bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Progress in 3D-Oriented MOF Systems
Authors: Falcaro Paolo 
Published: December 2024

Metal-organic frameworks (MOFs) are promising materials for a variety of applications including sensing, microelectronics, and optics. Despite their exceptional functional properties, protocols for the microfabrication of MOF-based components are still underdeveloped. However, this is a key-enabling process: controlling the geometrical position, shape, and crystal orientation in micropatterns will enable the implementation of MOF materials in technologically relevant devices.[1]
In this presentation, we will discuss recent developments in the field of 3D-oriented MOF systems;[2,3,4] specific attention will be given to those procedures using ceramics as precursor materials. Protocols for the deposition of 3D-oriented polycrystalline Cu-based MOFs via hetero-epitaxial growth from Cu-based ceramics will be presented.[2,3] A recent strategy that enables the expansion of photolithography for the microfabrication of 3D-oriented MOF patterns will be examined.[4,5] Films and patterns of 3D-oriented MOFs show polarization-dependent fluorescent properties.

References

[1] P. Falcaro, D. Buso, A.J. Hill, C.M. Doherty, Adv.Mater.
2012, 24(24):3153–68; M. Linares‐Moreau, L. A Brandner, M. de J Velásquez‐Hernández, J. Fonseca, Y. Benseghir, J.M. Chin, D. Maspoch, C. Doonan, P. Falcaro Adv.Mater.
2024, 36, 2309645
[2] P. Falcaro, K. Okada, T. Hara, K. Ikigaki, Y. Tokudome, TA.W. Thornton, A.J. Hill, T. Williams, C. J. Doonan, M. Takahashi Nat. Mater.
2017, 16(3), 342-348.
[3] M. Linares-Moreau, L. A. Brandner, T. Kamencek, S. Klokic, F. Carraro, K. Okada, M. Takahashi, E. Zojer, C. J. Doonan, P. Falcaro, Adv. Mater. Interf.
2021, 8, 2101039.
[4] M.d.J. Velásquez-Hernández, M. Linares-Moreau, L.A. Brandner, B. Marmiroli, M. Barella, G.P. Acuna, S.D, Zilio, M.F.K. Verstreken, D.E. Kravchenko, O.M. Linder-Patton, J.D. Evans, H. Wiltsche, F. Carraro, H. Wolinski, R. Ameloot, C. Doonan and P. Falcaro. Adv.Mater.
2023, 35, 2211478.
[5] M.Tu, B. Xia, D.E. Kravchenko, M. L. Tietze, A. J. Cruz, I. Stassen, T. Hauffman, J. Teyssandier, S. De Feyter, Z. Wang, R. A. Fischer, B. Marmiroli, H. Amenitsch, A. Torvisco, M. de J. Velásquez-Hernández, P. Falcaro & R. Ameloot Nat. Mater., 2020, 20, 93–99

Figure 1
(Invited) air/Liquid Interfacial Formation Process of Electrically Conductive Metal-Organic Framework Nanosheets
Authors: Makiura Rie 
Published: December 2024

