid density functional (QSDFT) kernel due toits inherent assumption of slit like pores. A “Degree of Confinement” parameter accounting for the
local pore geometry is employed to determine an alternative size distribution for purely slit likepores from the SAXS model, which shows good agreement with the corresponding GSA data. Potential
applications of the approach may particularly be helpful for closed pore systems such as nonactivated hard carbons.
References:
1. C. Prehal, S. Grätz, B. Krüner, M. Thommes, L. Borchert, V. Presser, O. Paris, Comparing pore
structural models of nanoporous carbons obtained from small-angle scattering and gas adsorption,
Carbon, 152 (2019) 416-423

49

Use of Ultrasonic Monitoring for In situ Diagnostics of Zeoliteand MOF Crystallization
Martin Hartmann1, Hasan Baser2, Marcus Fischer1, Rebecca Reber1, and Wilhelm Schwieger2
1 Institue of Chemical Reaction Engineering, Friedrich-Alexander-Universität Erlangen-Nürnberg(FAU), Egerlandstraße 3, 91058 Erlangen, Germany
2 Erlangen Center for Interface Research and Catalysis (ECRC), Friedrich-Alexander-Universität

Erlangen-Nürnberg (FAU), Egerlandstraße 3, 91058 Erlangen, Germany
Email for correspondence: martin.hartmann@fau.de
The investigation and understanding of the underlying mechanisms for the crystallization ofmolecular sieve materials such as metal-organic frameworks (MOFs) and zeolites have received
increasing interest in recent years. This is mainly because improvements of the corresponding
equipment were made that is essential for in situ diagnostics. In contrast to classical techniques, suchas X-ray diffraction and neutron scattering, nuclear magnetic resonance or infrared and Raman
spectroscopy, ultrasonic monitoring has not received proper attention [1]. Thereby, especially forzeolites, important insights have been gained with this technique already. In the present study, we
report the successful use of ultrasonic device as a real-time, in-situ diagnostic tool for monitoring the
crystallization progress of zeolite A from homogeneous, colloidal solutions with the composition 0.4
Na2O : 10 SiO2 : 1.4 Al2O3 : 16 (TMA)2O: X H2O (X: 650, 750, 850, 950, 1050). Kinetic information likereaction rate or reaction order of crystal growth can easily be calculated from the measured
ultrasonic signal data. For the mathematical description of the crystallization curves, theexperimental curves were fitted with different kinetic models. The crystallization proceeds in morethan one step suggesting a change of the kinetics during the formation of the crystalline material. The
evaluated reaction exponents for the different steps could only be described with Avrami-Erofeyev
nucleation model. The results indicate that - depending on amount of water in synthesis mixture first a three dimensional and then a one dimensional crystal growth takes place.
The understanding of metal organic framework syntheses is still a challenging task in the field of
porous materials. Proposed models for the MOF formation mechanisms includes the formation of
pre-nucleation building units (PNBU), which are “the minimum assembly of atoms, ions or molecules
which, by condensation of the group with others (identical or different) give rise to the final solid”[2]. The nature of these PNBUs is widely discussed, but detailed insights are still rare. In this study,
ZIF-8 with varying particle size and morphology is synthesized from zinc nitrate hexahydrate, 2methylimidazole and CTAB in different solvents. In our study, we found that the ultrasonicattenuation already increases rapidly within the first minute of the ZIF-8 syntheses. Depending on
the molar ratio of linker to metal, not only the final particle size, but also the course of the ultrasonicsignal changes. After stopping the syntheses at different times of during the attenuation increase, it
can be seen that in the synthesis with higher linker excess a second phase, namely ZIF-L is formed in
the first three minutes, while in the synthesis with an antilogarithmic course of attenuation
HMIM/Zn2+ = 60 only reflexes of ZIF-8 and the linker are visible.
References:
1. M. Ermer, R. Reber, H. Baser, M. Fischer, W. Schwieger, M. Hartmann, Perspective on the Use of
Ultrasonic Monitoring for In Situ Diagnostics of Zeolite and MOF Crystallization, Cystal Growth &Design 23 (2023) 3795-3807 (2023)
2. H. Embrechts, M. Kriesten, M. Ermer, W. Peukert, M. Hartmann, M. Distaso, Role of Prenucleation
Building Units in Determining Metal-Organic Framework MIL-53(Al) Morphology, Crystal Growth &Design, 20 (2020) 2631–3649.

50

Correlations of NMR Relaxometry Data and Polymer Surface
Chemistry
Murilo T. Suekuni1 and Alan M. Allgeier1
1 Dept. of Chem. & Petrol. Eng., University of Kansas, Lawrence, KS 66045 USA

Email for correspondence: alan.allgeier@ku.edu

Nuclear magnetic resonance (NMR) relaxometry enables facile characterization of a variety of porous
materials filled with liquids and gases. This study identifies quantitative correlations between
surface chemistry and NMR relaxation rates for a series of polymeric particle dispersions, serving aswell controlled examples of surface fluid interactions [1].
In NMR relaxometry, the measurement of the rate at which certain nuclei, e.g., 1H, re-equilibrate withan externally applied magnetic field upon radio-frequency excitation provides insight about pore sizeand pore surface chemistry. A solid-fluid affinity parameter (surface relaxivity, ρ2), linearly regressedfrom transverse relaxation data, reflects the constrained motion of adsorbate molecules interactingwith surfaces. Despite the increasing interest by the characterization community, the role of surface
chemistry upon the characterization of wetted surface area and pore volume distribution using
solvent relaxometry remains underexplored. D’Agostino et al. have correlated adsorption strength[2] and Schlumberger et al. have correlated water intrusion [3] to relaxation data for silica surfaces.
The present study explores wide-ranging polymer particle surface chemistry from hydrophobicpolyethylene to hydrophilic polyacrylic acid suspended in water and decane. The observed trends
showed a positive relation between heteroatom (oxygen, nitrogen) content and interactions withwater, with an opposite behavior for n-decane. This work supports the development of a transverse
surface relaxivity database, with values ranging from 0.1 to 8.4 μm s-1 and notable correlations towater contact angles. Ongoing investigation indicates that relaxometry has promising applications invarious fields, including heterogeneous catalysis, petroleum reservoir exploration, and drug delivery
mechanisms.

References:
1. M.T. Suekuni, A.M. Allgeier. Correlating Surface Chemistry to Surface Relaxivity via TD-NMR
StudiesofPolymer
Particle
Suspensions.
JACS
Au.
3
(2023)
2826-34.
2. C. D’Agostino et al. Interpretation of NMR Relaxation as a Tool for Characterising the Adsorption
Strength of Liquids inside Porous Materials. Chemistry - A European Journal, 20 (2014) 13009–
13015.
3. C. Schlumberger, M. Thommes and coworkers. Characterization of functionalized chromatographic
silica materials: Coupling water adsorption and intrusion with NMR-relaxometry . ChemRxiv.
Cambridge: Cambridge Open Engage; 2023. https://10.26434/chemrxiv-2023-jmjs8-v351

Advanced Textural and Surface Chemistry Characterization by
Combining Adsorption and Liquid Intrusion with NMR
Relaxometry
Carola Schlumberger1; Carlos Cuadrado Collados1; Jakob Söllner1; Lukas Sandner1; Jincheng Xu1;
Matthias Thommes1
1

Institute of Separation Science and Technology, Friedrich-Alexander-University ErlangenNuremberg

Emails for correspondence: matthias.thommes@fau.de, jincheng.xu@fau.de,carola.schlumberger@fau.de, jakob.soellner@fau.de, carlos.cuadrado@fau.de, lukas.sandner@fau.de
During the last decades, major progress has been made concerning the synthesis of nanoporous
materials allowing for the custom design of nanoporous materials for targeted applications in various
areas such as chromatography or catalysis. Enhancing the efficiency of these processes requires thetuning of the selectivity of the porous material to certain compounds of interest. Textural properties,
such as the specific surface area and pore (entrance) size may affect the process efficiency. Within
this context, we have recently shown that NMR relaxometry can be developed into a methodology forsurface area assessment of nanoporous materials immersed in a liquid phase. We also demonstrated
that NMR relaxometry shows potential to be developed as novel methodology for fast determinationof pore entrance sizes. In this sense, the choice of probe molecules with varying kinetic diameters
enables one to get information about the pore entrance size due to their different accessibility to thepore system 1.
In addition to textural properties, the surface chemistry plays an important role since it can enhance
the affinity and selectivity of certain compounds. The design of these processes therefore requires
the detailed investigation of the relation between structural properties, surface chemistry and theresulting process performance. Hence, reliable surface chemistry characterization of porous
materials is crucial.
In this context, the quantification of the surface chemistry inside of pores is very challenging and usually requires a combination of different experimental tools. Within this context, we demonstrate that
NMR relaxometry can be a valuable complementary tool for the fast characterization of the surface
chemistry of nanoporous materials. The ratio of the spin-lattice to spin-spin relaxation time (T1/T2)
has been suggested for surface chemistry and wettability characterization in the past. However, therelaxation time ratio of a certain sample may be affected by the surface chemistry as well as texturalproperties such as the surface area and pore size. Hence, quantification and comparison of the surface chemistry of different nanoporous materials is challenging. To address this limitation, this study
suggests a novel methodology for surface chemistry and wettability quantification based on the ratioof the spin-spin to spin-lattice surface relaxivity, which can be related to the spin-lattice to spin-spin
relaxation time ratio of the adsorbed liquid film on the pore surface (T1,ads.film/T2,ads.film−ratio).
This novel approach allows for the determination of a characteristic value, which is solely affected by
the surface chemistry. This is demonstrated using mesoporous stationary phase materials functionalized with different hydrophilic and hydrophobic surface functional groups. The study shows, for the
first time, the correlation between the T1,ads.film/ T2,ads.film−ratio of water and the contact angleof the adsorbed water film determined with water vapor adsorption and water intrusion.
References:
1.
C. Schlumberger, L. Sandner, A. Michalowski, M. Thommes. Reliable Surface Area Assessmentof Wet and Dry Nonporous and Nanoporous Particles: Nuclear Magnetic Resonance Relaxometry and
Gas Physisorption. Langmuir 2023, 39 (13), 4611–4621.

52

Brain Tissue Modeled as a Porous Medium with parameters
derived from Micro-Iontophoresis Experiments
Charles Nicholson1
1Dept. Neuroscience and Physiology, New York University School of Medicine, 435 E 30th St., New

York, NY 10016, USA
Email for correspondence: charles.nicholson@nyu.edu

The cellular structures of the brain are separated by a narrow fluid-filled extracellular (interstitial)
space giving brain tissue properties of a porous medium. The porosity and tortuosity can bemeasured by releasing tetramethylammonium cations from a micropipette and measuring the timedependent concentration about 100 µm away using an ion-selective microelectrode (ISM), as shownin Fig. 1 [1].
Fitting the results of experiments to an appropriate solution to the diffusion equation [1, 2] revealed
that that the typical porosity is
f ~ 0.2 and the tortuosity is t ~1.6, where tortuosity =(D/D*)0.5, D is free diffusivity
and D* is effective diffusivity.
These results were modeled byregarding the brain as an
ensemble of cubic cells of side
2a with cubic voids (expansionsof interstitial space) of side b ateach corner. Cells were
Fig.1. Experimental setup. Diffusion measurements made inseparatedbysheetsof*agarose (D) or brain slice (D ). Analysis with custom MATLAB
interstitial space of width 2w
software (Wanda and Walter) [1].
and the packed cells formed
composite voids of width 2b, as shown in Fig. 2.
Monte Carlo simulations took
place in this ensemble using theMCell program [3]. It was foundthat, to obtain the experimental
f and t, the required geometry
was a = 0.742 µm, b = 0.379µm and w = 20 nm [4]. The
presence of voids was essential
to obtain the measured
Fig. 2. Model of brain tissue. (a) unit cell with cubic corner
tortuosity and this feature wasvoids. (b) top view of cell (c) ensemble of cells spaced 2w apart.
consistent with freeze-fixed
In practice, 323 or 643 cells used for Monte Carlo simulations
electron microscopy and super[4].
resolution optical imaging [4].
References:
1. J. Odackal, R. Colbourn, N. J. Odackal, L. Tao, C. Nicholson, and S. Hrabetova. Real-time iontophoresis
with tetramethylammonium to quantify volume fraction and tortuosity of brain extracellular space,
JoVE: e55755 (2017).
2. E. Syková, and C. Nicholson. Diffusion in brain extracellular space, Physiological Reviews, 88 (2008)
1277-1340.
3. J.R. Stiles, and T.M. Bartol. 2001. Monte Carlo methods for simulating realistic synaptic
microphysiology using MCell. in E. De Schutter, Editor, Computational Neuroscience: Realistic
Modeling for Experimentalists, CRC Press: London; 2001, p 87 - 127.
4. C. Nicholson, Sheet and void porous media models for brain interstitial space, Journal Royal SocietyInterface, 20 (2023): 20230223.

53

3-D Density Functional Reory to Describe Adsorption of Pure
Substances and Their Mixtures on Crystalline and Amorphous
Adsorbents
Frederico Wanderley Tavares1
1Federal University of Rio de Janeiro, Rio de Janeiro, Brazil

Email for correspondence: tavares@eq.ufrj.br
The 1-D, 2-D, and 3-D classical Density Functional Theory (cDFT) consistent with the PC-SAFT
equation of state are used to investigate the adsorption isotherms and local densities of purehydrocarbons, H2, and CO2 and their mixtures in crystalline-structure materials (like MOF-5)
and amorphous materials (like nanoporous carbons). The cDFT calculations reveal that theadsorption process is influenced by the fluid-fluid spatial correlations between the fluid
molecules and the external potential produced by the solid structure. These findings aresupported by a comparison with experimental data and Grand Canonical Monte Carlo (GCMC)
simulations of the adsorbed amount and density profiles of the adsorbed fluid inside the solid.
One important parameter related to the accuracy involved in the DFT calculations is choosing
the appropriate grid size. We proposed a priori grid size that is crucial in 3-D-DFT calculations.
We also explore the impact of the non-crystalline structure of amorphous carbon nanopores on
fluid structure and adsorption isotherms, as well as fluid-fluid and fluid-solid interactions. We
offer insights for selecting computational methods in the fluid-structure analysis of nanoporous
materials, guiding future research and optimization in advanced material development fordiverse applications.

References:
1) Lucas J. dos Santos, Vítor M. Sermoud, Amaro G. Barreto Jr., Frederico W. Tavares,“Adsorption-Induced Deformation of Nanoporous Carbons: Insight from Classical Density
Functional Theory Based on the PC-SAFT Equation of State,” Fluid Phase Equilibria, 574, 113882(2023).
DOI: 10.1016/j.fluid.2023.113882
2) Elvis Soares, Amaro G. Barreto Jr., Frederico W. Tavares, “Classical Density Functional Theory
Reveals Structural Information of H2 and CH4 Fluids Adsorption in MOF-5”, Fluid Phase
Equilibria, 574, 113887 (2023).
DOI: 10.1016/j.fluid.2023. 113887
3) Lucas J. dos Santos, Elvis Soares, Amaro G. Barreto Jr., Frederico W. Tavares, “Comparison of
3D-cDFT and GCMC Simulations for Fluid-Structure Analysis in Amorphous Carbon Nanoporous
Materials”, Adsorption, (2024). Submitted.

54

A non-local Density Functional Theory for water adsorbed in
nanoporous materials.
Antoine Barthes1, David Grégoire1 and Christelle Miqueu1
1 Université de Pau et des pays de l’Adour, CNRS, LFCR (UMR 5150), Mechanics and Physis in

Porous Media group, 1 allée du parc Montaury, Anglet, France
Email for correspondence: christelle.miqueu@univ-pau.fr

Water confined in nanoporous materials has focused many attentions due to its vast number oftechnical applications and scientific fields such as geosciences, biology, catalysts, gas separation, etc[1,2 Indeed, confinement of water in nanopores affects its thermodynamic properties such as its
density, its freezing temperature, the crystal structure, etc. For some years now, porosimeter
manufacturers have been integrating the ability to perform high-precision measurements ofadsorption of vapors at low pressure, including water. In parallel, thermoporosimetry appears to bea good alternative - or at least a good complementary technique - to gas porosimetry and mercury
intrusion, especially for the investigation of the samples that can be destroyed in drying process [3].
The common features between water vapor sorption analysis and thermoporosimetry is that a
reliable model of water adsorption inside nanopores is necessary to interpret the experimental data
and try to obtain structural information of the porous materials from these measurements. In thiswork, we present a new NLDFT framework for confined water based on the general formulation of
Wertheim's thermodynamic perturbation theory [4] and the statistical associating fluid theory [4].
The resulting model can be employed to determine the microscopic structure of inhomogeneous
water in pores of arbitrary 3D geometry. It is first used to compute the density distribution, adsorbed
amount, hydrogen bonding, pore pressure, adsorption-desorption behavior at pore scale. Then, theinformation is upscaled to compute water adsorption isotherms in microporous adsorbents andcompare them with experimental data.
References:1.
Zangi, R., Water confined to a slab geometry: a review of recent computer simulation studies,
Journal of Physics: Condensed Matter, 16(45) (2004) S5371–S5388.
2.
Giovambattista, N.; Rossky, P. J.; Debenedetti, P. G., Computational Studies of Pressure,
Temperature, and Surface Effects on the Structure and Thermodynamics of Confined Water, Annual
Review of Physical Chemistry. Annual Reviews, 63(1) (2012) 179–200.
3.
Majda, D.; Zimowska, M.; Tarach, K.; Góra-Marek, K.; Napruszewska, B. D.; Michalik-Zym, A.,
Water thermoporosimetry as a tool of characterization of the textural parameters of mesoporous
materials: Refinement of the methodology, Journal of Thermal Analysis and Calorimetry, 127 (2017)
207-220.
4. M. S. Wertheim, Fluids with highly directional attractive forces. II. Thermodynamic perturbation
theory and integral equations, J. Stat. Phys., 35 (1984) 35–37.
5. G. Jackson; W. G. Chapman; K. E. Gubbins, Phase equilibria of associating fluids spherical moleculeswith multiple bonding sites, Mol. Phys., 65 (1988) 1–31.
Acknowledgements:
E2S UPPA hub Newpores supported ANR (ANR-16- IDEX-0002) are acknowledged for the funding of
this project and A. Barthes PhD grant.

55

Coupling between poroelasticity and the density functional
theory for the estimation of adsorption-induced swelling in
nanoporous materials
Youssef Khaldouni1, Laurent Perrier1, Thomas Bernet2, Christelle Miqueu1 and David Grégoire1
1 Universite de Pau et de Pays de l’Adour, E2S UPPA, CNRS, LFCR, Anglet, France 2

Department of Chemical Engineering, Imperial College London, UK
Email for correspondence: david.gregoire@univ-pau.fr

Natural and synthesised porous media are generally composed of a double porosity: a microporosity
where the fluid is trapped as an adsorbed phase and a meso- or a macroporosity required to ensure
the transport of fluids to and from the smaller pores. In nanometer-scale pores, the molecules of fluid
are confined. This effect induces that fluid-fluid and fluid-solid interactions sum at the pore scale andhave significant consequences at the macroscale, such as instantaneous deformation, which are notpredicted by classical poromechanics. If adsorption in nanopores induces instantaneous deformation
at a higher scale, the matrix swelling may close the transport porosity, reducing the global
permeability of the porous system.
This contribution aims at modelling the linear poroelastic behavior of isotropic porous media
saturated with an adsorbable fluid. A poromechanical model is coupled with the molecular density
functional theory (DFT) and experimental comparisons are performed in term of excess adsorption
isotherms and induced strain in an activated carbon saturated with methane and carbon dioxide.
First, a version of non-local DFT [1] coupled with
SAFT-VR-Mie state equation is used for theestimation of the adsorption of methane (CH4) andcarbon dioxide (CO2) on an activated carbon. For
this purpose, the material is firstly characterized
by argon porosimetry at 87K to determine its poresize distribution (PSD).
Thereafter, the adsorbed quantities at the porescale are estimated for CH4 and CO2 respectively
at 303K and 318K. The upscaling is performed
through the PSD, so the adsorption isotherms are
obtained and compared to experimental
measurements [3].
Then, the classical poroelasticity theory is extended to consider the fluid confinement effects [2] atthe nanoscale based on the DFT-SAFT estimation of the global adsorption isotherm. The estimateddeformationis in good agreement with experimental measurements [3] without any fitting
parameter (see Figure 1).
References:
1. Bernet, T., Müller, E.A. and Jackson, G. (2020). J. Chem. Phys. 152 (22), 224701.
2. Perrier, L., Pijaudier-Cabot, G. and Grégoire, D. (2018). Int. J. Solids Struct. 146, 192-202.
3. Perrier, L., Plantier, F. and Grégoire, D. (2017). Rev Sci Instrum 88 (3), 035104.
Acknowledgements:
This work is partially financed by the Institut Carnot ISIFOR and the Investissement d’Avenir
French programme(ANR-16-IDEX-0002) under the framework of the E2S UPPA hub Newpores

56

Framework-dependent kinetics of adsorption-induced structuraltransition in flexible metal-organic frameworks
Shotaro Hiraide,1 Yuta Sakanaka,1 Iori Sgawara,1 Hajime Uematsu,1 Shogo Kawaguchi,2 Minoru T.
Miyahara1 and Satoshi Watanabe1
1 Department of Chemical Engineering, Kyoto University, Nishikyo, Kyoto 615-8510, Japan

2 Japan Synchrotron Radiation Research Institute, SPring-8, 1-1-1 Kouto, Sayo, Hyogo 679-5198,

Japan
Email for correspondence: hiraide@cheme.kyoto-u.ac.jp

Flexible metal–organic frameworks (MOFs) exhibit a guest-induced structural transition upon gas
adsorption, called “gate opening” or “breathing,” and are expected to be applied to gas separation
processes due to their high selectivity and stepwise change in the amount adsorbed. [1] While themechanism of the adsorption-induced structural transition has been explained by thermodynamics,[2] the kinetic nature of the structural transition has not been fully investigated. In this study, we
aimed to elucidate the dynamics of the structural transition on ELM-11 ([Cu(BF4)2(4,4’bipyridine)2]n) induced by CO2 adsorption using time-resolved in situ X-ray powder diffraction(TRXRD) measurements.
The TRXRD patterns of ELM-11 during CO2 gate opening were continuously obtained with
0.5 s exposure for each data at SPring-8, Japan. During the measurements, the CO2 pressure wasincreased with constant pressurization rates at 0.005, 0.08, 0.32, and 0.8 kPa/s, and the temperature
was controlled at 223, 248, and 273 K.
Fig. 1a shows the TRXRD patterns at 248 K and 0.80 kPa/s. All of the patterns have peaks
belonging to the closed state (cl) and/or peaks belonging to the open state (op), which indicates theabsence of an intermediate phase. Thus, the fraction
transformed α was determined from the intensity ratio of
op to cl (Fig. 1b). A detailed analysis of the measured data
revealed that the transition rate could be expressed as thedifference between the gas pressure and the gate-openingpressure (P – Pg) multiplied by the autocatalytic reaction
model ((k1α + k2)(1 – α)), which is in good agreement withthe experimental results. (solid lines in Fig. 1b). The
autocatalytic reaction model of ELM-11 was found toreflect the existence of two pathways for CO2 penetrationin the framework. Moreover, the same analysis was
conducted for CO2 breathing in MIL-53(Al) ([Al(OH)(1,4benzendicarboxylate)]n) and CO2 gate opening in CuFB([Cu(fumarate)(trans-bis(4-pyridyl)ethylene)0.5]n),revealing that their structural transition rates are modeledby first-order model and zero-order model. This result
confirmed that the adsorption kinetics of flexible MOFs ishighly dependent on their framework structure. [3]References:
1.

S. Hiraide et al., Nat. Commun. 11, 3867 (2020).

2.

F. X. Coudert et al., J. Am. Chem. Soc. 130, 14294 (2008).

3.

