Adsorption-Biased Characterizationof Porous Materials
Katsumi Kaneko
Research Initiative for Supra-Materials, Shinshu University

9th CPM+mesopores

FloridaMay 19-23, 2024

Onlymicropores
Y. Tao et al, Chem. Rev.(2006)

FOA
COPS
CPM

PBAST

International Conferences on Adsorption

International Science Community
on Adsorption-Biased Characterization of Porous Solids
COPS:Characterization of Porous Solids

Europe1987(Bad Soden)- Chemistry, Materials science
F. Rodriguez-Reinoso, J Rouquerol, KSW Sing, KK Unger

FOA: Fundamentals of Adsorption

World wide
Chemical engineering Materials SciencePBAST: Pacific Basin Adsorption Science and Technology
Asia and Oceania
Chemical engineering Materials Science
Asian countries USA(European countries)

CPM: Characterization of Porous Materials

FloridaMaterials science, Chemical engineering, Chemistry,-A.V. Neimark TRI-Princeton(First-5 th) 1997—2009
A. V. Neimark, M. Thomas CPM(6 th-9 th ) 2012—2024

COPS: Characterization of Porous Solids
1987(Bad Soden)- Chemistry, Materials science
F. Rodriguez-Reinoso, J Rouquerol, KSW Sing, KK Unger

In front of my poster
with Paco

New Leaders
Tina Düren(UK)Maurin Guillaume(France)

Stefan Kaskel(Germany）

Joaquin Silvestre（Spain）

Next COPS
2026, Dresden
Photos from HP

FOA: Fundamentals of Adsorption
FOA 3 1989 Sonthofen, Germany
A. B. Mersmann
Chemisorption assisted micropore filling of NO
FOA 4 1992 Kyoto, Japan
M. Suzuki
Ultramicroporosimetry of porous solids by He adsorption
FOA 5 1995 California, USA
M. D. Le Van
Organize molecular states in micropores
FOA 6 1998 Giens, France
F. Meunier
Nanoclathrate-assisted adsorption of supercritical gases in hydrophobic pores
FOA 7 2001 Nagasaki, JapanK. Kaneko
Fundamental problems in high pressure adsorption of supercritical gases
FOA 8 2004 Arizona, USA
O. Talu
Plenary: Nanospace molecular science and adsorption
FOA 9 2007 Italy
M. Mozzotti
FOA10 2010 Japan
M. Miyahara
FOA11 2013 USA
P. A. Monson
FOA12 2016 Germany
A. Seidel-Morgenstern
FOA 13 2019 Australia
P. Webley
FOA 14 2022 Colorado, USA
C. Jones
Plenary: In-solid Nanostructure-Derived Routes for Future-Responsible Engineering

FOA 15 2025 Portugal 18 - 23 May 2025 in Porto

José Paulo Mota

Pacific Basin Conference
on Adsorption Science and Technology
Kisarazu (Chiba) Japan 1997

We have 9th PBAST in Malaysia
this fallProf. D. D. Do (2nd) Prof. C. –H. Lee (3ird)

日本化学会 ３月２１日 ２０１８年
Prof. L. R. Radovic Prof. F. Meunier Prof. Z. Li Prof.T. Bandosz
Prof. M. Jaroniec Prof. M. Suzuki Prof. A. Myers Prof. P. Wu
Prof. W. A. Steele Prof. J.U. Keller Prof. Y. H. Ma Dr. K. S. KnaebelProf. S. Sircar Prof. T. Takaishi Prof. K. Ttsutsumi

Prof Yeoh Fei Yee
University Sains Malaysia

https://pbast2024.eng.usm.my/email: pbast9.msia@gmail.com

Characterization of Porous Materials:From Ångstromes to MillimetersÅ

Ultrafast graphene wrapped zeolite membrane
Industrial
separation

１00 nm

30 mm

1m

R. Kukobat et al. Sci. Adv.2022,8. eabl3521

Home Party
at The first Characterization ofPorous Materials, Princeton, 1997
Prof. Neimark

Prof. Unger

Dr.
Nicholson

KK

Dr.
AbramsProf.
Gubbins

Prof.
Prof.
Rodriguez
Roquerol-Reinoso

Prof. Steele
Prof. Sing

Ms. NeimarkProf.
Findenegg

Dear Katsumi,
Time is flying by very fast, and we are pleased to announced that the 6 thInternational Workshop "Characterization of Porous Materials: from Angstroms
to Millimeters"(CPM-6) will be held in Palm Beach, Florida, on April 30 - May 2,
2012. The CPM series is organized on a tri-annual basis, alternating with COPS
symposiums and FOA conferences. This time, we decided to change the location
to make this meeting more attractive for its regular participants, some of whom
attended all five previous meetings in New Jersey.
The meeting will take place in a beautiful setting of Delray Beach Marriott
located on Florida's Atlantic Ocean Gold Coast,
overlooking sandy beaches in the midway between Ft. Lauderdale and Palm
Beach.------------------------With warmest wishes,Alex Neimark

Ruthgers The State Universityof New Jersey

Matthias ThommeFriedrich-Alexander-University
Erlangen-Nürnberg

World wide Issues

The first text appearedin 1972
The third text
by D. Meadows
J. Raders
D. Meadows(MIT, USA)
2004
Chelsea Green Pub. Co.