Development of rational methods for creating ordered two-dimensional (2D) structures with nanometer scale precision is one of the central issues in the nanoscience and nanotechnology fields because of their intrinsic physical-chemical properties which are seen in those of their equivalent bulk state. Inclusion of highly regulated nanopores into the nanosheet structure will further open the possible applications such as nanosieves, molecular/ion storage and sensor devices as well as introducing guest molecules into the nanopores tune variedly the sheet properties (electric conduction, nanoheterojunction). Utilizing molecular building units are suitable for creating such porous nanosheets because of rich variety of design and facile modification of size and shape.
Here, I present a facile bottom-up synthesis of molecular nanosheets with both positional and size regulated nanopores utilizing air/liquid interfaces[1-5]. By applying liquid interfaces, growth direction of the object can be well controlled with utilizing self-assembly feature of the molecules under mild conditions. We have succeeded to tune finely the nanosheet structures by rational modification of molecular building units . The highly crystalline structure remains after transferring a solid substrate from the liquid surface as well as without any supports. Notably, such highly oriented porous crystalline structure is obtained specifically by applying bottom up synthesis at air/liquid interfaces, not by other techniques.
I also present detailed insights into the formation process of electrically conductive MOF nanosheets composed of 2,3,6,7,10,11-hexaiminotriphenylene (HITP) and Ni(II) ions (HITP-Ni-NS) at the air/liquid interface [6-8]. The morphological and structural features of HITP-Ni-NS strongly depend on the standing time—the time without any external actions involved, but leaving the interface undisturbed after setting the ligand solution onto the metal-ion solution. We find that the fundamental features of HITP-Ni-NS are determined by the standing time with conductivity sensitively influenced by such pre-determined HITP-Ni-NS characteristics. These findings will lead towards the establishment of a rational strategy for creating MOF nanosheets at the air/liquid interface with desired properties, thereby accelerating their use in diverse potential applications.
1. R. Makiura et al. Nature Mater. 9, 565 (2010).
2. S. Motoyama, R. Makiura, O. Sakata, H. Kitagawa, J. Am. Chem. Soc. 133, 5640 (2011).
3. R. Makiura, O. Konovalov, Sci. Rep. 3, 2506 (2013).
4. R. Makiura et al. ACS Nano, 11, 10875–10882 (2017).
5. R. Makiura et al, Coord. Chem. Rev. 469, 214650 (2022).
6. R. Makiura et al, ACS Appl. Mater. Interfaces, 13, 54570 (2021).
7. R. Makiura et al, J. Colloid Interface Sci. 651, 769 (2023).
8. R. Makiura et al, Langmuir. 39, 8952 (2023).

Figure 1
(Invited) Color e-Paper Technology with Electrochemistry Toward Energy Conservation
Authors: Kobayashi Norihisa 
Published: December 2024

Multifunctional electrochromic (EC) materials which control multiple colors, various color density, and specular reflection are expected to be potential candidate for light-modulation device and novel reflective display device. Electrodeposition is also attractive method to create colors1-6) because silver (Ag) nanoparticles exhibit various optical states based on their localized surface plasmon resonance (LSPR). LSPR bands of metal nanoparticles are affected by the size and shape. The control of LSPR, therefore, must enable dramatic changes in color for the surface where nanoparticles are deposited. We successfully demonstrate the first LSPR-based multicolor EC device enabling reversible control of six optical states—transparent, silver mirror, cyan, magenta, yellow and black. We will discuss the mechanism of electrodeposition and a wide range of its applications.
References; 1) Adv. Mater., 24, 122 (2012), 2) Adv. Mater., 25, 3197 (2013), 3) Chem. Mater., 26, 6477 (2014), 4) Nanoscale,
12, 23975 (2020), 5) Adv. Mater. Tech., 6, 200081 (2021), 6) Sol. Ener. Mater. & Sol. Cells, 251, 112 (2023).
Development of High Durable Catalyst for PEFC
Authors: Akiyama Tomohiro , Kagawa Masaru , Matsutani Koichi 
Published: December 2024

PEFC is focused as highly efficiency and clean energy device to reduce emission of CO2. Pt/C and PtCo/C are widely used as cathode electrocatalyst for PEFC. But there are many issues required for catalyst such as low platinum and high durability for the widespread use of PEFC. We tried to improve catalyst durability against potential cycles attributed to Pt dissolution. We prepared barrier layer on the Pt/C cathode catalyst surface to prevent the increasing in particle size due to Pt dissolution and reprecipitation.
The ORR mass activity at 0.90V and electrochemical surface area (ECSA) of catalysts were measured by 25cm2-MEA. Durability evaluation was carried out by conducting potential cycles of 650mV-1050mV attributed to Pt dissolution and measuring the activity every constant potential cycles. Fig.1 shows mass activity and ECSA of standard Pt/C and improved Pt/C catalyst with potential cycles. ORR mass activity and ECSA of Pt/C catalyst was significantly decreased after cycles. It seems that the dissolution of Pt remarkably progressed. On the other hand, decreasing in mass activity and ECSA of improved-Pt/C catalyst with barrier layer was significantly suppressed compared to Pt/C catalyst. It was shown that decreasing in surface area due to dissolution and reprecipitation of Pt would be prevented and high activity was maintained even after potential cycles by barrier layer.
To understand Pt dissolution phenomenon of each catalysts, we investigated the MEA after the durability test by TEM and EPMA analysis. From analysis results, increasing in particle size and Pt band formation of improved Pt/C catalyst were significantly suppressed after durability test compared to standard Pt/C catalyst. These results suggest that barrier layer on the catalyst surface is much effective for improving catalyst durability against potential cycles.