Y. Sakanaka et al., Nat. Commun. 14, 6862 (2023).

57

Impact of a kerogen network on the behavior of confined hydrocarbon liquids
Dmitry N. Lapshin1, Bennett D. Marshall2, Peter I. Ravikovitch2, Erich A. Muller1,*
1 Department of Chemical Engineering, Imperial College London, United Kingdom
2 ExxonMobil Research and Engineering Company, Annandale, New Jersey, United States

Email for correspondence: e.muller@imperial.ac.uk
Kerogen is an intrinsically complex, heterogeneous, and disordered material [1]. Depending on its
geological origin and maturity, the chemical composition of kerogen may vary significantly alongwith its structural properties, such as the cross-link density of the network and its intrinsic porosity[2]. Furthermore, upon hydrocarbon migration in shales, extraction, and adsorption, the cross-linked
networks dynamically change, making the experimental and modelling of this porous media very
challenging.
This work presents recent advances in utilizing molecular dynamics simulations to explore theadsorption and transport of high-pressure liquid hydrocarbons such as toluene, cyclohexane, and ndecane and their impact on the dynamic behavior of a kerogen nanostructure. Kerogen structures
are developed following a mimetic algorithm using chemically-accurate coarse-grained models. We
postulate that kerogen structures can be assembled as a combination of aliphatic and aromatic
molecular building blocks such as n-dodecane, triphenylene, benzopyrene, perylene, and coronene[3]. Combining these molecules and adopting the SAFT force field [4] for their coarse-grained models,
we generate fully cross-linked structures representative of four types of kerogens of different
maturity, including 1A, 2B, and 2D. The models are validated against available experimental data andin-silico data [3]. The developed CG models offer a unique platform for studying thermodynamic andtransport properties of hydrocarbon fluids.
This work presents recent advances in utilizing molecular dynamics simulations to explore theadsorption and transport of high-pressure liquid hydrocarbons such as toluene, cyclohexane, and ndecane and their impact on the dynamic behavior of a kerogen nanostructure. Kerogen structures
are developed following a mimetic algorithm using chemically-accurate coarse-grained models. We
postulate that kerogen structures can be assembled as a combination of aliphatic and aromatic
molecular building blocks such as n-dodecane, triphenylene, benzopyrene, perylene, and coronene[3]. Combining these molecules and adopting the SAFT force field [4] for their coarse-grained models,
we generate fully cross-linked structures representative of four types of kerogens of different
maturity, including 1A, 2B, and 2D. The models are validated against available experimental data andin-silico data [3]. The developed CG models offer a unique platform for studying thermodynamic andtransport properties of hydrocarbon fluids.
References:
1. E. Rezlerová, S. K. Jain, M. Lísal, Adsorption, Diffusion, and Transport of C1 to C3 Alkanes andCarbon Dioxide in Dual-Porosity Kerogens: Insights from Molecular Simulations, Energy Fuels, 37,
492-508, 2023.
2. D. Ertas, S. R. Kelemen, T. C. Halsey, Petroleum Expulsion Part 1. Theory of Kerogen Swelling in
Multicomponent Solvents, Energy & Fuels, 20, 295-300, 2006.
3. P. Ungerer, J. Collell, M. Yiannourakou, Molecular Modeling of the Volumetric and Thermodynamic
Properties of Kerogen: Influence of Organic Type and Maturity, Energy Fuels, 29(1), 91-105, 2015.
4. E. A. Müller and G. Jackson, Force-Field Parameters from the SAFT-γ Equation of State for Use in
Coarse-Grained Molecular Simulations, Annu. Rev. Chem. Biomolec. Eng., 5, 405-427, 2014.

58

CPM9 | REPORT OF ABSTRACTSWEDNESDAY, MAY 22, 2024

59

Structure characterization-mediated designing of novel carbonbased nanostructured materials
Katsumi Kaneko1
1Research Initiative for Supra-Materials, Shinshu University, Nagano, Japan

Email for correspondence: kkaneko@shinshu-u.ac.jp
Carbon has outstanding physical properties such as high electrical conductivity and excellent
mechanical strength and chemically and physically robustness. The nanostructured carbon such as
nanoporous carbons, single wall carbon nanotube (SWCNT) and graphenes have promisingpotentials for giving solutions to the global warming issue. This presentation introduces theimportance of structural characterization in the following four key topics.
The supercapacitors using ionic liquid (IL)s can realize very high energy density. The structureof ionic liquid, EMI-TFSI, in 0.7 nm pores of carbide-derived carbon was studied with HRMC
simulation-aided X-ray scattering. We evidenced the partial breaking of Coulombic law for theassembly structure of IL ions1.
The ambient pressure storage of high density methane in nanoporous carbons enables todevelop convenient methane cartridges irrespective of the severe difficulty2. We coated nanoporous
carbon with graphenes which have a thermally switchable valve function. The nanographene valves
open at 473 K and close at ambient temperature3. The stored methane of large amount can be stably
stored for two weeks at least.
The mechanical energy storage using multi-wall carbon nanotube was reported by Baughman
et al4. However, their stored energy is not necessarily remarkable. We prepared the SWCNT ropes
which have the gravimetric energy density (GED) of up to 2.1 MJ kg-1 exceeding by over four ordersof magnitude that of mechanical steel springs and by a factor of 3 that of advanced LIBs in addition
to the low temperature stability5.
Ultrafast-permeable graphene-wrapped crystal membranes which give an excellent separation
ability, as evidenced by marked upward-deviation from the upper bound of Robeson plot for H2/CH4.
The graphene-wrapped zeolites6 have the subnanoscale channels of < 0.4 nm in width between
graphene and their crystal faces, which induce a high selectivity.
References:1). R. Futamura, T. Iiyama, Y. Takasaki, Y. Gogotsi, M. J. Biggs, M. Salanne, J. Ségalini, P. Simon,
K.Kaneko, (2017) Nature Mater. 16, 1163-1273.
2). K. Kaneko and F. Rodriguez-Reinoso Eds. (2019) Nanoporous Materials for Gas Storage, Chaps. 2
and 3, Springer,3). S. Wang、F. Vallejos-Burgos, A. Furuse, J. P. Marco-Lozar, M. Nagae, H. Tanaka, H. Kanoh, J.
Silvestre-Albero, T. Hayashi, K. Kaneko. Nature Energy, In revision4). M. Zhang, W.Cai, Z. Wang, S. Fang, R. Zhang, H. Lu, A. E. Aliev, A. A. Zakhidov, C. Huynh, E. Gao, J.
Oh, J. H. Moon, J. W. Park, S. J. Kim, R. H. Baughman, (2023) Nature Energy, 8, 203-213.
5). S. Utsumi, S. Kumar, S. Takahashi, R. Shimodomae, T. Yamura, R. Okuda, R. Kobayashi, O.Takahashi,
S. Miyazono. P. Ahuja, A. Furuse, D. Tomanek, K. Kaneko, Nature Nanotech. In second revision.
6). R. Kukobat, M. Sakai, H. Tanaka, F. Vallejos- Burgos, C. Lastoskie, M. Matsukata, Y. Sasaki, K.
Yoshida, T. Hayashi, K. Kaneko, (2022) Sci. Adv. 8, eabl3521 (1-11).

60

Designing Macroporous-Mesoporous Adsorbents for Sustainability
Freddy Kleitz1, Aaron Brewer1, Changxia Li1, Patrick Guggenberger1 and Justyna Florek1
1Department of Functional Materials and Catalysis, Faculty of Chemistry, University of Vienna,

Währinger Strasse 42, 1090, Vienna, Austria
Email for correspondence: freddy.kleitz@univie.ac.at
Nanoporous materials offer significant advantages for application as selective sorbents, catalysts or
nanocarriers for biomedical technologies, owing to their high specific surface area and well-calibrated
pores large enough to perform reactions or processes involving adsorption and diffusion of bulky species.
Here, we discuss synthesis concepts for the design of functional nanoporous materials containing both
mesopores and macropores, that could offer interesting prospects for separation technologies. Emphasis
is placed on hierarchically-porous monolith and powder sorbents for critical materials recovery andpollutant removal.
Monolithic
macroporous-mesoporous
silicagenerally exhibits high surface area for adsorption,and silica monoliths display exceptional
adaptability, due to the range of options forfunctionalization and excellent tunability in termsof pore size, pore volume, and framework
structure. Furthermore, hierarchically-porousmonoliths have superior mass transport properties
compared to traditional particulate adsorbents.[1]This attribute permits large volumes of feedstock to
be rapidly processed through the sorbent, greatly
elevating the potential scalability of the system, circumventing issues such as pressure buildup and column
clogging. Recently, we described a way to use designed (powdered) hierarchically porous monoliths inpractical, scalable metal extraction systems. We apply the sorbents in continuous flow columns for
Scandium extraction at conditions realistic for industrial use (Fig 1).[2]Covalent organic frameworks(COFs) are also of great potential
as adsorbents owing to theirtailorable functionalities, lowdensity, and high porosity.
However,
theirintrinsicallystacked 2D structure limits thefull use of their surface forsorption, especially the internalpores. The construction ofultrathin COFs could increase theexposure of active sites to the targeted molecules in a pollutant environment. We show that an ultrathin
COF can be prepared with uniform thickness of ca. 2 nm employing graphene as the surface template [3].
The resulting hybrid aerogel with ultralow density (7.1 mg cm-3) has the ability to remove organic dyes ofdifferent sizes with high efficiency (Fig. 2). The 3D macroporous structure and well-exposed adsorption
sites permit rapid diffusion and efficient adsorption of organic pollutants, greatly contributing to an
enhanced uptake capacity.
References:
1. A. Brewer, J. Florek, F. Kleitz, A Perspective on Developing Solid-Phase Extraction Technologies for
Industrial-Scale Critical Materials Recovery, Green Chem. 24 (2022) 2752-2765.
2. A. Brewer, C. Reicher, O. Manatschal, H. Bai, K. Nakanishi,,F. Kleitz, Powdered Hierarchically Porous
Silica Monoliths for the Selective Extraction of Scandium, ACS Sustainable Chem. & Eng. 11 (2023)
15432-15439.
3. C. Li, P. Guggenberger, S. W. Han, W. L. Ding, F. Kleitz, Ultrathin Covalent Organic Framework Anchoredon Graphene for Enhanced Organic Pollutant Removal, Angew. Chem. Int. Ed. 61 (2022), e202206564.
Acknowledgements:
The authors thank the funding support of the FWF and the University of Vienna, Austria.

61

Tuneable mesoporous silica materials for gas storage applications
via nanoconfined clathrate formation
Pegie Cool1
1Laboratory of Adsorption and Catalysis, Department of Chemistry, University of Antwerp,

Universiteitsplein 1, B-2610 Wilrijk, Belgium
Email for correspondence: pegie.cool@uantwerpen.be
The safe storage and utilisation of gases, such as hydrogen, is an ongoing research area and has thepotential to promote hydrogen as a major substitute for carbon-based fuels. Clathrates (gas hydrates)
are water-based crystal structures (ice-like) able to trap hydrogen or methane molecules in the cages
formed by the scaffold arrangements. As only water is required for the construction of the cages, theclathrates have been identified as a potential solution for safe gas storage. However, as the pure gas
clathrate still requires harsh synthesis conditions, we propose an approach which exploits theextraordinary change of the water properties when confined in a nano-space. Specifically, it will beshown that a hydrophobic mesoporous silica can act as the nano-confinement for the ice-like hydrate.
The research presented focuses on the possible surface chemistry effect of mesoporous silicas, aswell as the pore network influencing the clathrate formation, showcasing applications of CH4 and H2
gas storage.
For example, a hydrophobized SBA-15 is demonstrated to promote methane hydrate formation [1].
In comparison to as-synthesized SBA-15, hydrophobization by C8-grafting accelerates the kinetics ofmethane storage in and delivery from the hydrate. X-ray diffraction demonstrates formation of
Structure I hydrate on SBA-15 C8. At 7.0 MPa and 248 K, the water-to-hydrate conversion onhydrophobized SBA-15 C8 reaches 96% as compared to only 71% on a pristine SBA-15 sample withcomparable pore size, pore volume and surface area. Fast loading and unloading of methane on themodified silica was achieved in 19 subsequent cycles without losses in kinetics.
A Mesoporous Cellular Foam (MCF) grafted with a THF like functional group was tested for H2
hydrate formation at 7 MPa, 262-268 K under 100% pore volume saturation of 5.56 mol% THF
solution [2]. The materials exhibit rapid hydrate formation, and the THF-like functionalized MCF
material showed an excellent promoting effect on H2 storage compared to non-functionalizedmaterial MCF despite having a pore-volume ≈ 16% and 24% lower than MCF, respectively.
References:
1. E.J. Beckwée, M. Houlleberghs, R-G Ciocarlan, C. V. Chandran, S. Radhakrishnan, L. Hanssens, P.
Cool, J. Martens, E. Breynaert, G.V. Baron, J.F.M. Denayer, Structure I methane hydrate confined in C8grafted SBA-15: a highly efficient storage system enabling ultrafast methane loading and unloading,Applied Energy 353 (2024) 122120.
2. N. B. Kummamuru, G. Watson, R.-G. Ciocarlan, S.W. Verbruggen, P. Cool, P. Van Der Voort, P.
Perreault, Accelerated methane storage in clathrate hydrates using mesoporous (organo) silica
materials, Fuel 354, (2023) 129403.
Acknowledgements:
P. Cool acknowledges VLAIO for Moonshot funding (ARCLATH, nr. HBC.2019.0110, ARCLATH2, nr.
HBC.2021.0254).

62

Effect of surface chemical heterogeneity of carbon textiles on theirdetoxification activity against CWA surrogate
Marc Florent1, Paola S. Pauletto1 and Teresa J. Bandosz1
1Department of Chemistry & Biochemistry, The City College of New York ,160 Convent Ave, New

York, NY 10031 USA
Email for correspondence: tbandosz@ccny.cuny.edu
Activated carbon textiles, owing to their physical form and developed porosity might have a potential
to replace activated carbon layers in either gas masks or warfighters’ garments. In order to increase
their detoxification activity modification of surface chemistry is needed. It is well known that certain
functional groups on the carbon surface might increase the catalytic activity [1] and even can provide
photoactivity [2], leading to the oxidation of toxic compounds to less toxic species or theirdecomposition. This heteroatom catalytic activity can be also enhanced by an introduction of anadditional active phases [3].
In this work porous carbon textile swatches were first oxidized using various treatments to modify
their porosity and to create anchoring sites for an introduction of nitrogen and sulfu -containing
functional groups It is interesting that a very strong level of oxidation led to a complete blocking ofporosity while preserving a textile morphology and elasticity. NH3 and H2S treatments at 500 and
900 oC were applied to introduce surface groups. The low treatment temperature was expected tofunctionalize the carbon surface with N and S groups, respectively, and the high one - to dope theheteroatoms to the carbon rings, leading also to a decrease in their surface contents. The samples
were characterized by adsorption of nitrogen, thermal analysis, potentiometric titration and XPS.
The decomposition of 2-chloroethyl ethyl sulfide (CEES, > 97% purity), mustard gas surrogate, wastested by dropping 5 µL 2-chloroethyl ethyl sulfide (CEES, > 97% purity), to the center of roundshaped textile samples (0.5-in diameter), which were already placed in hermetically closed glass
vessels. The vials were closed and kept in direct light for various periods of time. Then, 2 mL ofacetonitrile (> 99% purity) was introduced through the septum and the vial was shaken to extract
the species remaining, and weakly bonded, to the surface. The extracts were analyzed by GC-MS.
The results indicated the various levels of catalytic activity which led to the decomposition of CEES
to variety of compounds. The level of catalytic activity depended on the strength of CEES interactions
with the carbon surface, affected by porosity and hydrophobicity level, on the specificity of groups,
and on the absolute amounts of catalytic centers. Overall, the introduction of S and N to the carbon
rings increased the speciation of oxidation products/decomposition efficiency, owing to theactivation of molecular oxygen by these species
References:1.

M C.O. Ania and T. J. Bandosz. Surface Chemistry of Activated Carbons and its Characterization .
In Activated Carbon Surfaces in Environmental Remediation, Bandosz, T. J. Ed. pp. 159-230.
Elsevier, Oxford, 2006
2. T.J. Bandosz, C.O. Ania. Origin and Perspectives of the Photochemical Activity of Nanoporous
Carbons. Advanced Science 2018, 5, 1800293.
3. D. A. Giannakoudakis , T J. Bandosz. Detoxification of Chemical Warfare Agents: From WWI toMultifunctional Nanocomposite Approaches, Springer 2018
Acknowledgements:
This work was supported by US DoD by grant #W911NF2310204.

63

Adsorption separation of CO2 from CH4/CO2 mixture by Low
Silica X zeolite and Recovering of Adsorption Heat for Further
Applications
Akihiko Matsumoto1, Keiichi Hasegawa1, Yuji Hasegawa1
1 Department. of Applied Chemistry and Life Science, Toyohashi University of Technology,

Tempaku cho,Toyohashi 441-8580, Japan
Email for correspondence: aki@tut.jp

Biogas produced by anaerobic fermentation of sludge contains approximately 60% of methane(CH4), and 40 % of carbon dioxide (CO2) with small impurities. The biogas has been attracting
attention as a clean energy because it is carbon neutral unlike fossil fuels. It is important to separateof CO2 from the biogas. The low-silica X zeolite (Na-LSX) is one of useful candidate to the adsorbent
because of its strong adsorption ability of CO2 by the strong interaction between the quadrupole of
CO2 and the strong electric- field gradient by cation in zeolite cavities. However, the strong
interaction brings about high heat evolution which reduces adsorption efficiency. This study focuseson the recovering of the adsorption heat by
CO2 adsorption from a model biogas of theCO2- CH4 mixture (CO2/CH4 = 2/3). The
laboratory- made heat recovering apparatus in
a flow adsorption system is applied to reduce
the temperature rise by adsorption. In thisapparatus, an adsorption tube containing NaLSX is placed in a water tank and the heat
evolved by CO2 adsorption was efficiently
conducted in water. The amount of recoveredheat was estimated by the temperature changeof water.
The adsorption isotherm of CO2 on Na-LSX at
298 K is of type II as shown in Figure 1; theadsorption uptake steely increases by 3
mmol/g at the equilibrium pressure pe of 0.8
kPa and increased linearly till pe = 55 kPa andattained 10 mmol/g. On the other hand, thezeolite scarcely adsorbs CH4. It indicates that
CO2 can be successfully separated from themixed gas by Na-LSX. The differential heat ofadsorption of CO2, Qdiff, is 55 kJ/mol at theinitial stage of adsorption and gradually
decreases with increasing the uptake by 10
mol/g since CO2 adsorption takes place fromhigh energetic sites. In this experiment, about
60 % of adsorption heat is recovered from thetemperature change of water and the CO2
uptake estimated by the breakthrough curve.

64

Separation Performance of Zeolitic-Imidazolate-FrameworkBased Membranes
Michael Tsapatsis1
1

John Hopkins University

Email for correspondence: tsapatsis@jhu.edu
Metal-organic frameworks (MOFs) hold promise as gas separation membranes due to their tunable
permeation properties enabled by the structural diversity stemming from the plethora of available
metal/organic combinations. Among MOFs, zeolitic imidazolate frameworks (ZIFs) have been studied extensively for their potential as selective separation membranes because their unique structuralproperties allow them to achieve high performance for certain important separations, like that ofpropylene from propane. Although relatively rapid progress for highly selective ZIF membranes has
been achieved, reliable and scalable thin film processing remains a challenge. In this talk, I will
discuss synthesis and post-synthesis modification methods we have been developing based on vapor
and liquid phase processing and use of electron-beam-, X-ray- and plasma-induced modifica- tions.
These methods may establish a new materials processing paradigm for thin film separation
membranes that could allow control of structure, and composition to achieve optimal separation
performance.

65Unique characterization data of graphene mesosponge
Hirotomo Nishihara1
1 Tohoku University

Email for correspondence: hirotomo.nishihara.b1@tohoku.ac.jp
Graphene MesoSponge® (GMS) is a new type of graphene-based mesoporous material synthesized
via template-directed chemical vapor deposition, followed by template removal and high-temperatureannealing at 1800 ℃1,2. GMS consists mainly of single-layer graphene walls with minimal numberof edge sites and enriched topological defects (non-hexagonal carbon rings)3. From its uniquestructure, the characterization data of GMS are distinct from other porous carbon materials, and it
makes us aware of the insight into the interpretation of common characterization techniques used
for carbon materials. In this talk, the unique properties of GMS are discussed with its extraordinary
characterization data.
X-ray diffraction (XRD) of GMS shows a weak carbon 002 and an intense 10 peaks, indicating notsignificantly stacked structures and developed graphene domain. Raman spectrum of GMS shows very
intense D-band, while exhibiting intense G- and 2D-bands, which are the characteristics of singlegraphene structures. Such XRD and Raman data indicate its “non-graphitic” structure, whereas
GMS exhibits extraordinaly oxidation resistance even better than single-walled carbon nanotubes(SWCNT)4. Moreover, the electric conductivity of GMS is higher than activated carbons and most ofcarbon blacks1. Thus, the “low crystallinity” of carbon does not directly related to its chemical
stability and conductivity, and XRD and Raman spectroscopy cannot properly evaluate these
performances of carbon materials. Is there any good method? Yes, our answer is high-sensitivity
temperature-programmed desorption (TPD) up to 1800 ℃, which can determine the number of edge
sites at a ppm-level in any sp2-based carbon materials. We found that the number of edge sites is
directly related to oxidation resistance1 as well as electrochemical stability5,6. Once the number ofedge sites is obtained, it is possible to calculate average graphene domain size which is directly
related to conductivity of carbon materials.
GMS shows unique elasticity due to its single-graphene walls7, inducing a significant degree ofadsorption-induced expansion8. We have developed home-made device which can evaluate adsorption/desorption induced by the application of mechanical force onto mechanically soft nanoporous
materials7.
References:
1. H. Nishihara et al., Adv. Funct. Mater. 26, 6418 (2016).
2. S. Sunahiro et al., J. Mater. Chem. A 9 (25), 14296 (2021).
3. W. Yu et al., Adv. Sci. 10, 2300268 (2023).
4. K. Nomura et al., Energy Environ. Sci. 12, 1542 (2019).
5. R. Tang et al., J. Mater. Chem. A 7, 7480 (2019).
6. G. B. Choi et al., Nano Lett. 20, 5885 (2020).
7. K. Nomura et al., Nat. Commun. 10, 2559 (2019).
8. H. Nishihara et al., Carbon Reports 1, 123 (2022).

66

Formation and Characterization of ZIF-8 Supraparticles and Their
Packings with Hierarchical Porosity
Satoshi Watanabe*1, Atsushi Fujiwara1, Shotaro Hiraide1, Minoru T. Miyahara1, and Nicolas Vogel2
1 Dept. of Chem. Eng., Kyoto University, Katsura, Nishikyo, Kyoto, 615-8510, Japan 2 Institute ofParticle Technology, Friedrich-Alexander-University Erlangen-Nürnberg, Haberstr. 9a, 91058
Erlangen, Germany
Email for correspondence: nabe@cheme.kyoto-u.ac.jp

Metal–organic frameworks (MOFs) are microporous adsorbents for high-throughput gas separation.
Such materials exhibit distinct adsorption characteristics owing to the flexibility of the crystal
framework in a nanoparticle, which can be different from its bulk crystal. However, for practicalapplications, such particles need to be compacted into macroscopic pellets, creating mass-transport
limitations. In this work, this problem is addressed by forming materials with structural hierarchy,
using a supraparticle-based approach. Spherical supraparticles composed of nanosized MOF
particles are fabricated by emulsion templating and they are used as the structural component
forming a macroscopic material. Zeolitic imidazolate framework- 8 (ZIF-8) particles are used as amodel system and the gas-adsorption kinetics of the hierarchical material are compared withconventional pellets without structural hierarchy. We first synthesized ZIF-8 particles with the sizeof ca. 200 nm, as building units, using a central collision type microreactor [1] and preparedZIF-8
suspension droplets by mixing an aqueous suspension with an oil phase in a microfluidic device [2],followed by the drying of droplets to form supraparticles. As shown in Fig. 1a, the microfluidic
process successfully produced monodisperse supraparticles with a diameter of ca. 40 μm composedof self-assembled nano-sized ZIF-8 particles (Fig. 1b; magnified image of a supraparticle). The
calculation of the void fraction of supraparticles based on the ZIF-8 particle concentration, droplet
size, and supraparticle size demonstrated that the supraparticles have close-packed structures.
Furthermore, it is demonstrated that a pellet packed
with supraparticles exhibits a 30 times faster
adsorption rate compared to an unstructured ZIF-8
powder pellet.
These results underline the importance of controlling
structural hierarchy to maximize the performance ofexisting materials. In the hierarchical MOFs, large
macropores between the supraparticles, smaller
macropores between individual ZIF-8 primaryparticles, and micropores inherent to the ZIF-8
framework collude to combine large surface area,
defined adsorption sites, and efficient mass transport
to enhance performance [3].
References:
1. S. Watanabe, S. Ohsaki, T. Hanafusa, K. Takada, H. Tanaka, K. Mae, M.T. Miyahara, Synthesis ofzeolitic
imidazolate framework-8 particles of controlled sizes, shapes, and gate adsorption characteristics
using a central
collision-type microreactor, Chem. Eng. J., 313 (2017) 724-733
2. N. Vogel, S. Utech, G.T. England, T. Shirman, K.R. Phillips, N. Koay, I.B. Burgess, M. Kolle, D.A.
Weitz, J.
Aizenberg, Color from hierarchy: Diverse optical properties of micron-sized spherical colloidal
assemblies, Proc.
Natl. Acad. Sci., 112 (2015) 10845-10850
3. A. Fujiwara, J. Wang, S. Hiraide, A. Gotz, M.T. Miyahara, M. Hartmann, B. Apeleo Zubiri, E. Spiecker,
N.Vogel, S. Watanabe, Fast Gas-Adsorption Kinetics in Supraparticle-Based MOF Packings with
Hierarchical Porosity, Adv. Mater., 35 (2023) e2305980

67

Functional porous physisorbent materials from phosphorite
waste: Advanced characterizations and applications
Ayalew H. Assen1, Ali Mohammed Yimer1, Youssef Belmabkhout1
1 Applied Chemistry and Engineering Research Centre of Excellence (ACER CoE), Mohammed VI

Polytechnic University (UM6P), Lot 660 - Hay Moulay Rachid, 43150 Ben Guerir, Morocco
Email for correspondence: Ayalew.assen@um6p.ma
Porous materials have sparked tremendous interest as solid sorbents for various applications due tochemical variability and tunability in building blocks, degrees of order, surface areas, pore sizes andshapes, and surface functionalities to optimize their performances. Among the industrially relevant
porous physisorbents, zeolites, mesoporous silicas, and metal-organic frameworks (MOFs) haveshown promising potential to circumvent the energy and environment-related drawbacks associatedwith the commonly employed chemical adsorbents. However, their large-scale deployment or
widespread adoption is hampered primarily by economic factors related to prohibitively expensive
precursors and a lack of green synthesis protocols with industrially feasible steps. Greening thesynthetic route for porous materials has piqued researchers’ interest as a critical step towardpractical industrial applications. In this work, we employed strategic synthesis method to transformthe main components of phosphorite waste into different classes of functional porous materials in
subsequent steps. The alumina and silica components were isolated to fabricate zeolites andmesoporous silicas while the residual metals were directed to grow MOFs in the subsequent step.
The successful assembly of the porous materials was confirmed using various characterization
techniques, including XRD, SEM-EDX, TEM, FTIR, TGA-DSC-MS, N2 adsorption at 77 K, CO2 adsorption
at different temperatures, and H2O sorption analyses. The resulting zeolites showed enhanced CO2
capture property. The obtained mesoporous silicas demonstrated to have practical applications forheavy metal capture from wastewater. One of the prepared MOFs with the optimal pore aperture size(~3.4 Å) also showed a potential for alcohol dehydration with a steep and fast moisture adsorption
profile and negligible alcohol uptake. Besides recycling waste byproducts, the approach allows the
economical production of high-value-added materials that are otherwise expensive to prepare fromcommercial-grade pure chemicals.