Global Warming
Renewable Energy Technologies
Energy Consumption (BP Energy Outlook, 2018, p.14)

RenewableenergyNuclearNatural gas

Oil, CoalSuperefficient
coal energy
technology

Chemical Industries use Distillation
Distillation

Pure
substances
AMixtures

Chemicalreaction

A+B= CB

Separation technologies are energy-intensive
due to distillation

Living wares

Energy for Separation of Chemicals is
about 50 % of Total Energy Used in Industries

1x1018 J

http://enko.co.jp/product/index.html

Energy consumption byDistillation, Drying,
Evaporation

Energy Saving Separation
Technologies
Adsorption separation
Membrane separation
By D. S. Sholl, R.P. Lively,
Nature, 2016, 532, 435.

Preservationof Our Earth

Porous Materials
Fundamental of Important Technologies

Adsorption, Storage, Separation
Futuristic Characterizationof Porous Solids

Intensive Demand forAdsorption and Nanoporous Materials
Adsorption
Storage Concentration Separation Removal …..
CO2 Energy（CH4, H2, O2) Water （H2O, H2:O2)
Resources
Environmental and Medical Technologies

Nanoporous Materials
ZeolitePorous carbon

m-Silica

MFI_010s

S.Inagaki et al,JACS (1999)

PCP(MOF)…

Surrounding Situation around 1990
Development of new activated carbons by Industries
Activated carbon fiber (ACF) around 1985
Superhigh surface area carbon 1989
Templating to Template-free synthesis in zeolite
B M Lock et al. Zeolite: Review (1983)
H. Awala et al. Nature Mater.(2015)

On stage of well-defined porous solids
Mesoporous SilicasC. Kato:K. Kuroda 1990, K.Kuroda; S. Inagaki 1993

C. T. Kresge et al (Mobil) USA 1992
Carbon nanotube

SWCNT

S. Iijima 1991 : MWCNT, 1993:SWCNT
SWCNT:S Iijima T. Ichihashi, D. S. Bethune et al.

DWCNT (2005) M. Endo et al.
Porous Coordination Polymer (PCP) or Metal organic framework (MOF)
W. Mori (1997) S. Kitagawa

O. Yagi

G. Férey(Gate adsorption

K. Kaneko 2001)

New Attempts in Adsorption Studies around 1990
Theoretical Approaches
Studies with Statistical mechanics on zeolites

R. M. Barrer

T. Takaishi D. Ruthven

Molecular simulation and molecular dynamics
W. Steele

Adsorption on graphite

D. Nicholson

Adsorption in pores

K. E. Gubbins

Adsorption in pores

N. Seaton, N. Quirk
P. Monson

Pore size distribution of carbons

Cavitation, --A. Neimark Pore size distribution, Cavitation, --[Now we have powerful and younger leaders]
Fractal analysis

D. AvnirP. Pfeifer

No detailed correlation with adsorption mechanism

Experimental Progresses
in Adsorption Studies around 1990
Comparison plot analysis

K. S. W. Sing

Calorimetric measurement

J. Rouquerol

CO2 adsorption

F. Rodriguez-Reinoso

Hot topics around 1990
Adsorption on mesoporous silica (MCM, FSM)
Adsorption hysteresis:

Dependence on temp. and pore width

K. Kaneko et al: Surface roughness model
Prediction of Hysteresis Disappearance in the Adsorption
Isotherm of N2 on Regular Mesoporous Silica
Langmuir, 14, 3079(1998).

by Prof. MorishigeRepresentative Nanoporous Materials
ZeoliteCarbon

PCP:MOFSilica×

◎×××

◎××

Thermal stability◎◎△◎Oxidation resistivity◎△×◎

Water resistivity○◎△△

Ion exchangeability◎△△△Pore structure

Micro poreMicropore

Mesopore

Uniform porosity◎

Micro- andmesopore

×◎◎○△

◎◎△○

◎

○

Electrical conductivity
Thermal conductivity

Tunability of pore size
high surface area
( >1000 m2 g-1)

Industrially Used Porous Adsorbents

Delivered by Dr. T. Golden (Air Products and Chemicals,Inc.) in Tutorial lecture at 14 th Fundamentals of Adsorption(Colorado, USA, 2022)

Challenges for Better Characterizationin Porous Carbons
High resolution N2 adsorption measurement
Ultramicropore characterization
He adsorption at 4.2 KQuantum effect
Ne at 23 KH2 77 K
Superwide P/Po range adsorption from ultrahigh vacuum region
In situ measurement of molecules adsorbed in pores
X-ray diffraction for water inside activated carbon fiber ACF
T.Iiyama et al, J Phys Chem(1995)