Figure 1
Carbon Interaction with Precious Metal Catalysts for ORR : More Than a Support
Authors: Roiron Camille , Ferro Giovanni , Chen Jiazhe Loki , Cosenza Alessio , Atanassov Plamen 
Published: December 2024

Proton exchange membrane fuel cells (PEMFC) are developed to lower the carbon footprint of the medium- and heavy-duty vehicles. To this day, the durability of the PEMFC catalysts, especially for the kinetically sluggish oxygen reduction reaction (ORR) that occurs at the cathode, remains a significant obstacle. Current state-of-the-art electrocatalysts are comprised of platinum-based nanoparticles anchored on high surface area carbon black supports (Pt/C). To prevent the catalyst degradation and meet the U.S. Department of Energy’s near-term activity benchmarks [1], employment of mesoporous carbon supports is considered. However, to understand how porosity affects the catalyst durability, model catalysts must be studied [2].
Here, we systematically investigate the effect of carbon support micro- and mesoporosity, chemical structure and position of the active nanoparticles on the support. Pt/C electrocatalysts are synthesized by decorating different carbon materials with spherical Pt nanoparticles. We developed a methodology to place the Pt nanoparticles at will inside or outside the carbon mesopores; this was done for several carbon supports, while keeping constant the particle size and crystallinity. The electrochemically active surface area (ECSA) and intrinsic activity are evaluated in liquid electrolyte rotating ring disk electrode (RDE). We demonstrate that the carbon chemical structure significantly affects the exposure of Pt surface and the catalyst performance. More specifically, two materials with very similar Pt loadings (based on thermogravimetric analysis), particle size distributions and XRD patterns demonstrate very different electrochemical behavior. ECSA and mass activity variation of 59 m2/gPt and 241 A/gPt (at 0.9 VRHE) respectively are obtained between the two catalysts. This stark difference highlights that carbon support effects should be studied in isolation from all other parameters and that their influence cannot be neglected when studying the effect of Pt locality and chemical modifications.
The controlled locality of Pt nanoparticles inside or outside the carbon mesopores provides us with a pathway to investigate how the metal and support interact. Leveraging this relationship we determine if surface modifications of the supports can tune Pt-carbon interactions to promote activity and durability for the next generation catalysts.
[1] M. Rezaei Talarposhti, T. Asset, S. T. Garcia, Y. Chen, S. Herrera, S. Dai, E. J. Peterson, K. Artyushkova, I. Zenyuk, P. Atanassov, ChemPhysChem, 21 (2020) 1331-1339.
[2] G.S. Harzer, A. Orfanidi, H. El-Sayed, P. Madkikar, H.A. Gasteiger, J. Electrochem. Soc. 165 (2018) F770-F779.
Scalable and Tunable Synthesis of Sustainable Nitrogen-Doped Hydrothermal Carbon Materials (N-HTC) As Support Material for Platinum/N-HTC ORR Catalysts
Authors: Martin Julian , Mitrovic Julian , Fischer Anna 
Published: December 2024

In electrochemical catalysis, carbon materials play a pivotal role as support material for catalytically active metal nanoparticles, e.g. Pt nanoparticles in case of fuel cells. The physicochemical properties of such carbon supports thereby significantly impact the catalytic activity and stability of thereof derived supported catalysts.
Hydrothermal carbonization (HTC) stands as a thermochemical process utilized in crafting functional carbon materials from biomass or its derivatives. Under elevated temperature and pressure in an aqueous milieu, biomass undergoes conversion into carbonaceous precursors [1].
Presented here is a lab-scale synthesis of nitrogen-doped carbon materials via hydrothermal carbonization, offering versatility as support material for electrocatalysis. The sustainable nitrogen-doped hydrothermal carbon materials (N-HTC) are synthesized from affordable precursors, namely glucose and ovalbumin, at mild temperatures. Subsequent thermal treatment of the resulting carbogels facilitates control over surface chemistry (nitrogen content), porosity, and graphitization/conductivity [2]. Significantly, the synthesis process has been successfully scaled up, while preserving the performance determining parameters of the resulting carbon supports.
Furthermore, these N-HTC materials are impregnated with platinum nanoparticles to create Pt/N-HTC catalysts for oxygen reduction reaction (ORR) in fuel cell applications. Electrochemical techniques are employed to investigate the influence of synthesis conditions, support properties, and nanoparticle characteristics on the ORR activity and stability of the developed catalysts.
References
[1] S. A. Nicolae, H. Au, P. Modugno, H. Luo, A. E. Szego, M. Qiao, L. Li, W. Yin, H. J. Heeres, N. Berge, M.-M. Titirici, Green Chem.
2020, 22, 4747–4800.
[2] J. Martin, J. Melke, C. Njel, A. Schökel, J. Büttner, A. Fischer, ChemElectroChem
2021, 8, 4835–4847.
Science of Scale-up: Electrocatalysts from Lab to Pilot Scale
Authors: Serov Alexey , Lyu Xiang , Yu Haoran , Cullen David A. , Chuahy Flavio 
Published: December 2024