68Porous silica-coated magnetic nanoparticles for moleculardiagnostics of virus infection
Adriana Zelenakova1*, Eva Beňová2, Nikolas Király2, Pavol Hrubovčák1, Jaroslava Szücsová1, Luboš
Nagy1, Ján Košuth3, Vladimír Zeleňák2
1Institute of Physics, P.J. Šafárik University, Park Angelinum 9, 04001 Košice, Slovakia
2Institute of Chemistry, P.J. Šafárik University, Moyzesova 11, 04001 Košice, Slovakia
3Institute of Biology and Ecology, P.J. Šafárik University, Šrobárova 2, 04154 Košice, Slovakia

Email for correspondence: Adriana.zelenakova@rutgers.edu
Magnetic separation is one of the most efficient and rapid methods currently used for nucleic acid
isolation and was used during the COVID-19 pandemic. Magnetic nanoparticles can easily separate
viral RNA and DNA from complex clinical samples without the need for centrifugation steps andlaborious traditional organic extraction or column separation techniques. Using an external magnetic
field, nucleic acids are easily separated and recovered after binding to magnetic nanoparticles. Silicacoated MNPs are widely used to extract biological molecules, including nucleic acids. To increase theyield of nucleic acid separation, MNPs are functionalised by covalently binding various ligands andpolymers to their surface, such as amines, aldehydes, polyacrylic acid or APTES (3aminopropyltriethoxysilane).
At the beginning of the pandemic in 2019, there was a severe shortage of many reagents andconsumables, especially RNA isolation kits, required for testing for SARS-CoV-2, due to high demand
worldwide. Here, we describe the synthetic procedures for the surface functionalisation of themagnetic core of magnetic nanoparticles to assess their efficacy in isolating viral RNA in diagnostic
RT-qPCR. The core is iron oxide Fe3O4 and the shell is a porous layer of silica. The nanoparticle beads
were characterised by HRTEM, SEM, FT-IR, XRD and magnetic measurements. The quality of the
prepared nanoparticles was verified by isolation of viral RNA from tissue samples infected with
hepatitis E virus - HEV and from biofluid samples from SARS-CoV-2 positive patients. The efficiency
of RNA isolation was quantified by RT-qPCR. Our results clearly indicate the organisation of amesoporous structure on the nanoparticle surface. Due to the pores, the specific surface area SBETof amorphous silica has increased to the order of magnitude comparable to the regular mesoporous
structures SBA-15 or SBA-16. The potential benefit of this modification is straightforward. The
increased surface area provides more silane groups available to bind RNA, improving the efficiencyof the particles.
Acknowledgements:
This work was supported by the Slovak Research and Development Agency under the contracts No.
APVV-20-0512, APVV-SK-SRB-21-0056, No. APVV-20-0072, by the VEGA No. 1/0829/21 and by
support from the Team TRIANGEL at the Faculty of Science, P. J. Šafárik University in Košice. This
work was also partially supported by the Operational Programme Integrated Infrastructure, project"NANOVIR", ITMS:313011AUW7, co-funded by ERDF. The authors are also grateful to synlab slovakia
s.r.o. for support and assistance with SARS-CoV-2 analyses.

69

CPM9 | POSTER PRESENTATIONCATEGORY: CHARACTERIZATION

70

Temperature-Dependent V-Type Isotherm Models: Applied toWater Vapor Adsorption on Metal-Organic Frameworks
Cristian Cardenas1
1 IFP Energies Nouvelles

Email for correspondence: cristian.cardenas-sarabia@ifpen.fr
Metal-organic frameworks (MOFs) are highly porous materials with tunable pore characteristics,
making them attractive for applications in gas storage, separation, and catalysis [1]. Their uniqueproperties have garnered significant attention in water vapor adsorption technology, crucial for humidity control, air conditioning, and heat pump systems. The Leibniz Supercomputing Center, incollaboration with IBM, has pioneered a water-cooled supercomputer utilizing a water adsorption
heat pump (AHP) for efficient waste heat utilization [2].
This study investigates the V-type isotherms displayed by Aluminum-fumarate and CAU-10 MOFs inwater vapor adsorption, a phenomenon not extensively studied. Unlike traditional materials like activated carbon, these MOFs exhibit a distinctive “S-shape” adsorption isotherm, indicating a complex
adsorption mechanism requiring comprehensive modeling. Existing models, including the Mahle
model [3] and Weighted dual-side-Langmuir model [4], while valuable, have limitations in accurately characterizing adsorption behavior, particularly at lower and higher relative pressures.
To address this, we propose a modified Mahle equation tailored for dynamic conditions andtemperature- dependent V-type isotherms. Our model extends the range of reliable relative
pressures up to 0.8, surpassing the capabilities of established models. Utilizing this model, we
conduct dynamic simulations to gain insights into the water vapor adsorption behavior of Aluminumfumarate and CAU-10 MOFs under diverse conditions.
This study holds significant implications for the advancement of MOF-based heat pump systems,
offering a sustainable alternative to traditional refrigerant-based systems. By enhancing our understanding of MOFs’ water vapor adsorption properties and developing accurate dynamic simulation
models, this research paves the way for more energy-efficient and environmentally friendly heatpump systems. Considering the global drive for sustainable energy solutions, our findings mark a
crucial step towards the broader adoption of MOFs in vital applications such as dehumidification, airconditioning, and heat pump systems.
References:
1. X. Chen, H. Gao, Z. Tang, G. Wang, Metal-Organic Framework-based Phase Change Materials for
ThermalEnergyStorage,
Cell
Reports
PhysicalScience1 (2020)
100218.
https://doi.org/10.1016/j.xcrp.2020.100218. 2. P. Kü sgens, M. Rose, I. Senkovska, H. Frö de, A.
Henschel, S. Siegle, S. Kaskel, Characterization of metal-organic frameworks by water adsorption,
MicroporousandMesoporous
Materials
120(2009)
325–330.
https://doi.org/10.1016/j.micromeso.2008.11.020.
3. J.J. Mahle, An adsorption equilibrium model for Type 5 isotherms, Carbon 40 (2002) 2753–2759.
4. M. Hefti, L. Joss, Z. Bjelobrk, M. Mazzotti, On the potential of phase-change adsorbents for CO2
capture by temperature swing adsorption, Faraday Discuss. 192 (2016) 153–179.
https://doi.org/10.1039/c6fd00040a.

71Facile Characterization of Pore Accessibility in Metal-Organic
Framework/Polymer Composites
Trenton Tovar1
1 U.S. Army, DEVCOM Chemical Biological Center
Email for correspondence trenton.m.tovar.civ@army.mil
Metal-organic framework (MOF)/polymer composites provide the possibility of combining the desired reactive and sorptive properties of highly porous MOFs with the desired mechanical propertiesof polymers to develop novel functional materials. Both MOF and polymer chemistries are complex
leading to various degrees of material compatibility. It is desired to develop a facile measurement of
the accessibility of MOF pore space within the composite matrix. Traditionally, N2 isotherms at 77K
have been used to characterize pore space in porous materials. We found that using N2 isotherms toassess pore accessibility in MOF/polymer composites underestimates the true value. This is mostly
due to the cryogenic temperature of the measurement being below the glass transition temperatureof elastomeric polymers. However, composite synthesis and morphology also play a role in the measurement. Measuring CO2 isotherms at 0 °C was shown to be a facile, more accurate measurement ofpore accessibility in MOF/polymer composites.

72

Characterization of hydroxyl groups in zeolite defects using
advanced temperature-programmed desorption
Shunsuke Shimizu1 ,Hirotomo Nishihara 2; Ryota Osuga 3; Takeharu Yoshii 2
1 Institute of Multidisciplinary Research for Advanced Materials, Tohoku University 2 Tohoku
University
3 Hokkaido University

Emails for correspondence: osuga@cat.hokudai.ac.jp, shunsuke.shimizu.q4@dc.tohoku.ac.jp,
takeharu.yoshii.b3@tohoku.ac.jp, hirotomo.nishihara.b1@tohoku.ac.jp
Zeolites are crystalline aluminosilicates that have a wide range of applications, including solid catalysts, adsorbents, and separation membranes. In zeolites, hydroxyl groups exist in various forms,
including Brønsted acid sites (BAS),
isolated hydroxyl groups, and hydroxyl
groups in defects (Fig. 1a). Despite
their significant impact on zeolite
performance, it has been challenging toquantify and qualify each of them by
conventional FT-IR and 1H NMR
methods [1,2]. Notably, hydroxyl
groups in defects that are hydrogenbonded to each other exhibit broad
bands, making it difficult to assign clear
peaks and perform absolute quantification. In this study, we propose employing advanced
temperature-programmed desorption (TPD) heating up to 1600 °C under vacuum as a new analytical method to qualitatively and quantitatively analyze hydroxyl groups in zeolite defects. Fig. 1bshows the TPD profile of dealuminated Mordenite (DeAl) in which hydroxyl groups in defects weregenerated by partly removing aluminum in the original Mordenite. H2O desorption was observed
above 300 °C, and H2 desorption started at temperatures above 600 °C, with complete elimination of
all hydrogen by 1600 °C. The increase in the amount of OH groups due to dealumination determinedby TPD was 1882 μmol/g. Considering the amount of Al removal determined by inductively coupledplasma (ICP) analysis, 2.4 hydroxyl groups per one Al defect on average were formed. Combined with
the FT-IR results and DFT simulations, we found that pairs of hydroxyl groups forming stronghydrogen bonds in defects desorbed as H2O, while distant pairs desorbed as H2 at high temperatures.
Therefore, advanced TPD up to 1600°C allows for the qualitative and quantitative determination ofhydroxyl groups while discerning hydrogen bond strength, which is difficult with conventional analytical methods.
References:
1. J. P. Gallas, J. M. Goupil, A. Vimont, J. C. Lavalley, B. Gil, J. P. Gilson, O. Miserque, Quantification of
Water and Silanol Species on Various Silicas by Coupling IR Spectroscopy and in-Situ Thermogravimetry,
Langmuir,
25(2009)
5825-5834.
2. E. Dib, I. M. Costa, G. N. Vayssilov, H. A. Aleksandrov, S. Mintova, Complex H-bonded silanol networkin zeolites revealed by IR and NMR spectroscopy combined with DFT calculations, Journal of Material
Chemistry A, 9 (2021) 27347-27352.

73CATEGORY: EXPERIMENTAL METHODSHigh sensitivity analysis of nitrogen in carbon materials using
temperature-programmed desorption up to 2100 °C
Takeharu Yoshii1 , Ginga Nishikawa 1; Hirotomo Nishihara 1
1 Tohoku University
Emails for correspondence: ginga.nishikawa@3dc.co.jp, takeharu.yoshii.b3@tohoku.ac.jp,
hirotomo.nishihara.b1@tohoku.ac.jp
Nitrogen-doped (N-doped) carbon materials are attracting attention in various fields, such as catalysis for oxygen reduction reaction. CHN elemental analysis and XPS were conventionally used foranalysis of N species, but their measurement accuracy is about 0.1 wt%. Thus, a technique fordetailed qualitative and quantitative analysis of N species is desired. Temperature-programmed desorption (TPD) has been popularly used for the analysis of inorganic catalysts and carbon materials.
In conventional TPD, a sample is heated to typically around 1000 °C at a fixed heating rate and thedesorbed gases are detected for chemical identification as a function of temperature. However, it has
not been developed as a quantitative method for an effective determination of the N species, mainly
due to the higher thermal stability of N in carbon materials than oxygen. Herein, we pro- pose hightemperature vacuum TPD up to 2100 °C as a new high-sensitivity analytical method for N-dopedcarbons. In TPD result of N-containing mesoporous carbons, desorption of N-containing gases, NH3,
HCN, and N2, was observed in a wide temperature range of 300-1900 °C. The nitrogen content
calculated from the total amount of desorbed gas was 7.9 wt%, which is in close agreement to the
CHN analysis (8.0 wt%) and XPS analysis (8.5 wt%). Combined with the results of XPS analysis and
DFT calculations, we found that the gas emission patterns of NH3, HCN, and N2 obtained by TPD canprovide quantitative and qualitative information on the different types of N species including pyrrolicN, pyridinic N, and graphitic N. Furthermore, TPD analysis was performed on a sample with a verysmall amount of N content and showed a high quantitative accuracy of the order of 10 ppm (0.001
wt%).

74

CATEGORY: EXPERIMENTAL METHODS

Explorations of the Molecules-to-Materials Continuum
Robert Szilagyi1
1 The University of British Columbia - Okanagan
Email for correspondence: robert.szilagyi@ubc.ca
A continuum in the chemical space linking molecules and materials encompasses promising physical and chemical properties that both extremes do not and cannot display. As we consider transitioning from well-defined structures and compositions toward materials, their surfaces, and grainboundaries through nanoparticles, new chemical reactivity, catalytic properties, and unique chemical functions may hide in plain sight. We have been exploring various continuums established for aluminosilicates [1], iron-sulfur nanoparticles [2], and carbon materials [3], as representative examples
for hard, tender, and soft materials, respectively. Our ambitious effort is the bridging of acid/basechemistry of exfoliated clays nanoparticles and Fe-S clusters with rich redox chemistry toward generating organic compounds and materials. Computational molecular cluster models, as maquettes ofreactive sites of interest are being employed for studying physisorption on CH<sub>4</sub> andH<sub>2</sub> on carbon surfaces, reactivity of H<sub>2</sub>, H<sub>2</sub>S, and other smallorganic molecules with on hybrid Fe-S–clay nanoparticles. The computational work is driving theatomic-level interpretation of spectroscopic features (FTIR, EPR, XANES/EXAFS) and analytical measurements (DTG/DSC-MS). X-ray synchrotron spectroscopy offers the connection between theoretical modeling and experimental work due to mining electronic and geometric structural information
for the reactive sites, as a key technique in validating the accuracy of theory and the adequacy of thecomputational maquettes.

75

Characterization of Mycelium-Based Leather Using SorptionUltrasonic Experiments
Gunel Nabiyeva1 , Ashoka Karunarathne 2; Christopher Rasmussen 3; Naila Assem 3; Jonathan
Bauer 3; Alexei Khalizov 4; Gennady Gor 2
1 Dept. of Chemical and Materials Engineering, New Jersey Institute of Technology, Newark, NJ, USA
2 Otto H. York Department of Chemical and Materials Engineering, New Jersey Institute ofTechnology, University Heights, Newark, NJ 07102, USA

3 Bolt Threads Inc., 2261 Market Street Suite 5447, San Francisco, CA 94114, USA
4 Department of Chemistry and Environmental Science, New Jersey Institute of Technology, 323 Dr.
Martin Luther King Jr. Blvd, Newark, NJ 07102, USA

Emails for correspondence: amt74@njit.edu, gn94@njit.edu, khalizov@njit.edu,
crasmussen@boltthreads.com, gor@njit.edu
Conventional leather is a product that has been used for millennia. Unfortunately, it suffers from asignificant carbon footprint due to its livestock source and tanning (the process of converting hides
to leather). In addition, there are ethical issues regarding the consumer use of animal-derived
products [1,2]. To mitigate these issues, engineering sustainable bio-based leather substitutes has
seen increased interest in material science over the past few years. Among the bio-based materials,
mycelium, the fungal “root”of a mushroom, is one of the promising alternatives due to its tunablephysico-mechanical properties [2].
Understanding the effect of humidity on leather material properties is essential to tailoring highquality leather products. To this end, we employed a novel adsorption-ultrasonic measurement
technique [3] to investigate the effects of water sorption on the elastic properties of mycelium-based
leather materials. The ultrasonic pulse-transmission method was used to measure the wave speed
through the materials while simultaneously measuring their adsorption isotherms. The changes in
the measured longitudinal modulus during water sorption and evaporation reveal the behavior of
the elasticity of the test materials (Fig 1b). Specifically, the observed irreversible change in the longitudinal modulus during the initial branch of water sorption allows to understand better how thematerial production process and the presence of additives affect the mechanical properties of thisbio-based leather material.
References:
1. Ziegler, A. R.; Bajwa, S. G.; Holt, G. A.; McIntyre, G.; Bajwa, D. S. Evaluation of physico-mechanicalproperties of mycelium reinforced green biocomposites made from cellulosic fibers. Applied engineeringinagriculture
2016,
32,
931–938.
2. Fredricks, J. L.; Jimenez, A. M.; Grandgeorge, P.; Meidl, R.; Law, E.; Fan, J.; Roumeli, E. Hierarchi- calbiopolymer-based materials and composites. Journal of Polymer Science 2023, 1–48.
3. Ogbebor, J.; Valenza, J. J.; Ravikovitch, P. I.; Karunarathne, A.; Muraro, G.; Lebedev,M.; Gurevich, B.;
Khalizov, A. F.; Gor, G. Y. Ultrasonic Study of Water Adsorbed in Nanoporous Glasses. Phys. Rev. E
108, 2023, 024802.

76

Validation of pore size distribution from a new GCMC kernel
based on a slit-pore model with carbon surface heterogeneity
Author: Kazuyuki Nakai1
1 MicrotracBEL Corp.

Email for correspondence: kazu@microtrac-bel.com
For porous carbons, which typically have hierarchical structures, the pore size distribution (PSD) is
one of the most important characteristics and is currently evaluated by using kernel fitting methods
represented by non-local density functional theory. Herein, we present new kernels for N2 andAr adsorption at 77 K and 87 K, respectively, derived from Monte Carlo (MC) simulations based on acarbon slit-pore model that considers energetic heterogeneity due to surface roughness. The model
consists of a locally scaled Lennard–Jones (LJ) 10-4 potential and Steele’s 10-4-3 potential, and thescaling factors of the LJ 10-4 potential are assumed to follow a normal distribution that mimics theadsorption behavior on real carbon black. In contrast to our previous MC kernel based on Steele’s
10-4-3 potential, the local isotherms of the new kernel did not show a steep increase due toadsorption layer formation. Despite the improved fit for adsorption isotherms, PSDs obtained fromthe proposed kernel unfortunately show a non-negligible valley around 1 nm, which is a major
artifact of the kernel fitting approach. A careful comparison of the smooth and rough surface models
indicated that the definitive cause of the artifact lies not in the formation of monolayers, which was
believed so far, but rather in the pore-filling behavior, which provides a major clue for constructing
a completely artifact-free kernel based on molecular simulations. Finally, the PSDs of fourcommercial activated carbons were evaluated using the new kernel[3] and compared with ourprevious GCMC- based kernel[1] and QSDFT[2] in Fig.1.

77

Kinetics of Adsorption-Induced Deformation in Microporous
Materials
Authors: Andrei Kolesnikov1; Gennady Gor2

1 Department of Chemical and Materials Engineering, New Jersey Institute of Technology
2 Princeton University, NJIT

Emails for correspondence: kolesnik@njit.edu, gor@njit.edu
Adsorption of fluids in porous media causes mechanical stress which results in deformation [1,2].
This phenomenon is ubiquitous but challenging to predict quantitatively due to numerous factors(pore size and geometry, adsorbent/adsorbate combination, temperature, etc.) affecting its manifestation. Since many industrial and real-world processes occur far from thermodynamic equilibrium it
is important to consider time as one of these factors. In this work, we proposed a kinetic model ofadsorption-induced deformation in microporous materials. The model is based on the osmotic
potential [3,4], written as a functional of two variables: strain and adsorbate concentration. From thethermodynamic potential, we constructed two differential equations describing the time evolu- tionof the coupled processes - diffusion of adsorbate inside the porous media and the correspond- ing
adsorbent deformation. The kinetic equations correspond to conservative and non-conservative
cases, respectively. By solving them numerically we calculated spatial concentration and deformation profiles as well as their evolution. We obtained that at sufficiently low strain relaxation rates thedeformation process hinders the diffusion, and becomes the limiting one. On the other hand, at highstrain relaxation rates, the deformation process is defined by the local adsorbate concentration and“follows” the diffusion. We believe that the proposed model can help in the interpretation of sorption
uptakes on microporous materials, including MOFs.
References:
1. G.Y. Gor, P. Huber, N. Bernstein, Adsorption-induced deformation of nanoporous materials—A
review,
Applied
Physics
Reviews,
4(2017)
011303
2. A. L. Kolesnikov, Yu. A. Budkov, G. Y. Gor, Models of adsorption-induced deformation: orderedmaterials
andbeyond,34(2021)
063002
3. D. Bousquet, F.-X. Coudert, A. G. J. Fossati, A. V. Neimark, A. H. Fuchs, A. Boutin, Adsorption
induced transitions in soft porous crystals: An osmotic potential approach to multistability andintermediate structures, The Journal of Chemical Physics, 138 (2013) 174706
4. A. V. Neimark, F.-X. Coudert, A. Boutin, and A. H. Fuchs, Stress-Based Model for the Breathing ofMetal-Organic Frameworks, The Journal of Physical Chemistry Letters, 1 (2010) 445.

78

Sorption-Ultrasonic Characterization of Water-Filled Xerogels
Ashoka Karunarathne1,Alexei Khalizov 2; Gennady Gor 3; Gudrun Reichenauer 4; Stephan
Braxmeier 4
1 New Jersey Institute of Technology

2 Department of Chemistry and Environmental Science, New Jersey Institute of Technology, 323 Dr.
Martin LutherKing Jr. Blvd, Newark, NJ 07102, USA
3 Princeton University, NJIT

4 Center for Applied Energy Research e.V. (CAE)
Emails for correspondence: gudrun.reichenauer@cae-zerocarbon.de, stephan.braxmeier@caezerocarbon.de, amt74@njit.edu, khalizov@njit.edu, gor@njit.edu
Many studies have proven that elastic properties of fluids confined in nanopores deviate from thevalues observed in bulk [1]. Interactions between the solids (pore wall) and fluids, and poregeometry are the key factors that determine the deviation in the elasticity of nanoconfined fluids.
Therefore, experimental measurements of elastic properties of confined fluids can provide
information about the porous solids themselves. In this work, we studied the elasticity of carbon
xerogels when they are gradually saturated with water. Here, a novel adsorption-ultrasonicexperimental setup [2] was employed to measure the ultrasonic wave speeds through the watersaturated carbon xerogel sample while measuring its water sorption isotherm. The measured water
sorption isotherm follows type V isotherm [3], which describes the mechanisms of fluid adsorption
to the nanopores. Elastic moduli of the xerogel-water composite, derived from the measured
ultrasonic wave speeds, were then used to calculate the bulk modulus of the confined water using
the Gassmann theory. The resulting elastic properties differ noticeably from those measured onwater-saturated Vycor glass [2]. We found that the measured elastic properties of the water
saturated carbon xerogels are strongly affected by adsorption-induced deformation [4].
References:
1. C. D. Dobrzanski, B. Gurevich, G. Y. Gor, Elastic properties of confined fluids from molecularmodeling to ultrasonic experiments on porous solids, Applied Physics Review 8, 021317 (2021)
2. J. Ogbebor, J. J. Valenza, P. I. Ravikovitch, A. Karunarathne, G. Muraro, M. Lebedev, B. Gurevich, A. F.
Khalizov, G. Y. Gor, Ultrasonic study of water adsorbed in nanoporous glasses, Physical Review E 108,024802(2023)
3. M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing,
Physisorption of gases, with special reference to the evaluation of surface area and pore size
distribution (IUPAC Technical Report), Pure and Applied Chemistry, 87 (2015) 1051-1069
4. C. Balzer, S. Braxmeier, A. V. Neimark, Gudrun Reichenauer, Deformation of microporous car- bonduring adsorption of nitrogen, argon, carbon dioxide, and water studied by in situ dilatometry,
Langmuir 2015, 31, 12512−12519
Acknowledgements:
A. K, A. F. K. and G. Y. G. thank the support from NSF CBET-2128679 grant.