Small angle X-ray scattering
Rotational-vibrational spectral study on CH4 inside SWCNH
EXAFS
HR-MC simulation aided in situ and/or operand X-ray scatteringEvaluation of Sub-nanometer Pores
Superwide-pressure range adsorption isotherm P/Po =10-9 ～1

Amount of adsorbed N2 / mg g-1

100Carbon black806040
Ultrahigh vacuum system200-8-6-4log(P/P0 )-20

M. Sunaga,et,J. Phys. Chem.
B, 2004, 108, 1065.

Rotational Vibration Spectra of CH4 inside SWCNH
Q branch
R branch

P/Po = 0.05
105 K

111 K

120 K

130 K

0.11 nm3boiling temp increases

P branch

Asymmetric stretchingvibration modeSingle wall carbon nanohorn

140 K
Bulk
Gas
111 K

In-situ apparatus
S.Hashimoto et al. JACS. 133, 2022 (2011).

Water Adsorbed State
from in-situ Small Angle X-ray Scattering
Fluctuation analysis of adsorbed water leads to adsorbed
state in carbon microporesadsorption; metastable

desorption

T. Ohba et al. Nano Lett. (2004). Chem. Eur. J. (2004). Mol. Phys. (2007).

Plausible 3D Structural Information
with Hybrid Reverse Monte Carlo (HRMC) Simulation
3DSynchrotron
X-ray scattering

EMI-TFSI in pores(0.7 nm,1.0 nm)
of nanoporous carbon

1D

Ionic liquid

HRMC
LJ, Electrostatic

3D

Anion-anion, cation-cation etc structure

Plausible 3D structure

Operand-Measurement of Anion Occupancy
around an Anion in Narrow Carbon Pores
In-situ Synchrotron
X-ray scattering

Operando Synchrotron
X-ray scattering

Anions (or cations)can gather eachother in narrowconductive pores

Apparent breakingof Coulombic law

Understanding highsupercapacitanceR. Futamura, et al, Nature Materials, 16, 1225 (2017)

Adsorption Isotherm leads toPore Size Distribution and 3D Local Nanostructure
Nanoporous carbons
are amorphous

The information on
local nanostructuresof porous carbon: Useful
Adsorption isothermsof N2 at 77 K
with data of model
3D nanostructuresand experimental
TEM images

Modelstructure

Adsorption
isotherms

TEM
image

3Dnanostructureof carbonsamples

3D Nanostructure Prediction of Porous Carbons via Gas Adsorption
Fernando Vallejos-Burgos et al. Carbon, 215, 118431 (1-7) (2023)

Nanoporous Solids are not “solid”
Breathing adsorption on MIL-53

Gate adsorption onMIL-11

C2H6

Chem. Phys. Lett. (2001) ,Nano Lett (2006), JACS, 133 (2011).

Theoretical study by Kyoto Group
P.L. Llewellyn et al.
JACS (2009) 131, 13002.

S. Hiraide, H. Tanaka et al.
Nature Comm. (2020)

Zeolites are Flexible
Variation of crystal celldimension with temperature

Visualizing the Flexibility of RHO
Nanozeolite: Experiment andModelingE. B. Clatworthy,et al. ,JACS, 145,15313 (2023)

Flexibility of the Zeolite RHO Framework
D. R. Corbin et al, JACS,112, 4821(1990)(supported by Dr. L. Abrams)

Zeolites are not solidAdsorption Induced Deformation
G. Reichenauer
A. V. Neimark

Experimental studies
Theoretical studies

C. Balzer et al. Langmuir, 32, 8265 (2016)
A. V. Neimark, I. Grenev, J.Phys. Chem. C. 124, 749 (2020)

Nanoporous solids of large surface area
have superior adaptability
to their nanoscale environment

Adsorption-biased characterization withintegrated in sit and/or operand approaches

Advanced Porous Materials developed by Hornet Tech.
Layering“Nanostructured”
Porous Material“Meso”porous channel

Other merits
LightWater resistive
Highly ordered“micropores”

Weather resistive
Biomaterials-derived

New challenges forNovel porous materials
Better characterization
leads to beyond-porousmaterials

Scientific Trails are not necessarily easy.
You could get a great pleasure
on finding an excellent route for new science

Looking forward to challenges by young scientists

Thank you33

There are so many unsolved
issues in this areaResults SWCNTの細孔構造and discussion

SWCNTの細孔構造
Results anddiscussion
理論値

インタースティシャル
チューブ細孔径 1.4 nm
サイト
0.32 nm
チューブ径 1.7nm

PALS Ave.
1.1 nm

N2 Ads※Ave. 1.4 nm

Ar Ads※Ave. 1.3 nm※ N2 adsorption and Ar adsorption：QSDFT, cylinderical model≒ 1.1 nm PALS

インタースティシャルサイトを考慮すると、PALSは平均細孔径（rAve.）とほぼ一致！