Electrocatalysts for several reactions and processes are actively developed and under development by multiple research groups around the globe. These materials include catalysts for Oxygen Reduction Reaction [1], carbon dioxide reduction [2], hydrogen oxidation [3], oxygen evolution [4] and many other classes. While there is a significant interest to these materials both from scientific and industrial point of view a serious question of their scalability and manufacturability had arisen.
In this work aspects of materials scale-up through careful design of reactors, mixing conditions, reaction conditions monitoring and CFD modelling will be reported. A case study on the model system of unsupported silver nanoparticles will be discussed. Silver nanoparticles were synthesized on scale with variation of reagents concentration, different types of impellers and RPM. Materials were characterized by SEM, TEM, XRD, XPS and BET and the data were correlated to the scaleup variables. A CFD model was developed to model nanoparticles formation and was used to guid experimental scaleup effort.

Acknowledgements and Statements.

The authors acknowledge financial support from R2R and H2NEW consortia. This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE).

References.

[1] R. Ezhov, O. Maximova, X. Lyu, D. Leshchev, E. Stavitski, A. Serov, Y. Pushkar "Spectroscopic Characterization of Highly Active Fe–N–C Oxygen Reduction Catalysts and Discovery of Strong Interaction with Nafion Ionomer" ACS Applied Energy Materials 7 (2023) 604-613.
[2] Z. Li, P. Wang, X. Lyu, V. Krishna Reddy Kondapalli, S. Xiang, J. D Jimenez, L. Ma, T. Ito, T. Zhang, J. Raj, Y. Fang, Y. Bai, J. Li, A. Serov, V. Shanov, A. I Frenkel, S. D Senanayake, S. Yang, T. P Senftle, J. Wu "Directing CO2 electroreduction pathways for selective C2 product formation using single-site doped copper catalysts" Nature Chemical Engineering 1 (2024) 159-169.
[3] A. Roy, M. R. Talarposhti, S. Normile, I. V. Zenyuk, V. de Andrade, K. Artyushkova, A. Serov, P. Atanassov "Nickel-Copper Supported on Carbon Black Hydrogen Oxidation Catalyst Integrated into Anion-Exchange Membrane Fuel Cell" Sustainable Energy Fuels 2 (10) (2018) 2268-2275.
[4] X. Lyu, Y. Bai, J. Li, R. Tao, J. Yang, A. Serov "Investigation of oxygen evolution reaction with 316 and 304 stainless-steel mesh electrodes in natural seawater electrolysis" J. of Environmental Chemical Engineering 11 (2023) 109667.
High Performance Palladium-Ceria Anodes for Anion Exchange Membrane Fuel Cells
Authors: Bellini Marco , Pagliaro Maria Vincenza , Miller Hamish Andrew , Peruzzolo Tailor , Castello Carolina , Rossi Francesco 
Published: December 2024