79

Assessment of the Specific Surface Area by Small-Angle X-ray
Scattering
Andreas Keilbach1 , Armin Moser 1; Heike Ehmann 1
1 Anton Paar GmbH
Emails for correspondence: armin.moser@anton-paar.com, andreas.keilbach@anton-paar.com,
heike.ehmann@anton- paar.com
The reliable measurement of the specific surface area of many modern materials –porous or nonporous –is of vital importance both in research and industry. To date, the most commonly usedmethod for the determination of the specific surface area of any material is based on the BET(Brunauer-Emmet-Teller) method that relies on the physisorption of gas molecules at the sample
surface. The BET method has a number of limitations and challenges, e. g., time-consuming sample
preparation/measurement and that the size and effective cross-section of the adsorptive moleculesthat cover the sample surface is not always known. Small-angle X-ray scattering (SAXS) has goodpotential to overcome these limitations [1].
In this contribution we will present SAXS as an alternative and complimentary approach for reliable
and fast surface area assessment and compare it to the established BET method, showing data forboth dense nanoparticle systems as well as highly porous MOF/COF structures.
References:
1. C. Schlumberger, C. Scherdel, M. Kriesten, P. Leicht, A. Keilbach, H. Ehmann, P. Kotnik, G. Reichenauer, M. Thommes, Reliable surface area determination of powders and meso/macroporous
materials: Small-angle X-ray scattering and gas physisorption, Microporous and Mesoporous Materials 329 (2022) 111554.

80

Extruding diffusion constants from your extrudates: PFG-NMR
and chromatography
Sean Mclntyre1 , Daryl Williams 2; Paola Sá enz-Cavazos 2; Paul IACOMI 1
1 Surface Measurement Systems 2 Imperial College London
Emails for correspondence: paola.saenz-cavazos17@imperial.ac.uk,
smcintyre@surfacemeasurementsystems.com, d.r.williams@imperial.ac.uk,
piacomi@surfacemeasurementsystems.com, dburnett@surfacemeasurementsystems.com
The diffusion of molecules within the confines of a materials pores remains a relatively poorly understood research area. This is despite the diffusion process playing critical role in many adsorption
phenomena such as adsorbate selectivity and uptake kinetics. As such, in this work a new model forthe analysis of diffusion constants, obtained using a chromatographic Zero-Length Column method,
is derived and utilised to accurately determine the micro and macropore diffusion of small moleculesin zeolites Na-Y and ZSM-5. In addition to bridging the gap between the NMR and ZLC diffusion
analysis techniques.
The proposed mathematical model was derived from the system mass balance, and accounted for
fluid-phase
contributions,
which
can
be
significant
inliquidsystems[1].

Fig. 1. A) Simulated diffusion curves with increasing fluid-phase hold-up, γ B) Diffusion models
fitted to experimental toluene data from zeolite Y C) A comparison of NMR and ZLC diffusion
constants.
Diffusion constants were found to increase in extrudate materials, with a larger contribution ofmacropore diffusion contributing towards the overall diffusion coefficient. This extrudate diffusion
was less affected by surface diffusion, resulting in an increased correlation with diffusion constants
obtained from Pulsed-Field Gradient NMR when compared to those obtained from more crystalline
samples.
References:
1. Sean R. McIntyre, Elwin Hunter-Sellars, Paola A. Sá enz-Cavazos, Anthony R. Houghton, Daryl R.
Williams, Novel zero-length column analysis of desorption curves for single cylindrical pellets,
Powder Technology, 416, (2023), 118207.
Acknowledgements:
Thank you to the EPRC and Imperial College London Departmental Scholarship.

81Impact of Crystal Structure on Methanol Vapor Adsorption in MFIType Zeolites: Equilibrium Isotherms and Kinetic Insights
Coset Abreu Jauregui1 ; Francisco Murilo Tavares de Luna2 ; Igor de Mesquita Figueredo2 ; Joaquı́nSilvestre- Albero1; Leandro Martins3
1 University of Alicante

2 Universidade Federal do Ceará 3 Universidade Estadual Paulista
Emails for correspondence: muriloluna.ufc@gmail.com, joaquin.silvestre@ua.es, coset.abreu@ua.es
Porous materials stand at the forefront of adsorption research, offering versatile applications in separation processes and catalysis for both fundamental research and industrial purposes. Among thenumerous applications, methanol separation through adsorption mechanisms is an interesting topic
due to the high-value accessible derivatives (purified methanol, hydrocarbons, olefins). Therefore, asa first approach, this study focused on the adsorption behavior of methanol vapor on synthesized
MFI-type zeolites. Through a meticulous characterization process, including ill-crystalized (IC), fully
crystalized (FC), and hierarchical (HZ) zeolites, we aimed to unveil the influence of material properties on methanol adsorption capacity and accessibility. Equilibrium adsorption experiments conducted at 313.15 K provided critical insights by elucidating the distinctive adsorption behavior
across the zeolite samples. The observed isotherm pattern was accurately fitted with the
Dubinin−Astakhov model. Notably, the synthesized zeolites exhibited varying adsorption capacities,
with hierarchical structures demonstrating superior methanol adsorption over fully and illcrystalized counterparts, which was also confirmed by calorimetry immersion analysis.
Furthermore, our investigation fo- cused on the kinetics of the methanol accessibility within MFItype zeolites, employing three mod- els: Elovich, Weber-Morris, and Boyd. Estimation of kinetic
parameters allowed for a comprehensive evaluation of the adsorption behavior at different loading
conditions. The findings showcased dis- tinct kinetic behavior and exposed the influence of material
composition on the adsorption kinetics, finally elucidating the methanol-vapor interaction with MFItype zeolites. Overall, there is an evi- dent and intricate interplay between material chemical
properties, adsorption capacity, and vapor accessibility. These insights emphasize the prospect ofcustomizing materials to optimize their per- formance in diverse adsorption applications.
References:
1. M. Thommes, R. Guillet-Nicolas, K.A. Cychosz, Physical Adsorption Characterization of Mesoporous Zeolites, in: Mesoporous Zeolites, John Wiley & Sons, Ltd, 2015 p.349–384.
2. F. Bisinella Scheufele, A. Nivaldo Mó denes, C.E. Borba, C. Ribeiro, F.R. Espinoza-Quiñ ones, R.
Bergamasco, N. Curvelo Pereira, Monolayer–multilayer adsorption phenomenological model: Kinetics, equilibrium and thermodynamics, Chemical Engineering Journal, 284 (2016) 1328-1341.
3. P.Y. Ramos Suzaki, M. Tombini Munaro, C. Contini Triques, S. Jaiana Kleinü bing, M.R. Fagundes
Klen, L.M. de Matos Jorge, R. Bergamasco, Biosorption of binary heavy metal systems: Phenomenological mathematical modeling, Chemical Engineering Journal, 313 (2017) 364-373.
Acknowledgements:
Authors
acknowledge
financialsupportfromMINECO(PID2019-108453GB-C21),
MCIN/AEI/10.13039/ 501100011033, Conselho Nacional de Desenvolvimento Cientı́fico e
Tecnoló gico (CNPq), and EU “NextGeneration/PRTR (Project PCI2020-111968/ERANET-M/3DPhotocat, Maria Zambrano-08).

82

Quantification of Copolymer Microstructure from Liquid
Chromatography using a Statistical Interaction Model
Christopher Rasmussen1; Yefim Brun2
1 Bolt Threads Inc.

2 International Flavors and Fragrances
Emails for correspondence: crasmussen@boltthreads.com, yefim.brun@iff.com
Copolymers have a microstructure defined by their constituent monomers’ sequence. This
microstructure can have a wide-ranging impact on its structure-function properties and is often
difficult to control during polymerization, thus is crucial to understand. Quantification of synthetic
copolymer microstructure is challenging due to the large heterogeneity of molecular species and thelimited classes of analytical instrumentation available to study high molecular weight molecules.
Polymer chromatography is an attractive technique due to its ability to capture distributed
properties, and tune separation selectivity for molecular weight (i.e. chain length) or monomer
chemistry. It is per- formed using the broad tools of high-performance liquid chromatography(HPLC), but with careful attention paid to the thermodynamics of the polymer-solvent-porous
substrate interaction. The most common application of polymer chromatography is size exclusion
chromatography (SEC), where enthalpic interactions are minimized and the resulting separation isdriven by the entropic tendency of large molecules to avoid small pores. This results in a separation
by solute size and is the standard approach to quantify a polymer’s molecular weight distribution.
Other experimental situations are possible. For example, if a solvent-substrate pair is selected toapproximately balance entropic exclusion and enthalpic adsorption, the retention effects of chain
length can be muted. This phenomenon is called the critical point of adsorption (CPA) and has beenshown to be sensitive to copolymer composition and microstructure [1]. The elution of polymers canbe modelled in these conditions with a relatively simple interaction model [2], which was extended
numerically to more complex polymers [3]. This work further extends these approaches to a realworld characterization problem: assessing and monitoring the transesterification of a novel
polyester with PET. This was accomplished by including a Markov Chain model to describe thecopolymer microstructure [4] and development of suitable chromatographic and spectrographic
conditions. We show that the degree of transesterification can be quickly and accurately assessedusing these methods. Further, we show how this approach is applicable to any copolymer system thatelutes at a CPA.
References:
1. Y. Brun; C.J. Rasmussen. Chapter 11 –Interaction Polymer Chromatography. In: S. Fanali, P.R.
Haddad, C.F. Poole, M.-L. Riekkola, editors. Liquid Chromatography (Second Edition); Elsevier, 2017p.
275–318.
2. Y. Brun; Peggy Foster. Characterization of synthetic copolymers by interaction polymer chromatography: Separation by microstructure; J. of Separation Science, 33 (2010) 3501–3510.
3. C.J. Rasmussen. Molecular Simulation of Simple Fluids and Polymers in Nanoconfinement. Doctoral dissertation, Rutgers, The State University of New Jersey. ProQuest Dissertations Publishing,2012.
4. F.P. Price. Copolymerization Mathematics and the Description of Stereoregular Polymers; J. Chem.
Phys., 36 (1962) 209–218.

83

Estimation of porous media transport properties solely based on
mercury intrusion porosimetry
David Gré goire1 , Gilles Pijaudier-Cabot 1; Fadi Khaddour 1; Lionel Ecay 1; Sara Khalil 1
1 Universite de Pau et de Pays de l’Adour, E2S UPPA, CNRS, LFCR, Anglet, France Corresponding
Email for correspondence: david.gregoire@univ-pau.fr
The relationship between the microstructure of porous media and their permeation properties is aproblem that has been addressed in many instances. Experimental measurement of intrinsic
permeability remains a challenge, especially for tight materials, and several approaches have been
proposed in the literature to directly compute the transport property of a porous medium (e.g.
network models or continuous-based upscaling). If these techniques can now be very powerful, theyremain quite computationally demanding. Other approaches, used widely in engineering
applications, rely on analytical formulas in which the input is the characterization of the pore size
distribution (PSD) of the material. Pioneering works by Kozeny (1927) have been followed by various
approaches where the PSD is first simplified, averaged or idealized to estimate the transport
properties. However, these simplifications can lead to important error in the final transport property
estimation, especially for tight material.
This contribution presents a model
capable of providing estimates of thetransport properties directly from thepore-size distribution without any
idealization. The model is based on ahierarchical assembly of capillaries withdecreasing diameter, generated randomly.
The technique yields a porous network,
which mimics the pore space measured
experimentally by mercury intrusion. The
intrinsic permeability and the evolution of
the apparent permeability with meanpressure are provided by equating Darcy’s
law and a combination of Poiseuille’s andKnudsen’s laws [1]. Gas and liquid relative
permeabilities can be also derived [2]. The
technique has the advantage of remaining
simple and engineering-oriented whileallowing accurate estimation over several
orders of magnitude of permeabilities(from 10-19 to 10-12) for very different
kind of porous materials (see Figure 1).
During the conference, new measurements
will be presented and discussed on various
synthetic and natural materials.

84

The influence of confinement effects on the thermophysicalproperties of 4-methoxyazobenzene
Timm Kraus1 ,Michael Frö ba 1
1 Universitä t Hamburg

Emails for correspondence: michael.froeba@uni-hamburg.de, timm.kraus@uni-hamburg.de
Due to global warming and the high global demand for energy, the research and development ofsustainable energy storage systems is of great interest. The photoswitchable phase change material
4-methoxy- azobenzene (4-MeO-Azo) allows simultaneous storage of two different forms of energy
which can be released after an external trigger, shown in Fig. [1]. Herein, we report the change of thethermophysical properties of 4-MeO-Azo in confinement. Mesoporous silica like SBA-15, KIT-6 andSBA-16 were impregnated with 4-MeO-Azo to investigate the influence of different pore sizes andpore shapes on the melting point of trans-4-MeO-Azo by differential scanning calorimetry (DSC). The
porous materials were impregnated with a load of 120 % of the theoretical pore volume measured
by N2-physisorption. The overload was used for internal signal calibration. So far, no crystallizationof the cis-isomer has been detected, but only a glass transition, which was not investigated due to its
weakness. In addition, the composites were irradiated for one hour with UV light (365 nm) to initiate
trans to cis isomerization. This was followed by DSC measurement to investigate the dependence ofthe thermally induced cis to trans reaction on confinement. The integral of the exothermic signal
enables the calculation of the conversion ratio. We were able to infer the following trends: (i) the
melting point of trans-4-MeO-Azo decreases with decreasing pore size, (ii) the higher the mean
curvature of the pores - from cylindrical (SBA-15) to curved cylindrical (KIT-6) to spherical (SBA-16)
with same pore width - the lower the melting point, a trend that can be explained by the GibbsThomson form factor, and (iii) the conversion ratio of the light-induced trans to cis conversion at r.t.
seems to be higher in confined space compared to 4-MeO-Azo in bulk, whereas the heat-induced backreaction seems to be unaffected by the confinement.

References:
1. Z. Zhang, Y. He, Z. Wang, J. Xu, M. Xie, P. Tao, D. Ji, K. Moth-Poulsen, T. Li, Photochemical
Phase Transitions Enable Coharvesting of Photon Energy and Ambient Heat for Energetic
Molecular Solar Thermal Batteries That Upgrade Thermal Energy, J. Am. Chem. Soc., 142(2020) 12256-12264.

85

CPM9 | POSTER PRESENTATIONCATEGORY: DATA / AI / ML86

PyCOSMOS: A Python Tool for Compartmentalization of Unit Cells
of Metal-Organic Frameworks
Shivam Parashar1 , Alexander Neimark 1
1 Department of Chemical and Biochemical Engineering, Rutgers University, New Jersey, USA
Emails for correspondence: sp1709@soe.rutgers.edu, aneimark@rutgers.edu
Metal-Organic Frameworks (MOFs) stand out as a prominent class of nanoporous materials, known
for their stability and customizable pore sizes and chemistry, particularly for gas storage and separations. Notably, certain MOFs exhibit pH sensitivity, rendering them excellent candidates for drugdelivery applications. The precise characterization of MOFs is of paramount importance for effective
design and synthesis for a given application.
Real MOF samples often deviate from ideal crystals due to presence of binders, residual solvents, andpore blockage defects. To characterize this non-ideality at the pore level, we recently introduced themethod of calculating pore accessibilities by comparing the in silico calculated fingerprint isotherms
and experimental isotherms.1 However, accurate calculation of fingerprint requires knowledge ofthe shape, size and location of the pore which can be difficult to deduce from the structure alone. In
this work, we developed a python program, pyCOSMOS, to describe the shape, size, and location of
the pores of MOFs.2 Using the pore size distribution probe particles as input, a special cluster- ing
algorithm identifies the pores of different types. Later, the unit cell is decomposed into porecompartments, and Monte Carlo simulations of gas adsorption are performed for calculating thefingerprint isotherms. The generalizability of the program is demonstrated by application to mostpractical MOFs like Cu-BTC, IRMOF-1, UiO-66, PCN-224, ZIF-412, as well as various structures fromthe CoRE MOF database.
Acknowledgements:
This work is supported by the NSF CBET grant 1834339.
References:
1. Parashar, S.; Zhu, Q.; Dantas, S.; Neimark, A. V., Monte Carlo Simulations of Nanopore Compartmentalization Yield Fingerprint Adsorption Isotherms as a Rationale for Advanced Structure Characterization of Metal–Organic Frameworks. ACS Applied Nano Materials 2021, 4 (5), 5531-5540.
2. Parashar, S; Neimark, A.V.; Pore Structure Compartmentalization for Advanced Characterization ofMetal-Organic Framework Materials. Theo. & Comp. Chem. ChemRxiv. 2023.

87Modelling Kerogen Flexibility in Response to Hydrocarbon
Adsorption using Hybrid Molecular Dynamics/Monte Carlo
Shivam Parashar1 , Alexander Neimark 1, Peter I. Ravikovitch 2
1 Department of Chemical and Biochemical Engineering, Rutgers University, New Jersey, USA
2 ExxonMobil Research and Engineering Company
Emails for correspondence: peter.ravikovitch@exxonmobil.com, sp1709@soe.rutgers.edu,
aneimark@rutgers.edu
Shale gas reservoirs plays a pivotal role in natural gas production in the United States. Organic partof shale is both a source and reservoir of hydrocarbons. Kerogen, an insoluble organic part of shale,
exhibits an amorphous structure, and its composition and mechanical properties depend on the levelof maturity. It has been shown the kerogen matrix swells upon gas adsorption. It is critical tounderstand the structure and adsorption characteristics of organic porosity found in kerogen. Thisknowledge is crucial for predicting the storage capacities of oil and gas, as well as enhancing
hydrocarbon recovery.
To begin, we create three-dimensional molecular models of microporous kerogen matrix of type IIA with the same density and pore size distribution as an experimental sample. We also create slit
pores of different sizes using the equilibrated kerogen matrix.1 We study adsorption of CH4, CO2,
and octane in flexible kerogen matrix and slit pores. To incorporate the effect of adsorption stressexerted by the gas molecules on kerogen matrix, we use the hybrid molecular dynamics/Monte Carloapproach. This involves multiple cycles of grand canonical Monte Carlo simulations and molecular
dynamics in NPT ensemble until the convergence in the number of particles and unit cell volume isachieved. Through our hybrid approach, the study aims to gain a deep understanding of deformationof kerogen upon hydrocarbon adsorption. This holds significant implications for advancing
techniques for hydrocarbon recovery from shale reservoirs.
Acknowledgements:
This work is supported by the NSF CBET grant 1834339 and ExxonMobil.
References:
1. Parashar, S; Ravikovitch P.I.; Neimark, A.V. Molecular Modeling and Adsorption Characterizationof Micro-Mesoporous Kerogen Nanostructures. Energy & Fuels. 2022.

88

Characterization of Nanoporous Carbons Using Generative Models
Lucas J. Santos1; Elvis do A. Soares1; Amaro Gomes Barreto Jr.1; Frederico Wanderley Tavares1
1 Universidade Federal do Rio de Janeiro

Emails for correspondence: elvis.asoares@gmail.com, lucasjs@eq.ufrj.br, amaro@eq.ufrj.br,
tavares@eq.ufrj.br
Traditional methods of characterization of nanoporous carbons are based on the use of a simulated
kernel of isotherms obtained by classical density functional theory (cDFT) in a series of independent
slit or cylindrical pore models to compute the pore size distribution. This approach cannot describe
the structure’s asymmetry, a feature characteristic of these materials. Vallejos et al. [1] used 3D
carbon structure models to generate kernels in recent work. They found relative contributions ofthese structures in experimental isotherms, calculating morphological parameters of the experimental sample and plausible simulated (Transmission Electron Microscopy) TEM images. In this work,
we try to predict molecular structures of real materials from a set of experimental data (adsorption
properties and images from TEM) using score-based diffusion models. The score-based diffusion
model is a deep generative model that has achieved state-of-the-art sample quality in several tasks,
including image generation by Computed Tomography (CT) and Magnetic Resonance Imaging (MRI).
In this approach, we perturb data with a sequence of noise distributions and generate samples bylearning to reverse this path from noise to data. The framework of score-based diffusion models involves gradually diffusing the data distribution towards a given noise distribution using a stochastic
differential equation (SDE) and learning the time reversal of this SDE for sample generation. Crucially, the reverse-time SDE has a closed-form expression that depends solely on a time-dependent
gradient field, called the score, of the perturbed data distribution. This gradient field can be efficiently
estimated by training a neural network from a score-based model with a weighted combination ofscore-matching losses as the objective. The coupling of adsorption properties and images from TEM
with score-based generative models to solve the inverse problems related to the reconstruction of
the porous material structure has enormous potential for broadly impacting the porous material
characterization area.
References:
1. F. Vallejos-Burgos, C. de Tomas, N. J. Corrente, K. Urita, S. Wang, C. Urita, I. Moriguchi et al. 3Dnanostructure prediction of porous carbons via gas adsorption. Carbon, 215 (2023) 118431
2. Y. Song, C. Durkan, I. Murray, S. Ermon. Maximum likelihood training of score-based diffusion
models. Advances in Neural Information Processing Systems, 34 (2021) 1415-1428
3. Y. Song, L. Shen, L. Xing, S. Ermon. Solving inverse problems in medical imaging with score-based
generativemodels.
arXiv
preprint
arXiv:2111.08005(2021)
4. Y. Song, J. Sohl-Dickstein, D. P. Kingma, A. Kumar, S. Ermon, B. Poole. Score-based generativemodeling through stochastic differential equations. arXiv preprint arXiv:2011.13456 (2020).
Acknowledgments:
The authors thank Petrobras and Shell, which provided financial support through the Research, Development, and Innovation Investment Clause in collaboration with the Brazilian National Agency ofPetroleum, Natural Gas, and Biofuels (ANP, Brazil). Additionally, this research was partially fundedby CNPq, CAPES, and FAPERJ.

89

CPM9 | POSTER PRESENTATIONCATEGORY: EXPERIMENTAL METHODS90

A Novel Method for Obtaining Carbon Molecular Sieves for N2/O2
Separation
Koki Urita1 ,Kaito Marubayashi 1; Miyu Hamasaki 1; Hideki Tanaka 2; Takashi Ishida 3; Yasuyuki
Yamane 3; Jin Miyawaki 4; HIroo Notohara 1; Isamu Moriguchi 1
1 Nagasaki University 2 Shinshu University 3 OGC
4 Kyushu University

Email for correspondence: urita@nagasaki-u.ac.jp
The use of oxygen-enriched air with high oxygen concentration is expected to reduce fuel consumption in industrial furnaces. The pressure swing adsorption method was used for the air separation.
However, temperature swing adsorption (TSA) using combustion exhaust heat is expected to savemore energy. To achieve highly efficient air separation by introducing TSA, a molecular sieve adsorbent whose pore entrance diameter is optimized for preferential adsorption of oxygen is required[1]. Because the electrochemical oxidation (ECO) process adds oxygen-containing functional groups(OCFGs) to carbon materials [2], ECO can be expected to narrow the pore entrance. ECO is usually
performed using block carbon electrodes obtained by mixing with a binder. On the other hand, a flowtype ECO is operated by pumping the suspension into the electric field using a suspension of theelectrolyte and carbon materials. In this study, we examined the conditions for the addition of OCFG
to porous carbons by flow-type ECO and aimed to create a molecular sieving carbon withoxygen/nitrogen selectivity. XPS analysis indicated that the oxygen content on the carbon surface
was increased by ECO, and the addition of OCFGs to the porous carbon surface is possible in the flowtype ECO method even though the carbon electrode is not fixed on a current collector. Oxy- gen
adsorption isotherms at 20 °C and 80 °C showed that effective oxygen adsorption was decreased in
the ECO-treated samples. The decrease in the adsorbed amount should stem from partial poreocclusion and pore size reduction by the addition of OCFGs to the pores. However, by compar- ing
the adsorption time required to reach the adsorbed amount to half the equilibrium adsorption
amount before and after ECO treatment, it was found that the adsorption rate of nitrogen was significantly reduced by the ECO treatment. These results suggest that the addition of OCFGs to the poreentrance of porous carbon by ECO is effective for the fabrication of carbon molecular sieves foroxygen/nitrogen separation.

91

INFRAsorp & MULTIport Rapid surface analysis by optical
calorimetry
Stefan Kaskel1 , Felix Spranger 2
1 Fraunhofer IWS; TU Dresden
2 Fraunhofer IWS

Emails for correspondence: stefan.kaskel@iws.fraunhofer.de, felix.spranger@iws.fraunhofer.de
The assessment of specific surface area and adsorption properties in advanced functional materials
is a key task for the characterization of porous materials such as activated carbons, porous polymers,
metal-organic frameworks, zeolites, nanoparticles and catalysts. The characterization of porous materials by nitrogen Physisorption at 77 K and gravimetric methods is widely used. However, a major
drawback of the methods is that a significant amount of time is required for a single experiment.
Especially in time critical applications like delivery- or production control or for material screening
applications, a fast characterization method would be desirable.
For this particular application, we introduce the approach of optical adsorption calorimetry. It measures the time-resolved temperature change (thermal response) of a porous sample, which occurs
during adsorption of a test gas due to the release of heat of adsorption [1,2]. The magnitude of temperature change depends on the heat capacity of the material, the number of adsorbed molecules;
the amount of heat released by each molecule, the speed of adsorption as well the heat transfer properties (convection, conduction, radiation) within the sample and the optical calorimeter.
The INFRAsorp is the optical calorimeter tool for a high throughput adsorption screening, developed
by Fraunhofer IWS. Additionally, the advanced MULTIport device is available. It enables automatic
measurements of up to 12 samples and different adsorptives. It is suited for various test gases like nbutane, VOCs, CO2, H2S and H2O among others [3]. Other advantages of the technique are the small
sample size (< 30 mg), that no cooling or liquid nitrogen is required due to measurement at 298 K
and the small footprint and compact design of the device.
References[1] P. Wollmann, M. Leistner, U. Stoeck, R. Grü nker, K. Gedrich, N. Klein, O. Throl, W. Grä hlert, I.
Senkovska, F. Dreisbach and S. Kaskel, “High-throughput screening: speeding up porous materials
discovery,”Chemical communications (Cambridge, England), vol. 47, no. 18, pp. 5151-5153, 2011. [2]P. Wollmann, M. Leistner, W. Grä hlert, O. Throl, F. Dreisbach and S. Kaskel, “Infrasorb: Opticaldetection of the heat of adsorption for high throughput adsorption screening of porous solids,”Microporous and Mesoporous Materials, vol. 149, no. 1, pp. 86-94, 2012.
[3] M. Wö llner, N. Klein and S. Kaskel, “Measuring water adsorption processes of metal-organic
frameworks for heat pump applications via optical calorimetry,”Microporous and Mesoporous Materials, vol. 278, pp. 206-211, 2019.

92Unique dissolution/precipitation phenomena in microspaceinduced by physisorption
Takeru Yokoyama1; Taku Iiyama2; Ryusuke Futamura2; Takahiro Ueda3; Yuka Matsuda4
1 Faculty of Science, Shinshu University 3-1-1 Asahi, Matsumoto, Nagano 390-8621, Japan 2
Shinshu University
3 Osaka Universty

4 Osaka gas chemical
Emails for correspondence: 22ss315a@shinshu-u.ac.jp, ueda@chem.sci.osaka-u.ac.jp,
ryu_f@shinshu-u.ac.jp
In this study, we used mesoporous silica MCM-41 as the vessel of the micro-solution, dibenzyl as
solute, and water and diethyl ether as solvents. The water adsorption isotherm of dibenzyl preadsorbed MCM-41 (MCM-Dib) shows a new type of isotherm shape which not classified by IUPAC.
The water adsorption amount is independent of the amount of dibenzyl (φ_Dib) and agreed with thepore capacity of a raw MCM-41. We confirmed by DSC, wide-angle X-ray scattering and NMR
measurement that the precipitation of dibenzyl occurs outside of the pores at second step of thewater isotherm. In this micro-solution system, opposite to the bulk, the solute precipitates as theamount of solvent increases. In the case of diethyl ether, the adsorption amount increased specificallyat high relative pressure, reaching 3.5 times that of a raw porous solid. This increase in adsorption is
attributed to the formation of the new solution phase on the outside of the pores. These results
indicate that the combination of dibenzyl and water, which is insoluble in the bulk, is soluble in thepore. The micro-solution formed in the pores is promising as a new reaction field, and their uniquereverse dissolution and precipitation behavior is expected to be used for drug delivery and otherapplications.

93

Reference Isotherms for Water Vapor Sorption on Nanoporous
Carbon: Results of an Interlaboratory Study
Huong Giang Nguyen1; Blaza Toman1; Roger van Zee1; Matthias Thommes2
1 National Institute of Standards and Technology

2 Friedrich-Alexander-University Erlangen-Nü rnberg
Emails for correspondence: huong.nguyen@nist.gov, roger.vanzee@nist.gov, blaza.toman@nist.gov
The ubiquitous nature of water makes understanding its effects on the chemical structure andproper- ties of materials important to the development, processing, and applications of materials
associated with food production, pharmaceuticals, construction, separation processes, sorbentbased industries, and emerging water sorption applications such as water harvesting and thermalenergy storage.
A water vapor sorption isotherm is a measure of water content as a function of relative pressure(P/P0) for pure water measurements or relative humidity (RH), when water is entrained in anothergas. With the large number of isotherms generated by automated instrumentation, there is an increasing need for standardized measurement protocols, reference materials, and reference data. The
National Institute of Standards and Technology (NIST) initiated a program to develop referencemate- rials, reference data, and measurement protocols to improve adsorption metrology. The NIST
Facility for Adsorbent Characterization and Testing (FACT Lab) recently led an interlaboratory study(ILS) to develop reference water vapor isotherms.
This ILS, sponsored by the Versailles Project on Advanced Materials and Standards (VAMAS), investigated water vapor sorption on a pelletized nanoporous carbon at 25 °C as a function of relative
pressure (P/P0) for pure water measurements and relative humidity, when a carrier gas is used. The
sorbent used in this study is a certified reference material (CRM) with a high BET specific surface
area produced by the German Federal Institute for Materials Research and Testing (Bundesanstaltfü r Materialforschung und prü fung or BAM) and is known as BAM-P109. This study examines both
static and dynamic measurements at sub-atmospheric and atmospheric pressures, because the saturation pressure of water at 25 °C is only 3.17 kPa. This study is the first ILS to report reference data
for a vapor sorption isotherm using a CRM. Thirteen laboratories participated in the study and contributed nine pure water vapor isotherms and four relative humidity isotherms, using nitrogen as
the carrier gas. From these data, were reference isotherms, along with the 95% uncertainty interval(Uk=2), were determined and are reported.

94

Small-angle neutron scattering reveals high-density adsorbedhydrogen in carbon micropores at low pressures andsupercritical temperature
Sebastian Stock1, Malina Seyffertitz ; Nikolaos Kostoglou ; Max Valentin Rauscher ; Bruno Demé ;Christian Mitterer; Osakr Paris
1 Montanuniversitä t Leoben, Chair of Physics
Emails for correspondence: christian.mitterer@unileoben.ac.at, max.rauscher@unileoben.ac.at,
sebastian.stock@unileoben.ac.at, nikolaos.kostoglou@unileoben.ac.at, deme@ill.fr,
malina.seyffertitz@unileoben.ac.at, oskar.paris@unileoben.ac.at
This study reports on the low-pressure supercritical Hydrogen (H2) and Deuterium (D2) adsorption
in a nanoporous activated carbon cloth, investigated by small-angle neutron scattering (SANS) to
elucidate pore size dependent adsorbate densification [1]. The changes of the SANS signal resulting
from the physisorption of adsorbate molecules in the pore space are described by analytical porescattering functions resembling slit-like pores. Based on a hierarchical pore model, we are able toquantify the pore-size-dependent physical density of the confined gas for three pore classes, resembling roughly the IUPAC classes of ultramicropores, supermicropores, and mesopores. Within thevery smallest pores, we find the adsorbate density of both, H2 and D2, approaching the bulk solid
density of the adsorbate for pressures of about 1 bar at 77 K, while the adsorbate density remains
much lower for larger pores. The implications of these results for the design of optimized carbons for
low pressure / high temperature hydrogen adsorption are discussed. Moreover, the limitations of
the approach and possible ways of overcoming them are also critically reviewed.

95

Scalable Continuous Flow Hydrogenation Using Structured
Catalyst Reactor
Authors: Andrea Adamo1; James Mannino2; John Holcombe2; Lorenzo Milani1; Steve Stark2;
Vladimiros Nikolakis2
1 Zaiput Flow Technologies

2 W.L. Gore & Associates Inc.

Email for correspondence: vnikolak@wlgore.com
In this talk we present a scalable solution for continuous heterogeneous catalysis, such as hydrogenation reactions. First, we discuss the Gore Structured Catalyst, a 3-dimensional PTFE mesh-based
structure embedded with particles of supported catalyst. This 3-dimensional structure has tunableproperties, such as porosity and catalyst loading, thus allowing for the construction of a structurewith good catalyst mass loading at a low resistance to flow. We discuss then a new modular andscalable reactor design conceived to take full advantage of the Structured Catalyst substrates. We
present design principles, scalability arguments, and experimental results with a model hydrogenation reaction. This case study highlights high catalyst utilization, tight temperature control, operation under high pressure, moderate pressure drop, quick scalability of the process, and no loss ofcatalyst material.

96

Solid-State Hydrogen Storage: Advancements in Nanoporous
Materials and Neutron Scattering Techniques
Authors: Haihua WangNone; Mi Tian1; Oana GhitaNone; Valeska Ting2; Xiayi HuNone
1 University of Exeter

2 The Australian National University
Emails for correspondence: m.tian@exeter.ac.uk, o.ghita@exeter.ac.uk, v.ting@bristol.ac.uk,
whh@sust.edu.cn, xi- ayihu@xtu.edu.cn
Hydrogen, lauded for its potential as a clean energy carrier, occupies a pivotal position in the quest
for sustainable energy solutions. Yet, the challenges tied to its safe and efficient storage persist, rendering conventional methods less suitable due to inherent safety risks and high operating pressures.
An innovative avenue emerges in solid-state storage within nanoporous materials, which promises
significantly enhanced storage densities and improved safety margins.
In this context, we present recent and ongoing research aimed at developing a robust solid-state hydrogen storage system using in situ neutron scattering [1, 2]. This cutting-edge approach has allowed
us to provide physical evidence of solidified hydrogen confined in the optimal porous structure. Advanced in situ neutron scattering techniques have been instrumental in this discovery, illuminating
the mechanisms at play within the porous materials.
Furthermore, based on the insights derived from this theoretical study, we have engineered porouscomposites with augmented hydrogen storage performance [3]. The marriage of theory and practicalapplication in this research underscores the potential for solid-state hydrogen storage, opening new
pathways toward realizing a more efficient and secure hydrogen energy landscape.

97Microscopic understanding of stability andadsorption/separation of CO2 from flue gas by MOFs in realindustrial conditions
M. Wahiduzzama1 ,P. Lyu 1; N. Heymans 2; N. Garcia-Moncada 3; G. Mouchaham 4; M. Daturi 3; G.
De Weireld 2; C. Serre 4; Sabine Devautour-Vinot 5; G. Maurin 1
1 ICGM, University of Montpellier, CNRS, France
2 University of Mons, Belgium

3 ENSICAEN, University of Caen, France

4 IMAP, ENS, ESPCI Paris, CNRS, PSL University, France 5 ICGM CNRS/ENSCM/UM
In light of the current environmental situation, reduction of anthropogenic CO2 emissions fromcarbon-intensive industries like power plants, cement, steel, or petrochemical industries become oneof the most pressing issues to combat global warming. Shifting towards a low-carbon economy requires cost-effective carbon capture utilization or sequestration (CCUS) technology to be developed.
Currently utilized amine-based absorption-regeneration process suffers from high energy penalties
for solvent regeneration. In this regard, adsorption-based processes are considered promising alternatives for CCUS. Metal-organic frameworks (MOFs) are a widely studied class of porous adsorbents
that offer tremendous potential, owing to their large CO2 adsorption capacity and/or high CO2 affinity. However, the performances of MOF-based CCUS technologies have not been fully evaluated inreal industrial conditions. For example, the industrial flue gas contains CO2, N2, H2O, and traces ofother contaminants, such as H2S, SO2, and NOx, which compete for different adsorption sites ormight impact the stability of the adsorbent materials. Therefore, it is crucial to understand thecompetitive adsorption of the various components of the flue gas. From an experimental standpoint,
such study is tedious and time consuming while molecular simulations provide a quicker route tounderstand their adsorption behavior and plausible degradation at the microscopic level. In thispresentation, I will outline a systematic joint computational/experimental approach to evaluate thestability and CO2 capture performance of a series of MOFs in the presence of various impurities
within the framework of MOF4AIR, a multidisciplinary H2020 EU project. A more detailed analy- siswill be provided for a few top-tier MOFs that were selected for large-scale deployment in theindustrial post-combustion capture process.
Acknowledgement:This project has received funding from the European Union’s Horizon 2020 research and innovation
programme under grant agreement No. 831975 (MOF4AIR project).

98Understanding wetting and drying of nanoporous media throughoptical and dilatometry experiments
Juan Sanchez1 , Laura Gallardo 1; Yannick Tetzner 1; Patrick Huber 2
1 Hamburg University of Technology (TUHH)

2 Hamburg University of Technology and Deutsches Elektronen-Synchrotron DESY
Emails for correspondence: patrick.huber@tuhh.de, juan.sanchez@tuhh.de,laura.gallardo@tuhh.de, yannick.tetzner@tuhh.de
While imbibition kinetics are well-understood in nanoporous materials [1], their drying dynamics
are still under investigation [2]. In this study, we present time-dependent macroscopic dilatometry
experiments on the deformation of nanoporous monoliths upon spontaneous, capillarity-driven infiltration of water as well as drying. During both processes, we find characteristic dynamical regimesthat can be quantitatively described in terms of Laplace pressure effects and changes in the surface
stress at the inner pore walls [3]. In the particular case of transparent nanoporous Vycor glass, additional imaging experiments are conducted, allowing direct optical access to the filling front. The
observed wetting-drying dynamics are consistent with our analysis of the strain regimes. Our study
demonstrates that it is possible to monitor the interplay of imbibition and drying dynamics by simple
dilatometry measurements, provided proper humidity control.
References:
1.
2.
3.

S. Gruener, T. Hofmann, D. Wallacher, A.V. Kityk, and P. Huber, Capillary rise of water in hydrophilic nanopores (Phys. Rev. E .), Stat. Nonlin. Soft Matter Phys., 79(6), (2009)
R. Al-Mandany, Experimental Study of Drying Process of Porous Materials (Conference
paper: YUCOMAT2018) (2018)
G.Gor,P.Huber,andN.Berrnstein.Adsorption-induceddeformationofnanoporousmaterials—
A review (Applied Physics Reviews) 4, 011303 (2017)99

CH4/H2O Competitive adsorption in Nano porous materials underclathrate hydrate formation conditions
JYOTI SHANKER PANDEY1 , Joaquin Silvestre Albero 2
1 DTU CHEMICAL ENGINEERING
2 University of Alicante

Emails for correspondence: jyshp@kt.dtu.dk, joaquin.silvestre@ua.es
In this study, we delve into the intricacies of gas adsorption behavior within nanoporous materials,
specifically focusing on the competitive adsorption of CH4 and H2O molecules under clathrate
hydrate formation conditions. We aim to elucidate how the presence of water or humidity affects thetotal gas adsorption capacity of these materials.
Under low-temperature hydrate formation conditions, water tends to transform into gas hydrate
crystals, thereby enhancing the overall gas storage capacity. However, this transformation process isfar from straightforward and is heavily influenced by the properties of the nanoporous material,
including its hydrophobicity, pore size, and surface chemistry. These material characteristics play
pivotal roles in dictating the kinetics, overall storage capacity, and thermodynamics of the hydrate
formation process.
To comprehensively examine CH4 gas storage and the competitive interactions with H2O molecules,
we conduct a series of high-pressure reactor experiments. These experiments are designed to generate gas isotherms at low temperatures (1-2°C) across varying water saturation levels. Our primary
focus is on understanding the profound impact of hydrophobicity and surface chemistry on theformation process within this hybrid system. Finally, we compare our results with those obtained
from a bulk water system to affirm the synergistic effects of nanoporous materials on gas storage
behavior.

100

Acoustic Response of Fluid Adsorption in Nanoporous Materials
Loriane Didier1, Alan Sam 2; Rodolfo Venegas 2; Benoit Coasne 1 1 CNRS/Univ. Grenoble Alpes
2 Universidad Austral de Chile (UACh), Valdivia, Chile

Emails for correspondence: alan.sam@univ-grenoble-alpes.fr, loriane.didier@univ-grenoblealpes.fr, rodolfo.venegas@uach.cl,
Email for correspondence: benoit.coasne@univ-grenoble-alpes.fr
Fluid adsorption and transport in nanoporous materials are at the heart of efficient technologies impacting our economy/ecology: energy storage/conversion, environment protection, health/humanwelfare, agribusiness/food science, etc. In particular, nanoporous solids shaped as membranes are
expected to play a leading role in the “seven key chemical separations to change the world”1 but also
to address increasingly complex problems such as bio/agropollutants removal, greenhouse gas
mitigation, drinkable water production, etc. With the goal to design efficient processes based on an
appropriate nanoporous material for a given application, the characterization of its textural andphysicochemical properties is essential to establish reliable structure/property relationships. In thiscontext, despite its generalized use in materials science, acoustics is often assumed to be unsuited fornanoporous due to their large wavelength compared to the pore size in this class of materials. Yet,
the adsorption/permeation footprint of a nanoconfined fluid is included in an average way in the signal emitted by the system subjected to fluid pressure or acoustic excitation2 (see also recent review
paper by Gor and coworkers on the elastic properties of confined fluids as probed using molecularmodeling and ultrasonic experiments) 3.
In this work, we employ molecular modeling and theoretical approaches to unravel the acoustic signature of adsorption in nanoporous materials. Different fluid models (coarse-grained versus molecular descriptions) and with different interactions (CH4 versus CO2) are studied in a prototypical
nanoporous material (zeolite) to probe pore size/interaction effects. We investigate the molecularmechanisms through which sound propagation and attenuation in nanoporous materials occur whensubjected to fluid adsorption. Both dynamic structure factors and vibrational density of states for the
fluid and solid phases are assessed to unravel the complex fluid/solid coupling at their interface andits impact on phonon modes (including their scattering which lead to sound attenuation). We will
also discuss the implication of the acoustic signature of fluid adsorption for the characterization of
nanoporous materials.
References:[1] D. Sholl, R. Lively, Nature 532, 435-437 (2016).
[2] M. Miansari, J. Friend, Advanced Functional Materials 26(43) (2016).
[3] C. D. Dobrzanski, B. Gurevich, G. Y. Gor, Appl. Phys. Rev. 8, 021317 (2021)

101

Supercritical fluid activation and in-situ adsorptionmicrocalorimetric system to directly measure the gas adsorption
amount, heat and kinetic data
Wentao Jiang1; liuliu long1 , Yue-Biao Zhang 1
1 ShanghaiTech University
Emails for correspondence: jiangwt@shanghaitech.edu.cn, zhangyb@shanghaitech.edu.cn,
liuliulong@163.com
Porous materials play a vital role in industrial and environmental systems due to their diverse applications. The adsorption capacity and associated heat during this process are crucial parameters forevaluating the performance of these materials. Achieving high sensitivity and accuracy is of utmost
importance in adsorption and microcalorimetry instruments. As a result, researchers continuously
strive to enhance the precision and repeatability of measurement results by employing various theoretical approaches to calculate the heat of adsorption.
In this work, we have designed a system for activating porous materials directly using supercriticalextraction. The system involves mixing supercritical carbon dioxide with organic solvents and directly introducing them into the sample chamber to achieve rapid and efficient activation of porous
materials with ultra-high surface area1. Additionally, we present a novel system comprising a Tian-Calvet microcalorimetry apparatus equipped with an automatic gas adsorption measuring unit or chemisorption instruments for in-situ measurement of physisorption and chemisorption heat, respectively2. To validate its feasibility and accuracy, we conducted experiments using different gases such as CH4, CO2 and C3H8. The obtained results effectively demonstrate
the instrument’s accuracy and convenience for mea- surements. Furthermore, this instrument allows
us to accurately measure the evolved energy even at extremely low adsorption capacities, commonlyreferred to as “the zero-point adsorption heat.” This valuable information sheds light on the mostactive sites within porous materials, thereby con- tributing to a better understanding of theirproperties.

References:
1. China, Design Patent, CN202011217334.6[P], Yue-Biao Zhang, Yu Tao, Zhaolin Shi, and Wentao
Jiang, Porous material supercritical extraction device and method, 2022-05-06.
2. China, Design Patent, CN 111272806 A, Liuliu Long, Fan Yang, Jun Cai, Yihua Ran, Lunjia Zhang, A
simultaneous adsorption and microcalorimetric device and method, 2020-06-12

102

Evaluation of a Commercial Chabazite-Type Zeolite Aging in the
Industrial Process of Dehydration of Natural Gas CO2-Enriched
Kalil Kashefi1 , Marcos Anacleto da Silva 2; Vera M.M. Salim 2; Frederico W. Tavares 3; NEUMAN
SOLANGE DE RESENDE 2; Amaro G. Barreto 4
1 Universidade Federal do Rio de Janeiro

2 Universidade Federal do Rio de Janeiro, PEQ

3 Universidade Federal do Rio de Janeiro, PEQ, EQ 4 Universidade Federal do Rio de Janeiro, EQ
Emails for correspondence: vera@peq.coppe.ufrj.br, ftavares@peq.coppe.ufrj.br, kalil@eq.ufrj.br,neuman@peq.coppe.ufrj.br, anacleto@peq.coppe.ufrj.br, amaro@eq.ufrj.br
In this work, a commercial zeolite, in two states of fresh and aged, is considered for investigation. The
aged sample obtained from an industrial natural gas (NG) dehydration plant was used as a reference. The effect of the aging process on the sample structure and the capability to perform theadsorption/desorption process were assessed using different characterization methods. Analyticaland spectrometry techniques such as XRF, XPS, DRIFTS, and EDS/SEM were applied for elemental
and bonding analysis, in addition to recognizing the type of carbon deposition. XRD was used to verify
any structural changes during the aging process, and N2 adsorption/desorption was employed tomeasure the specific surface and volume of the samples [1,2].
Abundant adsorption/desorption cycles for the gas dehydration process showed that the aging
mainly affected the activation of zeolite by hydrocarbon deposition. Minor changes, such as the size
and migration of cations, were detected in the structures. The TGA curves for the chabazite zeolite
used in the industrial plant showed the oxidation/burning of amorphous carbonaceous material(coke), between 250 and 400°C and the oxidation of carbonaceous material structurally organized in
the temperature range of 400-700°C. Therefore, TGA identified the presence of coke deposition on
the surface of the aged sample after use in the NG dehydration. The Temperature-programmed CO2
desorption (TPD-MS) showed significant deactivation of the adsorbent evidenced by the reduction
in CO2 adsorption from 128.8 μmols/g to 13.6 μmols/g after the adsorption and regeneration cycles
during the industrial operation of NG dehydration. The TPD-MS analysis was presented as an efficient technique to investigate the interaction of the adsorbent CO2 molecules with the solid surfaceof the studied zeolite, being an important tool for the evaluation of active surface sites. For thisreason, TPD-MS can provide crucial information for the qualification of molecular sieves for the NG
dehydration process.

103

Reference Isotherms using Reference Materials
H. Giang T. Nguyen, Blaza Tolman, Matthias Thommas & Roger D. van Zee
1

1

2

1

National Institute of Standards & Technology, Gaithersburg MD 20899 USA
Friedrich-Alexander-University Erlangen-Nürnberg, 91058 Erlangen, Germany
email for correspondence: roger.vanzee@nist.gov
1

2

Adsorbent materials have many applications, including those related to gas storage, gas
purification, catalytic reforming, and sustainable development. Despite major progress inadsorption technology and physical adsorption characterization during the past two
decades, measurement challenges still exist. For example, protocols for measuring highpressure gas adsorption isotherms on well-characterized porous materials have not beenstandardized. To address these measurement needs, the Facility for Adsorbent
Characterization and Testing (“FACT Lab”) at the National Institute of Standards andTechnology has undertaken a series of interlaboratory studies to measure and quantify
adsorption isotherms using reference materials. Reference isotherms of carbon dioxide
adsorption on ZSM-5 zeolite (NIST Reference Material 8852) have been determined,
including as a function of temperature, to 4.5 MPa [1], [2]. Additionally, a reference isotherm
for methane adsorption on zeolite y (NIST Reference Material 8850) has been determined,
to 7.5 MPa [3]. Simple, empirical functions describing these isotherms were derived, andvarious physical properties of these zeolites have been studied [4]. More recently, isotherms
for water adsorption on a nanoporous carbon (BAM Certified Reference Material P109)
have been determined to 95% relative humidity and for neat water [5].
TM

TM

References:
1. H. G. T. Nguyen et al, Adsorption, 24 (2018) 531-539.
2. H. G. T. Nguyen, B. Toman, J. Colon Martinez, D. W. Siderius & R. D. van Zee, Adsorption 28 (2022)
15-25.
3. H. G. T. Nguyen et al, Adsorption, 26 (2020) 1253-1266.
4. H. G. T. Nguyen, R. Tao, & R. D. van Zee J. Res. Natl. Inst. Stan., 126 (2021) 126047.
5. H. G. T. Nguyen et al, Adsorption, 29 (2023) 113-126.

Acknowledgements:
The FACT Lab was established through funding from the Advanced Research Project Agency•Energy
though an interagency agreement.

104

Converting Waste Tire to Activated Carbon Adsorbent Materials
for Landfill Gas Purification
Brandyn Nutter1 , Amirjavad Ahmadian Hosseini 1; Laura Rojas 1; Masoud Jahandar Lashaki 1
1 Florida Atlantic University
Emails for correspondence: bnutter2018@fau.edu, mjahandarlashaki@fau.edu,
aahmadianhos2021@fau.edu, lro- jas2021@fau.edu
Since 2013, the amount of scrap tire waste generated in the U.S. has increased by over 32%, while
the utilization of materials derived from tire waste has decreased by over 25%. This has led to anincrease in land disposal of tire waste by 123%. This trend necessitates the development of new
methods and markets for processing and recycling scrap tires. One possibility, based on thesustainability princi- ples of industrial ecology, is to use tire waste as a source of carbon, which canbe activated and used to make adsorbent materials which can be used in turn to purify landfill gas(LFG). LFG is generated when organic waste decomposes in the low-oxygen environment of a landfill.
It is an unavoidable byproduct of the landfilling of municipal solid waste (MSW), and it is rich inmethane (50-60 vol.%) and carbon dioxide (40-50 vol.%), with lower levels of hydrogen sulfide,water vapor, and siloxanes. Once purified, LFG can be used as renewable natural gas (RNG) togenerate electricity or fuel the natural gas grid. The treatment of LFG into RNG is not only beneficial
as a source of renewable energy but also benefits the environment by reducing greenhouse gas andodor emissions.
To explore the potential of using amine-modified adsorbent materials from waste tire-derived activated carbon (AC) to treat LFG, the following steps were taken. First, the waste tire was characterized
to determine its composition and to identify any potential treatment or processing required before
activation. Second, microwave heating was used to carbonize the tire in an oxygen-deficient environment, followed by converting the carbonized tire into AC. Third, N2 physisorption was used to
explore the textural and structural properties of the AC, and multiple samples were selected foramine modification. Fourth, amine-modified activated carbon (i.e., aminocarbons) were synthesizedwith various amine types and loadings. Fifth, the potential of the synthesized aminocarbons for carbon dioxide adsorption was determined in the presence of dry carbon dioxide (30 vol.% in nitrogen),with multiple performant samples being chosen for further analysis. Sixth, the potential of the performant samples from the last step was further explored in the presence of humid carbon dioxide,with multiple performant samples being shortlisted for further evaluation. Seventh, the hydrogensulfide adsorption potential of the previous performant samples was analyzed. Our preliminary results indicated that tire-derived AC materials are potential candidates to remove multiple impurities
from LFG.

105

Improving the robustness and reproducibility of gas adsorption
isotherm measurements on nanoporous materials
Author: Darren Broom1
1 Hiden Isochema Ltd

Email for correspondence: dbroom@hidenisochema.com
Gas adsorption is commonly used to characterize the surface area, pore volume and pore size distribution of porous materials, as well as to assess adsorbents for use in gas storage and separation
applications. Adsorption isotherms –plots of uptake versus pressure –can be measured using thevolumetric and gravimetric techniques, and commercial instruments are widely available for thispurpose. To determine the porous properties of materials, experimental isotherm data must then be
analyzed using one of a number of different models. Despite the widespread availability of commercial instrumentation and the associated data analysis software, published results have been subject
to irreproducibility [1-3]. This may be due to differences in the synthesis of different samples of thesame material, material instability, measurement error, or inconsistencies in the analysis of experimental data [4]. This poster addresses the last two of these sources of irreproducibility, by describing
five key steps that can be followed to make experimental gas adsorption isotherms on nanoporous
materials more robust and reproducible [5].
References:
1.
2.
3.
4.

5.

M.F.DeLange,T.J.H.Vlugt,J.Gascon,F.Kapteijn,Adsorptivecharacterizationofporoussolids:
Error analysis guides the way, Microporous and Mesoporous Materials, 200 (2014) 199-215
D. P. Broom, M. Hirscher, Irreproducibility in hydrogen storage material research, Energy &En- vironmental Science, 9 (2016) 3368-3380
J. Park, J. D. Howe, D. S. Sholl, How reproducible are isotherm measurements in metal-organic
frameworks? Chemistry of Materials, 29 (2017) 10487-10495
M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso, J. Rouquerol, K.S.W.
Sing, Physisorption of gases, with special reference to the evaluation of surface area and poresize distribution (IUPAC Technical Report), Pure and Applied Chemistry, 87 (2015) 10511069
D. P. Broom, How to make your research on gas adsorption in porous frameworks morerobust and reproducible, 2024, manuscript under review

106

CPM9 | POSTER PRESENTATIONCATEGORY: MATERIALS

107

Densification and Validation of Binderless MOF Monoliths Based
On Temperature-Pressure Swing Hydrogen Storage and Delivery
Conditions
Author: Ruthradharshini Murugavel1 Co-authors: Ali Rownaghi 2; Fateme Rezaei 1
1 Department of Chemical & Biochemical Engineering, Missouri University of Science andTechnology

2 Department of Chemistry, Cleveland State University
Emails for correspondence: rezaeif@mst.edu, rmdhp@umsystem.edu, rownaghia@mst.edu
Transitioning to a sustainable energy source is the first and most crucial step in combating climatechange. The critical bottleneck to using hydrogen (H2), an energy carrier, as a stationery and transportation fuel has been the development of materials capable of providing a viable storage capacity.
Metal-organic frameworks are a class of crystalline materials composed of metal ions or clusters
coordinated by organic ligands, structuring a highly porous material having a high surface area andporosity. Despite, having significant characteristics for practical implementation as viable materials
for H2 storage, the poor packing of powdered MOF needs to be improved based on volumetric energy
capacity. Thus, the densification of MOFs is crucial in reducing the void volume as they give way toenhanced gravimetric and volumetric storage capacities, improved kinetics, stability, and compatibility with storage tank designs. In this paper, we report the engineering of the best-performing highbulk-density monolithic MOFs in terms of their usable capacities, namely UiO-67 and MOF-177,
without binders or pressure compaction. After shaping, monolithic MOF-177 and UiO-67 stores up
to 49.95 g/L and 47 g/L at 77 K and 100 bar and deliver up to 47.02 g/L and 44 g/L operating in a
combined temperature-pressure swing (TPS) delivery conditions between 77 K/100 bar 160 K/5
bar. These findings substantially improve the deliverable capacities of the mechanically robust
densified MOFs based on onboard storage applications.

108Self-template Synthesis of Nanoporous Carbons from πconjugated Ionic Liquids with Molecular Nanocarbon
Functionalities
Ryusuke Futamura1,Toshinori Seki 1; Kento Nakamura 1; Ryuta Sekiguchi 2; Taku Iiyama 1 1
Shinshu University
2 Hirosaki University

Email for correspondence: ryu_f@shinshu-u.ac.jp
Nanoporous carbons gather much attentions as a key material for the achievement of Sustainable
Development Goals (SDGs), because of the high volumetric capacities and the molecular sieving
characters for industrially important gas molecules, like CH4 and CO2. Recently, the synthesis ofvarious types of nanoporous carbons has been reported, including top-down synthesis by activationof variety of parent carbon matrix and bottom-up synthesis by chemical vapor depositions of hydrocarbons. In particular, one can obtain distinctive nanoporous carbon materials with controlled poresizes and uniformed pore geometries from hard template synthesis methods with periodic mesoporous silica and zeolite. However, there are some problems on the template synthesis because of
the harmful mold removing process using highly corrosive agents like HF. Here, we report thepossibility of seif-template synthesis of nanoporous carbons from π-conjugated ionic liquids withmolecular nanocarbon functionalities without the harmful mold removing process.
Ionic liquids (ILs) are room-temperature molten salts which exist in a liquid state without any solvent
molecules. One of the most important characteristics of ILs is the diversity of the chem- ical
compositions and the structures because of the organic-inorganic hybrid materials. Recently, ourgroup have synthesized a new type of ILs in which π-conjugated molecular nanocarbons like
naphthalene are introduced in the cation flameworks, and we call them π-conjugated ILs. Since theπ-conjugated ILs are expected to have the both characteristics of molecular nanocarbons and of ILs,
we have clarified the relationship between the photo-luminescence properties and the domain structure formation of the naphthalene moieties of π-conjugated ILs.
Furthermore, we could succeed to synthesize a porous carbon with both meso- and micro-porosities
only by heat treatments of the π-conjugated IL without any template materials. The porosity could
be originated from the domain structure of molecular nanocarbon moieties existing in π-conjugated
ILs themselves. This fact indicates that we can precisely control the structures of porous carbon
flameworks by using variety of π-conjugated ILs as a precursor. In our presentation, we will dis- cuss
the characteristics of the porous carbon and the relationship between the porosity and themicroscopic structure of the precursor material of π-conjugated IL from hybrid reverse Monte Carlosimulation-aided X-ray scattering technique.

109

Investigating the effect of the extra-framework cation on propane/ propylene adsorption in LTA zeolites
Claessens Benjamin1,Emily Bloch 1; Gabriel Trierweiler-Conçalves 2; Gerald Chaplais 2; Jean Daou
3; Jean-Louis Paillaud 2; Mohammed-El Amine Benchaabane 4; Sandrine Bourrelly 1
1 Aix-Marseille University, CNRS

2 Université de Haute-Alsace, CNRS 3 Aptar Technologies
4 Aix-Marseille University

Email for correspondence: benjamin.claessens@univ-amu.fr
The separation of propane and propylene remains a challenging seperation process, due to the similar boiling points and size of both molecules. LTA zeolites have been shown to be promising adsorbents, but a systematic study of the effect of the extra-framework cations on propylene and propane
adsorption is lacking.
In this work, we prepared LTA zeolites exchanged with different cations (Na+, Li+, Ca2+, Mg2+, Cu2+,
Mn2+, Zn2+). All exchanged samples were synthesized with Na+ as counterion and then par- tiallyexchanged with the other cation (30% and 50%). Results were compared with a pure Si-LTA zeolite.
Adsorption isotherms were measured using a manometric system, coupled to an isothermal
microcalorimeter (Tian-Calvet type), allowing the simultaneous measurement of the released heatsof adsorption. While Si-LTA shows no preferential adsorption of propane or propylene and is essentially heterogeneous for both probe molecules, propylene shows a strong interaction with divalentcations. On the other hand, LTA zeolites with monovalent cations (Na+ / Li+) show slow diffusion of
propane, opening perspectives for a kinetic separation.

110

Carbon Dioxide Capture in NaOH-Impregnated Activated Carbon
Prapatsorn Borisut1, Atichat Wongkoblap 1 ; Chaiyot Tangsathitkulchai 1 ; Aroonsri
Nuchitprasitchai 1 ; Krittamet Phothong
1 Suranaree University of Technology
Email for correspondence: atichat@sut.ac.th
Carbon dioxide (CO2) adsorption at high pressures by alkali-impregnated activated carbons werestudied in this presentation. Four types of activated carbon were prepared with two-step activation
method and activation combined with oxidation method [1] and then impregnated in different concentration of alkali solution of 1, 4, 7 and 10%. The results of CO2 adsorption at 0 C
̊ up to saturatedpressure show that the maximum adsorption capacity was obtained from the activated carbon prepared by activation combined with oxidation method with 180 minutes of total activation time, twocycles for oxidation and 1% NaOH impregnation. The BET surface area of all activated carbons decreased with an increase in NaOH loading. Micropore volume of all activated carbons is maximum
when impregnated with 1% NaOH. It is seemed that the impregnation with appropriate NaOH loading can develop some micropore on activated carbon surface and lead to an increase in micropore
volume.

111

Metal Organic Framework Hollow Fibers for CO2 adsorption andChemical Warfare Agent Degradation
Author: John Landers1
1 Apollodyne

Email for correspondence: admin@apollodyne.com
MOFs are excellent candidates for the capture of CO2, in particular for the environmental control forlife support systems in space suits and onboard the space shuttle. Traditionally, beads of lithiumhydroxide, zeolites or polyamines have been employed for CO2 removal for the aforementioned applications. However, the use of beads can generate unfavorable large pressure drops. By employing
a high CO2 capacitance material such as MOF-74 in a novel form factor such as a hollow fiber we havefabricated a composite with a higher than conventional CO2 capacitance that also alleviates largepressure drops. Using a customizable injection molding process developed in-house, we can control
the dimensions of the hollow fiber (inner diameter, fiber wall, MOF loading) by tuning a combinationof parameters both at the macroscopic and nano scales. With the ability to fine tune fiber dimensions
and properties, the transport phenomena (CO2 vapor) through the fibers, and sub- sequently throughfiber arrays can be precisely controlled. Our approach is sub divided into three aims and are as
follows: 1) fiber dimensions can be controlled through a combination of nanoscale and macro scaleparameter tuning, 2) tuning of the fiber dimension results in difference performance for masstransfer, and 3) multiple fibers can be bundled into an array resulting in an flow through the arraythat approximates laminar flow. The fibers resulting from these aims have been charac- terized by
N2, CO2 adsorption, X-ray diffraction and diffuse reflectance infrared fourier transform spectroscopy(DRIFTS) in order to assess the structure-performance relationships of the fibers. The developmentof these metal organic framework hollow fibers have broad implications beyond filtra- tion, and may
serve as a lightweight alternative to conventional filtration media employed the across the defense,
space and healthcare industries.

112

Hydrophobic metal-organic frameworks with new fluorinatedligands
Vladimı́r Zeleň á k1 , Dá vid Princı́k 2; Adriá na Zeleň á ková 2

1 Faculty of Natural Science, Pavol Jozef Safarin University in Kosice, Slovakia
2 Faculty of Science, P. J. SŸ afá rik University, Moyzesova 11, Koš ice, Slovak Republic
Emails for correspondence: vladimir.zelenak@upjs.sk, david.princik@upjs.sk,
adriana.zelenakova@upjs.sk

The robustness and reactivity of a metal-organic frameworks depend on metal-ligand interactions,where the metal-containing clusters may be vulnerable to ligand substitution by water, leading to theframework collapse upon exposure to moist air. This instability limits the practical uses of many
MOFs. In order to further enhance the stability of the framework, many different approaches. One of
the approaches to synthesize moisture-stable MOFs is use of hydrophobic linkers. The fluorinatedMOFs are such option [1]. A novel fluorinated lanthanide-based metal-organic frameworks (Ln-FMOFs) were constructed from the deprotonated 3,3’-difluorobiphenyl-4,4’-dicarboxylic acid (H2L1)or the deprotonated 3,3’-bis(trifluoromethyl)- [1,1’-biphenyl]-4,4’-dicarboxylic acid (H2L2), see Fig.
1a [2]. Using the acids H2L1 or H2L2 and lanthanide ions, the complexes with the composition{[M2(L1 or L2)3(DMF)2]∙xDMF∙yH2O}n (M= Dy,Tb, Ho, Er, Eu for L1 and Ce, Pr, Nd, Gd, Eu for L2)
were prepared.

Fig. 1 a.) Structural formulas of acids H2L1 and H2L2. b.) Contact angle droplet test.
These complexes show high surface hydrophobicity with “rose petal effect”(see Fig. 1b), thermal
stability up to 300 °C and photoluminescence properties determined the characteristic f-f transitions
for the individual metal ions. The porosity of some activated coordination polymers was studied by
N2, CO2 and H2 adsorption isotherms. In compounds containing Pr(III), Gd(III) and Eu(III), themagnetic properties were investigated. The detailed information will be presented at the conference.
References:
1. M. Bosch, M. Zhang, H.-C. Zhou. Increasing the Stability of Metal-Organic Frameworks, Advances in
Chemistry,(2014)
18232746.
2. D. Princı́k, V. Zeleň á k, J. Bednarč ıḱ , J. Eleč ko, J. Macko, T. Zelenka, R. Gyepes, E. Dutková , Novelfluorinated MOFs with hydrophobic properties, Polyhedron, (2023) 116739.
Acknowledgements:
This work was supported by the Scientific Grant Agency of the Slovak Republic (VEGA) under Project
1/0865/21 and by the Slovak Research and Development Agency under Contract APVV-20- 0512.

113

Development of novel porous geopolymer monoliths based on
Moroccan oil shale for effective removal of heavy metals (Zn (II),Cu (II), Pb (II)) from wastewater.
said mansouri1,SANAE SBI 1; JONES ALAMI 1; HASSAN HANNACHE 1; YOUSSEF TAMRAOUI 1
1 Mohammed VI Polytechnic University, Benguerir
Email for correspondence: said.mansouri@um6p.ma
This study presents the synthesis of Porous Geopolymer Monoliths (PGMs) through the utilization of
metakaolin (MK) and oil shale (OS) as raw materials. MK contributed aluminosilicates, while OSplayed a multifaceted role, acting as a pore-forming agent upon mixing with phosphoric acid,enhancing the selectivity of geopolymers towards organic pollutants and heavy metals, and aiding inthe sustainable utilization of local natural resources. Employing experimental design method- ology,
we systematically optimized the synthesis conditions of these geopolymer monoliths, systematically investigating the influence of critical factors, including the solid-to-liquid ratio (L/S), oilshale mass percentage, and phosphoric acid molar concentration. The resulting adsorbents underwent rigorous evaluation, encompassing apparent porosity measurements and assessments of their
methylene blue adsorption capacity. Additionally, we assessed the optimal material’s performancein the removal of heavy metals from wastewater. An extensive array of characterization methodologies, such as scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area
analysis, optical microscopy, X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier-transform
infrared spectroscopy (FTIR), and UV-visible spectroscopy, was employed to comprehensively analyze the produced geopolymers. Our research findings unveiled that the highest heavy metal adsorption was achieved with monolithic geopolymers prepared under specific conditions, characterized
by L/S=1.08, OS=7.5%, and [H3PO4]=9.76M. These conditions demonstrated remarkable adsorption
metrics, with rates of 12.5 mg/g for Cu(II), 33.3 mg/g for Pb(II), and 30.30 mg/g for Zn(II), all aligningwith the expectations set by the Langmuir model.

114

Sorption of SF6 and SO2 on Modified Zeolites Materials
Katarzyna Zarębska1,Mikihiro Nomura 2; Megumi Irie 2; Jakub Szczurowski
1 Faculty of Environmental Engineering, Geomatics and Renewable Energy, Kielce University ofTechnology, 25-314 Kielce, Poland

2 Shibaura Institute of Technology, Department of Applied Chemistry

Emails for correspondence: lscathy@shibaura-it.ac.jp, mg22003@shibaura-it.ac.jp,
szczurow@agh.edu.pl, zarebska@agh.edu.pl
Information about the porous nature of adsorbents is important for understanding the pore structureof solids. Adsorption is widely used as a probe for pore structure. The measured adsorption behaviorof a sample reflects, in an aggregated manner, the adsorption behavior of individual pores. Sulfur
hexafluoride (SF6) and SO2 are industrial gases used in various applications. Compared to CO2, they
are among the most common gases whose presence is harmful in the atmosphere. Their conventional
capture methods are costly due to the energy required for phase transitions. These two gases differ
not only in their chemical nature but also in their structure, size, and shape, factors that significantly
affect transport and adsorption capacity.
In this study, the sorption of SF6 and SO2 was investigated on several selected inorganic materials.
Experimental studies of sorption isotherms at 298K showed that, for both sorbates, higher sorption
values were obtained for SO2 over the entire pressure range. Tests were conducted on samples
belonging to two material topologies: faujasite (FAU) and MFI-type frameworks, whose structuresdiffer in pore size and connectivity. This paper presents experimental data and proposes amathematical description of the sorption process. These materials behave like molecular sieves andcan be used for quite selective adsorption of the relevant gases. Furthermore, modification of thefaujasite with organic silane resulted in a drastic reduction of the sorbent’s surface area, leading tosignificantly lower sorption capacities for gases. This research is important not only for practicalapplications but also for modeling and predicting sorption processes, considering not only the effects
of molecular sieves but also the influence of surface nature and interactions with polar and non-polar
molecules.
Acknowledgements:
Funding: The project was carried out within the OPUS 2022. This research was fully funded by the
National Science Centre, Poland, grant number OPUS-22 UMO-2021/43/B/ST8/01636.

115

Trapped in the CO2 Loop: A Study of Carbon/MOF Composites for
Direct Air Capture (DAC)
Jakub Szczurowski1 , Adrian Lubecki 1; Katarzyna Zarębska 2; Patryk Bartulik 1

1 Faculty of Energy and Fuels, AGH University of Science and Technology, Al. Mickiewicza 30, 30059 Cracow, Poland; szczurow@agh.edu.pl
2 Faculty of Environmental Engineering, Geomatics and Renewable Energy, Kielce University ofTechnology, 25-314 Kielce, Poland; kzarebska@tu.kielce.pl

Emails for correspondence: pbartulik@student.agh.edu.pl, lubecki@agh.edu.pl,szczurow@agh.edu.pl, zarebska@agh.edu.pl
In response to the high demand for effective carbon dioxide (CO2) mitigation and removal strategies,
this study addresses the development and characterization of new materials - carbon/MOF (MetalOrganic Framework) composites. These materials represent a significant advance in the field of
direct air capture (DAC) technology, offering a promising avenue to address growing concerns about
elevated CO2 levels in the atmosphere. This study presents a comprehensive synthesis andcharacterization of carbon/MOF composites, tailored for efficient CO2 capture in DAC applications.
We started our research by developing a new method for synthesizing carbon/MOF composites. Thismethod focused on optimizing porosity and surface area, key factors for efficient CO2 adsorption.
The synthesized composites were then characterized to clarify their textural properties. Porosity was
mainly analyzed using argon adsorption isotherm measurements, which provided detailed insight
into the pore size distribution and surface area of the composites. The main focus of our research
was to evaluate the CO2 adsorption isotherms of these materials at different temperatures: 273K,
298K and 323K. These temperatures were chosen to simulate the range of environmental conditions
in which DAC systems can operate. CO2 adsorption isotherms at these temperatures offer a clear
picture of the CO2 capture efficiency. In addition to these measurements, we also focused on theisosteric heat of adsorption, a key parameter in assessing the energy efficiency of the adsorption process. This parameter provides insight into the strength of the interaction between CO2 molecules andthe adsorbent. Higher isosteric heat indicates stronger interactions, which may be beneficial for
initial CO2 capture, but may require more energy to regenerate. Our results showed significant
differences in adsorption capacity and isosteric heat, highlighting the temperature-dependent behavior of these materials in CO2 capture and the energy implications of their use in DAC systems. The
study not only reinforces the potential of these materials in environmental applications, but also sets
the foundation for future research to improve the performance and scalability of DAC technol- ogy a
crucial step in breaking free from the CO2 loop. Addressing scalability and cost challenges is essential
for advancing DAC technology. Research into adsorbent regeneration and durability will enhancereal-world application, paving the way for successful, efficient CO2 mitigation. Our findings
demonstrate significant advances in DAC technology, offering a hopeful outlook towards successfully
addressing the global challenge of elevated atmospheric CO2 levels.
Acknowledgements:
Funding: The project was carried out within the OPUS 2022. This research was fully funded by the
National Science Centre, Poland, grant number OPUS-22 UMO-2021/43/B/ST8/01636.

116

Applications of MOFs for the chemical warfare agents (CWAs)
simulant adsorption
Emily Bloch1 , Guillaume Maurin 2; Lotfi Boudjema 1; Sandrine Bourrelly 1
1 Aix-Marseille University - CNRS MADIREL
2 Institut Charles Gerhardt Montpellier, UMR-5253, Université de Montpellier

Emails for correspondence: emily.bloch@univ-amu.fr, sandrine.bourrelly@univ-amu.fr,
guillaume.maurin1@umontpellier.fr
Chemical warfare agents (CWAs), such as sarin and sulfur mustard, VX chemical components lead todeath with only traces of a few micrograms. The use of rapid decontamination of these compounds
under harsh conditions remains a great technological challenge. Adsorption is still considered one of
the most efficient methods that can be chosen to adsorb such compounds. Metal–Organic Frameworks (MOFs) are efficient materials for the decontamination of CWAs because of their high porosity
and tunable reactivity [1]. In this study, a serie of stable MOFs, differing in surface area/pore volume, secondary building unit (SBU) connectivity, defects, pore functionalization, and open metal sites
were examined in order to assess their adsorption performances. The simulants of CWAs have beentaken to mimic the real CWAs [2]. The adsorption microcalorimetry and the force field Monte Carlosimulation are employed to understand the adsorption behaviours of these systems.

Fig. 1. Adsorption microcalorimetry combines adsorption manometry with a Tian-Calvet
microcalorime- ter, allowing the direct measurement of adsorpion energies as a function of amountadsorbed
References:[1] Hong-Cai Zhou, Jeffrey R. Long, and Omar M. Chem. Rev. 112, 2, 673–674, 2012.
[2] C. Vieira Soares, A.A. Leitã o, G. Maurin. Microporous and Mesoporous Materials, 280, 97-104,
2019.

117

3D-printed hybrid zeolite structures constructed by a phase inversion process
Ben Sutens1 , Marleen Rombouts 1; Steven Mullens 1; Yoran De Vos 1
1 VITO

Emails for correspondence: marleen.rombouts@vito.be, steven.mullens@vito.be,ben.sutens@vito.be, yoran.devos@vito.be
Additive manufacturing is gaining increasing interest in the field of catalysis and gas separation
applications due to the geometric flexibility for a wide range of materials. However, this process
typically demands the use of a combination of organic and inorganic binders such as clays, silica oralumina to ensure mechanical integrity. As a result, these types of structures often are extremely brittle and require several post-processing steps involving thermal decomposition of the organic content
which could lead to poor adhesion between the various components. In this work, hybrid organicinorganic composites were developed using the 3D micro-extrusion technique in combination witha phase inversion process. Due to the combination of the capture efficiency of the inorganic materials and the flexibility or toughness of a polymer matrix, a non-brittle hybrid composite adsorbent
composed of a polymer skin encapsulating the uniformly distributed inorganic particles could be
developed. Moreover, the ability to eliminate the required thermal treatment in conventional binder
systems enables the direct shaping of a wide range of materials that are susceptible to oxidation or
thermal decomposition including carbon-based materials, metals and various types of metal-organic
frameworks (MOFs).
As a model case, zeolite 13X was used for H2O and CO2 adsorption while three different polymers
were compared to evaluate the effect of the polymer nature on the porosity and zeolite accessi- bility.
Extensive characterization was performed in terms of N2, Ar and Hg porosimetry as well as static
isotherm measurements and dynamic breakthrough curves. The developed polymer com- posites
were compared with a 3D-printed zeolite-clay structure and other conventional structured zeolites,
including pellets and wash coated honeycombs, to show the promising potential of this approach andthe industrial applicability.

118

Novel nanoporous composites for hydrogen storage
Alex PennetierNone; Jean-Philippe Torré None; Laurent PerrierNone; Christelle Miqueu1
1 Université de Pau et des Pays de l’Adour

Emails for correspondence: cmiqueu64@gmail.com, laurent.perrier@univ-pau.fr
Given the current environmental problems, renewable energy resources (such as photovoltaics orwind power) are now an absolute necessity. However, the intermittency of these resources in the
production of electricity is a key factor and energy storage and efficient energy conversion systems
are required. In this context, hydrogen could be used as a vector energy for renewable energy. Indeed, hydrogen can be produced by electrolysis and then the energy contained in this molecule canbe released thanks to a fuel cell. But to achieve this, the issue of hydrogen storage needs to be overcome.
Organic molecular crystals, like hydroquinone clathrates, could be promising hydrogen storage materials. Clathrates are supramolecular compounds consisting of a guest molecule (here H2) andcavity-forming host molecules. The formation of hydroquinone (HQ) clathrates with gases such as
CO2 [1] or CH4 [2] is well known in the literature. But, for hydrogen capture, some important restrictions limit the development of this material, like high pressures and low kinetics of clathrate
formation. Han et al. [3] were able to obtain a hydrogen HQ-clathrate by pre-forming a guest-freestructure, and then filling it with H2 at 350 bar. Other attempts were done to improve the storage capacity of hydroquinone clathrate, like the addition of C60 [4] but not optimal system has been foundto date. The strategy developed in this work consists in the impregnation of hydroquinone inside themicropores of a porous material in order to use the confinement effect both to initiate the formationof the confined clathrates and to improve the kinetics of enclathration. To do so, a novel method of
impregnation is developed and tested on several materials of different chemical nature (carbon,
polymer, silica) and having various pore size (between 1 and 15 nm). TGA-DSC, Argon porosimetry
and MAS-NMR are used for the characterization of the new composites. The impregnation rate oforganic crystals can reach up to 35% by mass of the hybrid material. For the case of HQ impregnatedin a porous polystyrene-based material, the formation of the HQ clathrate can be reached with cycling the temperature between 0 and 100°C. The storage capacity of the sample increases from 0.1 to
1.3 wt.% per gram of sample (or 7 wt.% per gram of HQ) of H2 in ten temperature cycles. Moreover,the system is stable at room temperature and P = 1 bar of H2 with a storage capacity of 5.7wt.% of
H2 per gram of HQ and H2 can be totally released at 100°C. Similar storage capacities are also
obtained with other materials such as MCM-41+HQ.

119

In situ pXRD monitoring of compliant MOFs under combined
mechanical and gas pressure
Paul IACOMI1; Pascal Yot2 ,Christian Serre 3; Frederico Alabarse 4; Sujing Wang 3; Guillaume
Maurin 5
1 Surface Measurement Systems
2 ICGM, Univ. Montpellier, CNRS, ENSCM, 34095 Montpellier, France
3 Institut des Maté riaux Poreux de Paris, Ecole Normale Supé rieure, ESPCI Paris, CNRS PSL
University, 75005 Paris, France

4 lettra Sincrotrone Trieste Basovizza, 34149 Trieste, Italy 5 Université Montpellier/CNRS
Emails for correspondence: piacomi@surfacemeasurementsystems.com,
dburnett@surfacemeasurementsystems.com, guillaume.maurin1@umontpellier.fr
Compliant MOFs are known to respond to external stimuli, such as pressure, temperature, and adsorbed guests by undergoing remarkable structural changes [1]. Here, the coupling of two or morestimuli presents the opportunity of tuning a process like gas separation, affording control over theun- derlying framework’s state [2]. However, structural information of materials undergoingcombined guest adsorption and mechanical pressure application has been insofar limited to closedsystem di- amond anvil cells [3].
We here detail a unique clamped diamond window cell prototype specially developed for use with
soft porous materials. For the first time, uniaxial mechanical pressure (up to 0.5 GPa) and gas dosing(up to 20 bar) were combined in an in-operando PXRD experiment, where the two stimuli can be
decoupled and independently controlled. The cell was first validated using reference materials (NaCland SiO2), followed by a study of a CO2 sorption under pressure in the metal-organic framework
MIL-53, known to undergo “breathing”compliance under both stimuli [3,4]. The cell allowed a direct
observation of MIL-53 phase existence throughout a gas-mechanical pressure space. In particular, it
was possible to obtain tentative evidence that mechanical pressure can maintain this material’s poresin a closed state throughout gas adsorption, confirming previous experimental and computational
results [2].
References[1] Z. Liu, et al., Chem. Commun., 56, 66, (2020) 9416–9432; [2] N. Chanut et al., Nat Commun, 11, 1,(2020) 1216; [3] V. Bon et al., Adv. Funct. Mater. 30, (2020) 1907847. [4] S. Bourrelly et al., JACS, 127,
39 (2005) 13519–13521; [5] P. G. Yot et al., Chem. Commun. 50, 67 (2014) 9462–9464.

120

Impact of Carbon Content in Single-Wall Carbon NanotubeTitanium Dioxide Composites Interfacial Modulation and Catalytic
Behavior
Coset Abreu Jauregui1, Antonio Sepú lveda-Escribano 1; Joaquı́n Silvestre-Albero 1
1 University of Alicante

Emails for correspondence: joaquin.silvestre@ua.es, asepul@ua.es, coset.abreu@ua.es
Advanced oxidation processes driven by natural sunlight are the key to the next generation of water treatment technologies. Photocatalysis using semiconductor materials constitutes a promising
approach to degrade organic contaminants in wastewater with minimal generation of secondary
pollutants. In this scenario, carbon-based nanomaterials have emerged as promising modifying cocatalysts. The incorporation of the carbon structure manages to enhance the photocatalytic activity
under visible light and the overall yield of the reaction. The improved behavior is attributed to theadsorption behavior associated with this type of nanostructures and the newly developed highlyextended heterojunction. More specifically, single-walled carbon nanotubes (SWCNTs) have been
anticipated as superior modifiers to enhanced the photocatalytic performance of catalysts like TiO2.
However, the characterization of the synthesized photocatalysts unveiled intriguing interfacial phenomena directly associated with the presence of important electronic effects at the interface. With
these premises, this study presents a comprehensive investigation into the effect of the quantitative
modification of commercial titanium dioxide - P25 - using four distinct ratios of single-walled carbon
nanotubes (SWCNTs) 5, 10, 20, and 30 % w/w. Physicochemical characterization revealed a porosityconstrained material with high crystallinity and well-disperse titania-carbon phases. In particu- lar,
XPS analysis suggests augmented electron-hole mobility at the carbon/oxide interface, which was
also confirmed by RAMAN spectroscopy. The photocatalytic performance was assessed for
Rhodamine-B (RhB) removal. Overall, complete degradation was achieved promptly under visiblelight exposure. These promising results are attributed to intrinsic physicochemical alterations at theformed heterojunction structures and the composite’s dual-role capability of simultaneous adsorption and photodegradation of RhB. Notably, the induced structural features are in correspondencewith the composite’s potential for improved photocatalytic performance. These findings validate ourinitial hypothesis and underscore the crucial importance of thoughtful design in synthesizing
photocatalytic materials, particularly for applications aimed at environmental remediation.
References:
1. J. Zhang, M. Vasei, Y. Sang, H. Liu, J.P. Claverie, TiO2@carbon photocatalysts: The effect of carbon thickness on catalysis, ACS Appl. Mater. Interf., 8 (2016) 1903-1912
2. P. Suyana, P. Ganguly, B.N. Nair, S.C. Pillai, U.S. Hareesh, Structural and compositional tuning in
g-C3N4 based systems for photocatalytic antibiotic degradation, Chem. Eng. J. Adv., 8 (2021) 100148
3. S.S. Ghumro, B. Lal, T. Pirzada, Visible-light-driven carbon-doped TiO2-based nanocatalysts forenhanced activity toward microbes and removal of dye, ACS Omega, 7 (2022) 4333-4341
Acknowledgements:
Authors acknowledge financial support from MINECO (PID2019-108453GB-C21) andMCIN/AEI/10.13039/501100011033 and EU “NextGeneration/PRTR (Project PCI2020111968/ERANET-M/3D-Photocat).

121

Tailoring the Adsorption Properties of Hierarchical Porous Silicasfor High-Capacity Water Sorbents
Pasquale Fulvio1 , JiaJi Lin 1; Krista Walton 1
1 Georgia Institute of Technology

Emails for correspondence: pfulvio@gatech.edu, jlin650@gatech.edu, krista.walton@gatech.edu
Hierarchical mesoporous-macroporous silica materials (HS-PEG) were prepared via a one-pot hydrothermal synthesis method using tetraethyl orthosilicate (TEOS) as the silica source, NH4OH as
condensation catalyst, and a combination of alkylammonium bromide surfactants (CnTAB) and different polyethylene glycols (PEG) as structure directing agents (SDAs). Once the SDAs were removed by calcination in air, periodic and wormhole mesopores within primary particle units, andmacropores formed by particle agglomerates were obtained. Similar to MCM materials [1], we report the control over the mesopore size using different alkyl chain lengths within 2 to 4nm range.
Moreover, the solvent system used, namely, water, and water-ethanol, also dictated the adsorption
properties of the materials. For instance, when water was the single solvent used, mesopores were
nearly 1nm larger and pore volumes were nearly double than the counterparts prepared in waterethanol. Higher ratios of NH4OH also led to higher mesopore volumes. Hygroscopic salts including
anhydrous LiCl, MgCl2, MgSO4, CaCl2, and SrCl3.6H2O and SrBr3.6H2O, were then impregnated inthese silicas by a modified incipient wetness method with pre-determined salt to silica weight ratios.
For LiCl containing composites, the water uptake increased proportionally to the LiCl target contents[2]. Moreover, composites having different pore volumes and pore widths were found to adsorb
similar amounts of water. The composites were found stable for salt loadings of up to 60wt.%. As for
Mg salts, composites did not deliquesce for loadings of less than 40wt.%. Such salts form hydrates as
MgCl2.6H2O and MgSO4.7H2O, that have larger unit cells, and cannot be dehydrated unless thermallytreated to temperatures greater than 300oC, which exceed the operation range of atmospheric water
harvesting (AWH) or of thermal energy storage (TES) devices. These results indi- cate that the freemesopore volume in the composites is required for the strong nanoconfinement of salt hydrates, andto the high-water uptakes exceeding 150wt.% at 80% relative humidity, as in case of LiCl composites.
Finally, the current synthesis method for HS-PEG represents an improvement over previously
reported monolith syntheses [2, 3] that required multiple steps. The present method yields powders
with fine distributions of sizes, and that can be easily integrated with AWH or TES devices.
References:
1. J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz, C. T. Kresge, K. D. Schmitt, C. T. Chu, D. H. Olson,
E. W. Sheppard, S. B. McCullen, J. B. Higgins, A new family of mesoporous molecular sieves preparedwith liquid crystal templates, J. Am. Chem. Soc., 114 (1992) 10834-43.
2. C Chen, J. L. Salinger, M. E. Essig, I. M. Walton, P. F. Fulvio, K. S. Walton, Hierarchical silica
composites for enhanced water adsorption at low humidity conditions, ACS App. Mater. Interfaces,
underreview.
3. J. H. Små tt, S. Schunk and M. Linden, Versatile Double-Templating Synthesis Route to Silica Monoliths Exhibiting a Multimodal Hierarchical Porosity, Chem. Mater., 15 (2003) 2354-2361.
Acknowledgements:
The authors acknowledge financial support from the DARPA Advanced Research Project Agency
Atmospheric Water Extraction Program under Grant No. HR001120S0014.

122

Quantifying Structural Rigidity in Metal–Organic Frameworks
with Increased Linker
Dimensionality Courtney Smoljan1; Omar Farha1; Randall Snurr1
1 Northwestern University

Emails for correspondence: courtney.smoljan@northwestern.edu, snurr@northwestern.edu
Given that chemical separations account for 15% of the world’s total energy consumption, it is criticalto design energy-efficient pathways for the purification of chemical mixtures.1 Membrane separations and adsorption processes are promising nonthermal alternatives to energy-intensive
separation technologies, as they separate molecules by size or chemical affinity. Metal–organic
frameworks or MOFs are some of the best materials for these applications due to their nanoporosityand high tun- ability. When tuning MOFs toward separating molecules with sub-A¤ ngstrom
differences in size, a common challenge in industrial separations, defining a MOF’s local poreenvironment is the most important factor. However, researchers typically focus on thedimensionality of the overall structure when designing MOFs, rather than considering thedimensionality effects of the linker component itself. We sought to leverage increased linker
dimensionality to achieve precise, nano-scale con- trol over a MOF’s pore size by mitigating effects ofstructural flexibility. Specifically, 3-dimensional linkers (3DLs) are sterically bulky, preventing global
breathing transitions in MOFs. Additionally, they occupy the same amount of space, regardless of
their orientation, alleviating the impact of linker rotation on pore size.2 Our groups havedemonstrated that installation of 3DLs in structures analogous to MIL-53 –a structure known for its
flexibility –results in global rigidity, allowing them to separate molecules with sub-A¤ ngstrom
differences in size, like hexane isomers and xylene iso- mers.3,4,5 Herein, we aimed to investigate
the relationship between linker bulkiness and rigidity by using variable pressure X-ray diffraction
studies to quantify each material’s bulk modulus. Addition- ally, we used density functional theory(DFT) calculations to generate electronic energy profiles for MIL-53 and its 3DL isostructural
analogues. These electronic energy profiles show energies obtained from fixed volume geometry
optimizations as a function of unit cell volume. Finally, we used DFT to derive the elastic constants ofthese materials, which were used to calculate values of Young’s moduli and to better understand thestructural dynamics of these frameworks.

123

Carbon Dioxide Capture from Flue Gas using 13X binder free
Zeolite: effect of the presence of Sulfur Dioxide
Authors: Celio Cavalcante1; Diana Azevedo1; Enrique Vilarrasa-Garcia1; Eurico Torres1; Moises
Bastos-Neto1, Rafaelle Santiago1
1 Universidade Federal do Ceara
Email for correspondence: celio@ufc.br
Carbon dioxide (CO2) capture is a subject of extensive research, particularly with Carbon Captureand Storage (CCS) methods gaining attention, notably those based on gas-solid adsorption. However,there is a notable gap in the literature concerning the impact of contaminants present in gaseous
streams, particularly sulfur and nitrogen oxides, on CO2 adsorption. This study evaluated the ef- fectof sulfur dioxide (SO2) presence in gas streams on the performance of CO2 adsorbents using acommercial Kö strolith 13X binder free (13XBF) zeolite (Chemiewerk Bad Kö stritz GmbH ,Germany),
with a magnetic suspension balance (Rubotherm, Germany) [1].
Before and after exposure to SO2, the 13XBF zeolite underwent physical and chemical characterizations. N2 adsorption/desorption isotherms at 77K revealed a decrease in the amount of adsorbed
N2 post-SO2 exposure, while the isotherm shape remained consistent, indicating a type I isotherm
according to the IUPAC classification [2]. The decrease in textural properties post-SO2 exposure wasattributed to the irreversible adsorption of sulfur species, confirmed through elemental analysis and
X-ray photoelectron spectroscopy. The S2p spectrum for 13XBF zeolite after SO2 exposure displayed
peaks corresponding to elemental sulfur and sulfate ions, whereas no sulfur species were evident on
the zeolite surface before SO2 exposure. Even at low partial pressures (0.045 bar) and constant flow,
exposure to SO2 led to irreversible adsorption, with residual SO2 adsorbed even after thermal
regeneration under typical zeolite degassing conditions (300 °C in vacuum for 10 hours). This residual SO2 caused a reduction in CO2 adsorption at 0.15 bar across the studied temperature range.
In any cyclic adsorption process, whether thermal swing adsorption (TSA) or pressure swing adsorption (PSA), it is crucial to assess the adsorbent behavior through several adsorption/desorption
cycles. After the initial SO2 exposure, a ~35% decrease in CO2 adsorption capacity was observed.
However, in subsequent adsorption/desorption cycles, the CO2 adsorption capacity remained essentially constant over 10 cycles.
References:
1. Dreisbach, F et al., Highest Pressure Adsorption Equilibria Data: Measurement with Magnetic
Suspension Balance and Analysis with a New Adsorbent/Adsorbate-Volume, Adsorption, 8 (2002),
95–109.
2. M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing,
Physisorption of gases, with special reference to the evaluation of surface area and pore size
distribution (IUPAC Technical Report), Pure and Applied Chemistry, 87 (2015) 1051-1069.
Acknowledgements:
The authors gratefully acknowledge support of RCGI/USP, sponsored by FAPESP (2014/50279-4 and2020/15230-5) and Shell Brasil, and the strategic importance of the support given by ANP (Brazil’s
National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation.

124

A Comparative Study of Physical and Chemical Modification for
Improved CO2 Capture in Fixed-Bed Adsorption
Suravit Naksusuk1
1 School of Chemical Engineering, Suranaree University of Technology
Email for correspondence: suravit@sut.ac.thAdsorption is a promising technique for CO2 capture, and improving adsorbent properties is cru- cialfor enhancing CO2 selectivity. This study compares the efficiency and differences between two
modification methods: physical treatment to increase mesopore volume and active sites, and chemical impregnation with triethylamine (TEA) for CO2 capture in a fixed-bed adsorption system. N2
isotherm analysis revealed an increase in mesopore volume for physically treated activated carbon.
Conversely, BET surface area decreased for chemically impregnated samples with increasing TEA
concentration, compared to the original activated carbon. Fixed-bed adsorption experiments demonstrated increased CO2 uptake with TEA-impregnated activated carbon, while physically treated carbon exhibited CO2 adsorption capacity similar to the original material. However, diffusivity in the
fixed bed remained constant initially, but decreased with increasing TEA concentration due to pore
blocking. Despite this, the study identified an approach for enhancing CO2 capture selectivity with acost-effective preparation method that is scalable for industrial applications and real-world CO2
capture processes.

125Analyzing the Performance of Propylamine-Grafted Mesoporous
Silica for Direct Air Capture Applications
Amirjavad Ahmadian Hosseini1 ,Laura Rojas 1; Masoud Jahandar Lashaki 1
1 Florida Atlantic University

Emails for correspondence: mjahandarlashaki@fau.edu, lrojas2021@fau.edu,
aahmadianhos2021@fau.edu
The development of adsorbent materials for CO2 capture from the atmosphere is the focus of thisstudy. There is a widespread agreement among scientists that greenhouse gases (GHGs) are responsible for trapping heat in the atmosphere. The concentration of CO2 in the atmosphere grew from
320 to 425 parts per million by volume (ppmv) between 1960 and 2024. According to NASA, this risecontributed to the 1.2 °C increase in average world temperature compared to the average of the late19th century. In 2018, the Intergovernmental Panel on Climate Change (IPCC) called for a reductionof 45% in CO2 emissions by 2030, relative to the levels in 2010, to limit the global tem- perature
increase to 1.5 °C. The Blue Map Scenario developed by the International Energy Agency (IEA)
suggests various methods to reduce CO2 emissions. These strategies include shifting to renew- ableenergy sources and putting CO2 capture technologies into action. However, most CO2 capture studies
have been focused on large point sources such as power plants that run on fossil fuels. CO2 capture
from the air, also recognized as direct air capture (DAC), has recently received increased attention.
The United States Department of Energy acknowledges the significant contribution that DAC canmake in resolving the climate challenge and moving toward the goal of reaching net-zero emissions
by the year 2050. Due to their superior performance, DAC applications involving cyclic adsorptiondesorption of CO2 by amine-functionalized silica materials (also known as “aminosilica”) havereceived great attention from both the scientific community and industry. Most relevant re- searchconcentrates on near-equilibrium CO2 adsorption while adsorbent stability and adsorption kinetics
are considered secondary factors in many studies. While the stability of aminosilicas deter- mines
their operational lifetime, it is vital to have fast adsorption kinetics to increase the amount of CO2
captured over a given time. This study aims to employ a novel approach by emphasizing ad- sorbent
stability and rapid adsorption kinetics more than adsorption uptake to create aminosilicas that arehighly effective and long-lasting in DAC applications. Aminosilicas were synthesized by utilizing
mesoporous silica that is commercially available (CARiACT G-10, Fuji Silycia). The aminefunctionalization of silica was completed via grafting instead of impregnation to enhance adsorption
kinetics and long-term stability of the adsorbent. Amine grafting was conducted using isolated
primary amines (i.e., 3-aminopropyltrimethoxysilane; APTMS). Thermogravimetric analysis (TGA)
was performed on all the materials to quantify amine loading, equilibrium CO2 uptake, amine
efficiency, and CO2 adsorption kinetics in the presence of dry CO2 (400 ppmv, balance nitrogen) at
an adsorption temperature of 25 °C. Selected performant materials were further investigatedregarding cyclic adsorption-desorption performance, long-term thermal and oxidation stability, andcolumn- breakthrough experiments in the presence of dry and humid gas streams. Our preliminary
results indicated that propylamine-grafted silica materials achieved a delicate balance between
enhancing CO2 uptake, improving adsorption kinetics, and securing thermal and oxidation stability.

126

Triamine-Grafted Mesoporous Silica Materials for CO2 Capture
from the Atmosphere
Laura Rojas1 , Amirjavad Ahmadian Hosseini 1; Masoud Jahandar Lashaki 1
1 Florida Atlantic University

Emails for correspondence: mjahandarlashaki@fau.edu, lrojas2021@fau.edu,
aahmadianhos2021@fau.edu
The concentration of CO2, the primary anthropogenic greenhouse gas (GHG) responsible for global
warming and climate change, has experienced a rapid increase since the Industrial Revolution. The
present levels of CO2 surpass any recorded in human history, indicating a global average concentration of 425 parts per million by volume (ppmv) in 2024, as opposed to 315 ppmv in 1958.
Additionally, there is a potential for it to reach 800 ppmv if multifaceted solutions are not
implemented. This in- crease in emissions has caused a nearly 2-degree Fahrenheit rise in global
temperatures since the pre-industrial era. CO2 capture from the atmosphere, also known as direct
air capture (DAC), might help us address this problem. The U.S. Department of Energy has endorsed
DAC as one of the help- ful strategies to achieve net-zero emissions by 2050. Owing to their superior
performance, DAC applications involving cyclic adsorption-desorption of CO2 by amine-modified
silica materials (i.e., “aminosilica”) have gained momentum in recent years. These technologies haveachieved significant attention because of their potential for commercialization and positiveenvironmental impact to miti- gate climate change. To that end, this project aims to develop materials
suitable for DAC applications. This research involves the synthesis of triamine-grafted silica
adsorbent materials. Triaminosilane was chosen for this purpose because it possesses two secondaryamines and one primary amine, providing a high affinity for CO2 capture. CARiACT G-10 silica (Fuji
Silysia Chemical Ltd.) was used as support for the synthesis of aminosilicas. G-10 silica iscommercially available at a low cost and has a high pore volume (1.2 cm3/g), large surface area (300m2/g), small particle size (5 μm), and wide pores (20 nm), enabling it to attain high amine loadings
and CO2 uptakes, without compromis- ing adsorption kinetics. Different materials were produced by
implementing the grafting technique and varying factors such as the amount of water and triamine
to synthesize unique samples. Using thermogravimetric analysis (TGA), the materials were screened
for equilibrium CO2 uptake, amine efficiency, and adsorption kinetics in the presence of dry CO2 (400ppmv, balance nitrogen) at 25 °C. One best-performing material with the highest CO2 uptake andfastest CO2 adsorption kinetics was chosen for rigorous 50-cycle testing under the above adsorption
conditions, followed by regen- eration at 120 °C in the presence of N2. The results indicated stableperformance as evidenced by maintaining 99% of the initial CO2 uptake throughout cycling. Using
column-breakthrough testing, the performance of the final candidate was also evaluated in thepresence of humid CO2, confirming previous reports that humidity boosts the CO2 uptake of aminemodified materials. These results suggest the high potential of aminosilicas for DAC applications.

127

CPM9 | POSTER PRESENTATIONCATEGORY: SIMULATION / THEORY

128

Molecular mechanisms of water intrusion and extrusion inhydrophobic nanopores
Abdelraheem Abdella1; Kolattukudy P. Santo1; Alexander Neimark1
1 Rutgers, The State University of New Jersey

Emails for correspondence: santotheophys@gmail.com, aneimark@rutgers.edu
Lyophobic nanoporous particle suspensions are being explored as promising materials for energy
absorption and storage. In these systems, known as nanoscale energy absorption systems (NEAS),
the non-wetting solvent intrudes into nanopores when subjected to mechanical compression,
converting and storing the impact energy that can be further released upon solvent extrusion when
the compression force is removed.1 While various NEAS have been explored experimentally, themolecular level mechanisms of the intrusion-extrusion cycles are not well-understood. Using
atomistic molecular dynamics simulations (MD), we investigate the dynamics of shock impact
induced intrusion and extrusion of water in hydrophobic cylindrical channels. MD simulations performed for nanopores of different sizes at quasi-static and dynamic conditions demonstrate threedifferent stages of the compression process: (1) initial elastic compression of the solvent, (2) fluid
intrusion into the pore upon reaching a threshold intrusion pressure and (3) elastic compression of
the solvent upon pore-filling (see Fig. 1). Extrusion of the solvent from a completely filled nanopore
upon the release of pressure is initiated by the bubble nucleation. Our simulation results arecorrelated to the experimental observations. (1)References:
1 Belogorlov, Anton A., et al. “Suspensions of lyophobic nanoporous particles as smart materials forenergy absorption.” Journal of Colloid and Interface Science 600 (2021): 229-242.

129

Molecular simulation of separation of C60 and coronene in silica
Gyö rgy Hantal 1; Ana-Sunč ana Smith 2

1 PULS Group, Friedrich-Alexander-Universitä t Erlangen-Nü rnberg, Institute for Theoretical
Physics, Interdisciplinary Center for Nanostructured Films (IZNF)

2 1-PULS Group, Friedrich-Alexander-Universitä t Erlangen-Nü rnberg, Institute for Theoretical
Physics, Interdisci- plinary Center for Nanostructured Films (IZNF), 2- Division of Physical
Chemistry, Ruđer Boš ković Institute

Emails for correspondence: gyorgy.hantal@fau.de, rustam.durdyyev@fau.de, smith@physik.unierlangen.deClassical liquid chromatography is one of the most used techniques in the field of nanoparticle separation. This is achieved by driving the nanoparticle containing liquid through a column densely
packed with meso- and nanoporous particles. Separation efficiency can be improved through optimizing the interactions between the particles, the solvent and the pore surface using directed surface modifications or adjusting the solvent composition. Finding the best combination of solvents andfunctionalized surfaces is a complex optimization problem, which is often aided with molecular
dynamics (MD) simulations. In this study, the diffusive transport of model nanonparticles, C 60
fullerene and coronene was studied in nanoconfinement using molecular modeling. The MD simulations were carried out in a slit nanopore of fixed width made of crystalline, fully hydroxylated silica.
As solvents, n-hexane and toluene mixtures of different compositions were used. Nanoparticle diffusivities computed both in the bulk and at the surface were used in our 2-state diffusion model todetermine the solvent-dependent effective diffusivities of nanoparticles [1]. Our results help torationalize the observed experimental retention time trends measured for C60 and coronene.
1. Andreas Baer, Paolo Malgaretti, Malte Kaspereit, Jens Harting, Ana-Sunč ana Smith, Modelling
diffusive transport of particles interacting with slit nanopore walls: The case of fullerenes in toluene
filled alumina pores, vol 368, 2022, 0167-7322

130

Composite Boron Nitride-based Immobilized Nanohydride
Toward Self-Accelerated Reversible Hydrogen Storage
Maxwell Tsipoaka1; Fateme Rezaei1
1 Missouri University of Science and Technology
Emails for correspondence: mtbr5@mst.edu, rezaeif@mst.edu
Metal hydrides for on-board hydrogen storage play a key role in future conversion of the world to a
“hydrogen economy”. Nano-structuring these materials proves an effective strategy which cansimultaneously enhance their ab/de-sorption thermodynamics and kinetics. However, strategies tocombine catalysis and nanoconfinement for controlling factors governing their interfacial hydrogen
uptake and release processes are still lacking. In this study, we show how thermal emitting method
can be used for generating Mo2N sites to create electron-deficient boron and N-vacancies in inert
boron nitride host for LiBH4 activation. The generated Mo2N sites resulted in a shift of the electronic
band structure of the host which weakened the Li-B bond of nanostructured LiBH4 species. We
demonstrate the tailoring of a strong Mo2N–DBN hybrid structure and clarify the mechanistic originof its activity. Both experimental results and DFT investigations indicate a long-range interaction of
Li in the immobilized nanohydride with B atoms, which optimizes the adsorption energy for absent
LiBH4 phase transition and melting upon cycling. This study provides an approach to finely control
the host−guest nanointerface interactions of metal borohydride and scaffolds at the atomic level andis expected to guide smart thermodynamic or kinetic alteration of solid-state hydride materials.
Keywords: Density functional theory, Hydrogen economy, adsorption, storage, interfacial chargetransfer, nanointerface interactions, electronic band structure, nanoconfinement, thermodynamic or
kinetic alteration.

131Mechanical Properties of Gases Adsorbed in Micropores from theFluctuation Theory
Santiago Flores Roman1, Alina Emelianova 2; Gennady Gor 3
1 New Jersey Institute of Technology
2 Princeton University

3 Princeton University, NJIT
Emails for correspondence: saf5@njit.edu, ae3301@princeton.edu, gor@njit.edu
Fluids exhibit different thermodynamic properties in confinement compared to their bulk state.
Their boiling and melting temperatures shift, their densities are lower than their bulk phase, andtheir me- chanical properties, such as the elastic modulus, alter depending on the pore size [1]. Thesephenom- ena have been analyzed previously through computational models, such as molecularsimulations, although the focus on understanding the altered mechanical properties in confinement
has primar- ily centered on mesopores rather than micropores. There were previously only several
attempts to study such effects in micropores, including Dobrzanski et al. [2], who analyzed how
variations in pore geometry and size influence the mechanical properties of fluids confined in
micropores. How- ever, due to the distribution of fluid molecules, when confined in a micropore,
being far from the normal distribution, these studies presented a challenge for applying a fluctuation
theory to calculate the mechanical properties of a fluid through molecular simulations.
In this work, we studied the elastic properties of nitrogen and carbon dioxide adsorbed in micropores. As a model system, we focused on a recent molecular simulation study of gas adsorption in
LTA4A and NaX zeolites [3]. We extended the results obtained in [3] by calculating the mechanicalproperties of adsorbed nitrogen and carbon dioxide using the fluctuation theory. We found that theenhancement of the elastic modulus is observed in micropores, even when the densities of theadsorbed fluid are lower than in the bulk phase. We concluded that this effect is due to reduced
fluctuations in the adsorption of the fluid. We showed that similar calculations can be applied to any
fluid adsorbed in a micropore. Therefore, our results bring a deeper insight into the characterizationof confined fluids in micropores.
References:
1. C.D. Dobrzanski, B. Gurevich, G. Y. Gor, Elastic Properties of Confined Fluids from Molecular
Modeling to Ultrasonic Experiments on Porous Solids, Applied Physics Reviews, 8 (2021) 021317.
2. C.D. Dobrzanski, M. A. Maximov, G. Y. Gor, Effect of Pore Geometry on the Compressibility of a
Confined Simple Fluid, The Journal of Chemical Physics, 148 (2018) 054503.
3. A. Emelianova, C. Balzer, G. Reichenauer, G. Y. Gor, Adsorption-Induced Deformation of Zeolites 4A
and 13X: Experimental and Molecular Simulation Study, Langmuir, 39(2023) 11388-11397.

132

The Effect of Carbon Nanotube Diameter on Hydration of Critical
Material Ions from E-waste
Qing Shao1; Zachary Baker1
1 University of Kentucky

Emails for correspondence: zdba227@uky.edu, qshao@uky.edu
Critical materials such as lithium, nickel, and cobalt play an important role in the sustainable development of society. However, establishing a reliable supply of these critical materials has been achallenge for the USA. Meanwhile, electronic waste (E-waste) has become a societal burden due tothe quick spread of electronic devices and electric cars. E-waste contains a large amount of ex- posed
lithium, nickel, and cobalt, which will pollute the soil and water if not disposed of properly. Thus,
highly efficient technology that can recover critical materials from E-waste can help reduce thedetrimental effects of E-waste on the environment and resolve the supply chain issue for thosecritical materials. One challenge of recovering critical materials from E-waste is developing a separation technology that can differentiate between the materials themselves. Nanoporous materials
have shown their exceptional potential in separating substrates with similar chemical and physicalfeatures. However, the creation of such nanoporous materials must be based on a full understandingof the molecular thermodynamics of ionic hydration within nanoscale confinement. This work investigates the hydration structure and dynamics of three critical material ions for lithium-ion batteries(Li2+, Ni2+, and Co2+) within carbon nanotubes with a diameter from 1.0-2.0 nm using molecularsimulations. We deploy classical and ab initio molecular dynamics (MD) simulations to investigate
the structural and dynamic properties of water molecules with those ions within the carbon nanotubes. We also explore the development of deep learning force fields that enable us to investigate
the ionic hydration within carbon nanotubes as accurately as ab initio MD simulations, but much
faster. The simulation-revealed deviation will be used to develop membrane-based separation technology for recovering critical materials.

133

Molecular Simulation of Adsorption of Sarin and Simulants on
Metal–Organic Frameworks
Elizaveta Basharova1 , Alina Emelianova 2; Allen Reed 1; Gennady Gor 3; Andrei Kolesnikov 4
1 NJIT
2 Princeton University

3 Princeton University, NJIT

4 Department of Chemical and Materials Engineering, New Jersey Institute of Technology
Emails for correspondence: eb374@njit.edu, afr3@njit.edu, ae3301@princeton.edu,
kolesnik@njit.edu, gor@njit.edu
Even in 21st century, chemical warfare agents (CWA) remain a threat, and a lot of research and development is aiming to advance protection from CWA. Experiments with CWAs are dangerous and are
typically reduced to a minimum. Most of experiments are done on simulants –chemicals which have
similar structure, but much lower toxicity. For sarin simulants include dimethyl methylphosphonate(DMMP), diisopropyl methylphosphonate (DIMP), and diisopropyl fluorophosphate (DIFP). Unlike
experimental work, molecular simulations are not constrained with the toxicity, so in addition to
studies of simulants, simulations can be used for studies of the agents themselves.
In this work we focused on promising adsorbent materials for CWA protection – MOFs - metalorganic frameworks. MOFs are highly porous materials and some of them show strong capacity tocapture sarin [1]. We used the selected MOFs from the recent screening study [1] and performed
Monte Carlo simulations on adsorption of sarin and its simulants. Although sarin and its simulants
have close thermodynamic properties [2], their adsorption behavior can be different, and requires adetailed computational verification. The calculated adsorption isotherms, enthalpy of adsorption andradial distribution functions (RDF) allowed us to select the best MOF for capturing sarin and reveled
how similar the interaction between sarin-MOF and simulant-MOF [3]. Based on the calcu- lated
properties we have concluded that among all the simulants DMMP demonstrated the closest behavior
to sarin. Thereby the results provide insights in selection of the best simulant to study CWA
adsorption on MOF’s and synthesis new efficient compounds for capturing of chemical war- fareagents.
References:
1.
2.
3.

I.Matito-Martos,P.Z.Moghadam,A.Li,V.Colombo,J.A.Navarro,S.Calero,D.Fairen-Jimenez.
(2018). Discovery of an optimal porous crystalline material for the capture of chemical
warfare agents. Chemistry of Materials, 30(14), 4571-4579.
A.Emelianova, E. Basharova, A.Kolesnikov, E.V. Arribas, E.V. Ivanova, G. Y. Gor, Force Fields
for Molecular Modeling of Sarin and its Simulants: DMMP and DIMP. J. Phys. Chem. B; 2021,
125, 4086–4098
A.Emelianova, A.Reed, E. Basharova, A. Kolesnikov, G.Y. Gor, Closer Look at Adsorption ofSarin and Simulants on Metal–Organic Frameworks. ACS Appl. Mater. Interfaces 2023, 15,
14, 18559– 18567

134

A unified approach for bridging the gap between cDFT andequation of state for confined fluids
Amaro Gomes Barreto Jr.1; Dá rley Carrijo de Melo2; Felipe Rocha Pinto1; Frederico Wanderley
Tavares1; Vı́tor Sermoud3
1 Universidade Federal do Rio de Janeiro
2 CENPES/Petrobras S.A.

3 Federal University of Rio de Janeiro
Emails for correspondence: amaro@eq.ufrj.br, tavares@eq.ufrj.br, felipefrpinto@gmail.com,
darley@petrobras.com.br, vsermoud@gmail.com
In recent years, extensions of the cubic equations of state for fluids confined in different geome- tries
have been developed based on the Generalized van der Waals Theory. These equations make itpossible to describe the Helmholtz energy as a function of temperature, volume, and number ofcomponents, from which expressions for all other thermodynamic properties can be derived.
Extending the Equation of States to represent confined fluids in micro and mesopores is stillchallenging. Although different authors have modified classical expressions like Peng-Robinson1 tomodel ad- sorption, these models usually reduce the pore structure to simple geometries and porepotentials. Depending on the level of simplification, the methodology can struggle when representing
systems in a range of temperatures. Although they have a lower computational cost, they still do nothave the robustness seen in methods such as Monte Carlo (MC) simulations or those based on theclassical density functional theory (NLDFT). However, MC and NLDFT are the most recommended
for micro and mesopores, but it is challenging to use them to obtain thermodynamic properties for
fluids in larger pores, generating a demand for a single methodology that covers all scales. Therefore,
this work simulates pore confinement with an NLDFT model and uses the fluid physicochemical
proper- ties to feed the Peng-Robinson extended to represent the confinement effect. To verify the
success of this approach, we carried out CO2 adsorption isotherms on faujasite zeolite in a magnetic
suspen- sion balance (Rubotherm) over a pressure range of up to 50 bar. The results show that when
we feed this NLDFT information into the equation of state for a confined fluid, the resulting model
can more adequately represent the CO2 isotherms in faujasite at different temperatures (Figure).

135

Hydrogen storage: predicting at room temperature in a series ofactivated carbons
José Carlos Alexandre de Oliveira1 , Daniel V. Gonçalves 1; Sebastiã o M. P. Lucena 1
1 Universidade Federal do Ceara

Emails for correspondence: danieldvg@live.com, lucena@ufc.br, jcadeoliveira1@gmail.com
Fuel cell vehicles hold significant promise for decreasing both energy consumption and carbon dioxide emissions. Hydrogen storage is the key technology towards the hydrogen society [1]. Vehicularhydrogen has been stored in special tanks at very high pressures (700 bar) with obvious disadvantages in the energy cost of compression and safety. The use of adsorbed H2 instead of compressed
H2 can be a solution to enable safer and more economical storage. Conducting experimental studiesof H2 adsorption at high pressures may present operational difficulties and risks. In this study wepropose the prediction of H2 adsorption up to 700 bar using the Monte Carlo algorithm in the grandcanonical ensemble and the representative pores method that we applied previously in the prediction of isotherms of C1 to C4 [2], H2S [3,4]. Based in that methodology, we predict the adsorption
capacity of H2 at 298K between 0.8 to 700 bar on different commercial carbons using textural information of N2 at 77K and CO2 at 273K. At pressures up to 100bar we obtained a good agreement withthe experimental data available.
The samples ACC10 and WKL20 have considerable volumes of pores concentrated in the region ofwell-defined micropores and show a maximum adsorption at 240 bar. The samples ACC15 andACC20, which have pore volumes in the mesopore region, reach maximum adsorption at pressureof 190. The ACC20 sample presents the highest adsorption amount of 3.15 mmol/g. Among thesimulated isotherms of figures 5 and 6, we highlight the carbon Maxsorb, the best result after that
presented by carbon ACC20, with 2.96 mmol/g at 130 bar. The Maxsorb sample has simultaneously
high volumes in the micro and mesopore regions. This means that an activated carbon that has
well- developed regions of microporosity and mesoporosity will have considerable adsorption
capacity at relatively small pressures. It was possible to determine the maximum pressure where
the highest adsorption of H2 occurs at 298 K with emphasis on Maxsorb that reached 6.14 wt % at
700 bar, near the US Department of Energy (DOE) target value of 6.5 wt.% .

References:
1. Mori D, Hirose K. Recent challenges of hydrogen storage technologies for fuel cell vehicles. Int J
Hydrogen
Energy(2009)
34:4569–4574.
doi:10.1016/j.ijhydene.2008.07.115
2. Lucena SMP, Gomes V a., Gonçalves D V., Mileo PGM, Silvino PFG. Molecular simulation of theaccumulation of alkanes from natural gas in carbonaceous materials. Carbon N Y (2013) 61:624–632.
doi:10.1016/j.carbon.2013.05.046
3. Gonçalves D V., Paiva MAG, Oliveira JCA, Bastos-Neto M, Lucena SMP. Prediction of the monocomponent adsorption of H2S and mixtures with CO2 and CH4 on activated carbons. Colloids Surfaces A Physicochem Eng Asp (2018) 559:342–350. doi:10.1016/j.colsurfa.2018.09.082
4. Menezes RLCB, Moura KO, De Lucena SMP, Azevedo DCS, Bastos-Neto M. Insights on the Mechanisms of H2S Retention at Low Concentration on Impregnated Carbons. Ind Eng Chem Res (2018)57:2248–2257.
doi:10.1021/acs.iecr.7b03402
Acknowledgements:
The authors wish to acknowledge financial support for this study from CAPES, CNPq and FUNCAP
and the use of the computer cluster at National Laboratory of Scientific Computing (LNCC/MCTI,
Brazil).

136

Study of Crystallization Pressure by Molecular Simulation
Authors: Bilal MAHMOUD HAWCHARNone; Laurent brochardNone, Florian osselin ; Jean-Michel
Pereira ; Matthieu Vandamme ; tulio honorio
Emails for correspondence: laurent.brochard@enpc.fr, tulio.honorio-de-faria@ens-paris-saclay.fr,
bilal.mahmoud- hawchar@enpc.fr, matthieu.vandamme@enpc.fr, florian.osselin@cnrs-orleans.fr,
jean-michel.pereira@enpc.fr
The in-pore crystallization of salts is considered one of the major sources of degradation of construction materials, geomaterials, and built heritage. When crystallizing, salts may exert mechanical pressure against the surface of the pore, which can damage materials. Crystallization within the porous
network remains one of the most misunderstood phenomena in porous media mechanics. We propose an investigation combining molecular simulations and theoretical development to quantify andclarify the origin of the crystallization pressure at the finest scale.
At thermodynamic equilibrium, crystallization pressure results from the change in the solubility of acrystal as it is compressed. Direct molecular dynamics simulations to compute the solubility of salts
are challenging because the time scale of dissolution and precipitation, microseconds or more, is at
the limit or beyond computing capabilities. For this reason, we use a thermodynamic integra- tion
approach to overcome this issue. With this approach, we can quantify the effect of stress on NaClsolubility, and more specifically the effect of stress anisotropy which has been disregarded so far. We
use these results to revisit the existing theory describing crystallization pressure and extend it toaccount for stress anisotropy. After investigating the case of bulk crystallization, we focus on theeffect of confinement by looking at the thermodynamics of a salt solution confined in a nanometricthin film at the interface between two crystals. We conduct molecular simulations to determine how
the thickness of the film decreases with the normal pressure exerted by the surrounding crystals.
Doing so, we identify the critical pressure threshold at which this wetting film, responsible for the
crystal growth, will disappear, providing an upper bound to the crystallization pressure
phenomenon.

137

Incorporating material flexibility effects into adsorption modelingusing non-local Density Functional Theory
Christelle Miqueu,1Raphael Labeyrie
1 Université de Pau et des Pays de l’Adour
Email for correspondence: cmiqueu64@gmail.com
Among theoretical developments, the molecular density functional theory (DFT) has emerged as oneof the most powerful and convenient molecular approach for the description of the thermodynamic
properties of inhomogeneous fluids. The development of DFT for classical fluids originates in the late
70’s [1] and its use is nowadays widespread for the description of fluid interfaces or flu- ids confinedin nanopores, the characterization of porous materials [2], etc. The success of DFT approaches is
explained by the fact that they preserve detailed information on the microstructure of
inhomogeneous fluids but with a much lower computational expense than molecular simulations.
Much progress has been made in recent years in the development of both: i) the formulation of more
realistic free energy functionals, necessary to account for complex fluids [3], ii) and more efficient
numerical algorithms to apply DFT to complex geometries [4]. DFT framework is naturally derived
in the Grand Canonical ensemble, which is suitable for fluid adsorption in rigid frameworks while theappropriate thermodynamic ensemble for the treatment of adsorption in flexible porous mate- rials
is the osmotic statistical ensemble. Hence, only a very limited number of DFT-based studies
addressed the flexibility of the porous network [5,6]. Few years ago, Coudert et al. [7] proposed a
simplification of the osmotic configurational partition function leading to a tractable formulation of
the osmotic potential to study the adsorption in flexible porous materials with molecular simulations.
In this work, we use this strategy to address the adsorption of fluids in breathing adsorbents with a
NLDFT framework. In particular, the adsorption in a material presenting two distinct shapes (largepore and narrow-pore) is investigated as a representative example of breathing metal-organic
framework (such as MIL-53).

138

Modeling Adsorption of Simple Fluids and Alkanes on 3D
Nanoporous Carbons
Nicholas Corrente1; Elizabeth Hinks1; Aastha Kasera1; Raleigh Gough1; Peter I. Ravikovitch2;
Alexander Neimark1
1 Rutgers University, New Jersey, USA

2 ExxonMobil Research and Engineering Company
Emails for correspondence: peter.ravikovitch@exxonmobil.com, cpm9.admin@rutgers.edu,
aneimark@rutgers.edu
Predicting adsorption on nanoporous carbonaceous materials is important for developing various
adsorption and membrane separations, as well as for oil and gas recovery from shale reservoirs.
Here, we explore the capabilities of 3D molecular models of disordered carbon structures toreproduce the morphological and adsorption features of practical adsorbents. Using grand canonicalMonte Carlo simulations, we construct a series of adsorption isotherms of simple fluids (CO2, N2, andSO2) and a series of alkanes from methane to hexane on two model 3D structures: purely
microporous structure A and micro-mesoporous structure B. We show that structure A reproduces
the morphological properties of commercial Norit R1 Extra activated carbon and demonstrates
outstanding agreement between the simulated and experimental adsorption isotherms reported in
the literature for all ad- sorbates considered. Good agreement is also found for simulated andmeasured isosteric heats. This work provides a new insight into the specifics of structural andadsorption properties of nanoporous carbons and demonstrates the advantages of using 3D
molecular models for predicting adsorption hydrocarbons and other chemicals by MC simulations.
This work is supported by the NSF CBET grant 1834339 and ExxonMobil.
N.J. Corrente, E.L. Hinks, A. Kasera, R. Gough, P.I. Ravikovitch, A.V. Neimark, Modeling adsorp- tion of
simple fluids and hydrocarbons on nanoporous carbons, Carbon 197 (2022) 526-533. DOI:
10.1016/j.carbon.2022.06.071

139

SAFT-DFT Studies of Nanoporous Carbon Deformation Induced byMulticomponent Adsorption
Nicholas Corrente1; Elizabeth Hinks1; Aastha Kasera1; Alexander Neimark1
1 Rutgers University, New Jersey, USA
Emails for correspondence: cpm9.admin@rutgers.edu, aneimark@rutgers.edu
We consider deformation of nanoporous carbons during adsorption of mixtures, focusing on thespecific context of carbon dioxide displacement of natural gas from coal and shale reservoirs. Density
functional theory calculations augmented by the perturbed chain statistical associating fluid theory(SAFT-DFT) are employed to model adsorption of fluid mixtures on carbon slit pores at geo- logically
relevant temperatures and pressures. The adsorption stress is calculated from the change in the
grand thermodynamic potential of the adsorbed fluid with respect to the change in pore volume.
Adsorption of methane and carbon dioxide mixtures is studied in pores of various size. We determine
the effect of pore size and fluid composition on the adsorption-induced deformation. The results ofthis method show good agreement with atomistic GCMC simulations at a fraction of thecomputational cost.
This work is supported by the NSF CBET grant 1834339.

140

Development and application of an advanced percolation model
for pore network characterization by physical adsorption
Jakob Sö llner1; Alexander Neimark2; Matthias Thommes3
1 Institute of Separation Science and Technology, Friedrich-Alexander Universitä t ErlangenNü rnberg

2 Rutgers University, New Jersey, USA

3 Friedrich-Alexander-University Erlangen-Nü rnberg
Emails for correspondence: jakob.soellner@fau.de, aneimark@rutgers.edu
Physical adsorption is one of the most widely used techniques to characterize porous materials because of being reliable and able to assess micro- and mesopores within one approach. However, challenges and open questions persist in characterizing disordered and hierarchically structured porous
materials. This study introduces a pore network model aiming to enhance the textural characterization of nanoporous materials. Our model, based on percolation theory on a Bethe lattice, includes allmechanisms known to contribute to adsorption hysteresis in mesoporous pore networks during
capillary condensation and evaporation. The model accounts for delayed and initiated condensation
during adsorption as well as equilibrium evaporation, pore blocking and cavitation during desorption. Coupled with dedicated non-local-density functional theory (NLDFT) kernels, the proposed
method provides a unified framework for modeling the entire experimental adsorption-desorption
isotherm, including desorption hysteresis scans. Hence, this model unveils key pore network characteristics like the effective connectivity, but also has the potential to determine pore size distributionsof mesoporous materials by taking quantitatively pore network effects into account.
The applicability of the method is demonstrated on a selected set of nanoporous silica materials
exhibiting distinct types of hysteresis loops (types H1, H2a, H1/H2a and H5), including orderedmesoporous silica networks, i.e, KIT-6 silica, hybrid SBA- 15/MCM-41 silica with plugged pores, butalso two disordered silica pore networks, i.e., a hierarchical meso-macroporous monolith and porous
Vycor glass. For all materials, good correlation is found between calculated and experimental primary adsorption and desorption isotherms as well as desorption scans allowing for a determinationof key pore network characteristics such as pore connectivity and pore size distributions as well as
a parameter correlated with the impact of pore network disorder and corresponding effects on theadsorption behavior. The versatility and enriched textural insights provided by the proposed novel
network model allows for a comprehensive characterization previously inaccessible, and hence willcontribute to a further advancement in the textural characterization of novel nanoporous materials.
It has the potential to provide important guidance for the design and selection of porous materi- alsfor optimizing various applications, including separation processes (such as chromatography),heterogeneous catalysis, gas-and energy storage. [1]141