High-performance anion exchange membranes (AEMs) recently developed for fuel cell (AEMFC) applications has stimulated catalyst developers to synthetize cheaper and more affordable materials in order to accelerate the development of AEMFCs. [1] Cathode catalysts based on not precious metals have been successfully developed (e.g. Fe and Co based cathodes). There are few examples of Pt free anode catalysts. [2] An alternative strategy is the development of high performing catalysts while at the same time reducing as much as possible the critic raw materials loading. We present here a high-performance Pd-CeO2@Cv anode for the hydrogen oxidation reaction (HOR) where an intimate contact between ceria and palladium nanoparticles allows a synergistic effect which improves the anode activity for HOR compared to traditional palladium based anodes (figure 1). [2] Moreover, Pd-CeO2@Cv is a versatile anode, showing high activity toward the oxidation of small and renewable organic molecules in Alkaline Direct Liquid Fuel Cells, such as the oxidation of ethanol and potassium formate. [3
]

Aknowledgements:

The authors acknowledge the FRESH project for funding. (EU, Horizon Europe, HORIZON-RIA-101069605.)

References:

[1] Energy & Environmental Science (2014), 7 (10), 3135-3191
[2] ACS Applied Energy Materials (2019), 2 (7), 4999-5008
[3] Energies (2018), 11 (2), 369
Figure 1: Scheme of the hydrogen oxidation mechanism on Pd-CeO2@Cv

Figure 1
Development of Anode Catalysts for Anion Exchange Membrane Fuel Cells Operating with Both H2 and Liquid Fuels
Authors: Miller Hamish Andrew , Pagliaro Maria Vincenza , Bellini Marco , Peruzzolo Tailor , Castello Carolina , Bartoli Francesco 
Published: December 2024

In 2016, for the first time a polymer electrolyte fuel cell with no Pt based electrocatalysts delivered more than 0.5 W cm-2 of peak power density from H2 and air (CO2 free).[1,2] This was achieved with an Ag oxygen reduction (ORR) cathode and a Pd-CeO2 hydrogen oxidation reaction (HOR) anodic electrocatalyst. The hydrogen oxidation (HOR) reaction under alkaline conditions is a kinetically slow process even with Pt group metals. In this presentation, we discuss our strategies to improve the alkaline HOR activity of transition metal nanoparticles. For example, through engineering strong interactions with transition-metal oxides such as CeO2 incorporated in the carbon based catalyst supports.[3] Another strategy involves utilizing novel carbon based supports such as onion like carbon (OLC). The combination of CeO2 and OLC in Pd–CeO2/OLC induces around 7% defects and modifies the electronic structure of the Pd-OLC interface, significantly improving the electrical conductivity due to enhanced charge redistribution, corroborated by density functional theory (DFT) calculations.[4] Alloying of Pd with oxophilic elements like Au and Cu also enhances fuel oxidation reactions by facilitating adsorption of OH- on the catalyst surface. Peak power densities of up to 2 W cm-2 are obtained when Pd-CeO2 is incorporated in AEMFC testing.[5] Regarding liquid fuels, we are currently developing a 100 W fuel cell system using anion exchange membranes and Pd alloy nanoparticle catalysts. The fuel cell stack will be fed with aqueous solutions of potassium formate produced from combining renewable energy and waste industrial CO2. This work is funded by EU Horizon Europe (Project FRESH - GA 101069605) [6].
References
[1] H. A. Miller, A. Lavacchi, F. Vizza, M. Marelli, F. Di Benedetto, F. D. I. Acapito, Y. Paska, M. Page and D. R. Dekel, Angew Chem Int Edit, 55, (2016) 6004.
[2] M. Bellini, M. V. Pagliaro, A. Lenarda, P. Fornasiero, M. Marelli, C. Evangelisti, M. Innocenti, Q. Y. Jia, S. Mukerjee, J. Jankovic, L. Q. Wang, J. R. Varcoe, C. B. Krishnamurthy, I. Grinberg, E. Davydova, D. R. Dekel, H. A. Miller and F. Vizza, ACS Appl Energ Mater, 2, (2019) 4999.
[3] M. V. Pagliaro, M. Bellini, F. Bartoli, J. Filippi, A. Marchionni, C. Castello, W. Oberhauser, L. Poggini, B. Cortigiani, L. Capozzoli, A. Lavacchi, H. A. Miller and F. Vizza, Inorg Chim Acta, (2022) 543.
[4] J. J. Ogada, A. K. Ipadeola, P. V. Mwonga, A. B. Haruna, F. Nichols, S. W. Chen, H. A. Miller, M. V. Pagliaro, F. Vizza, J. R. Varcoe, D. M. Meira, D. M. Wamwangi and K. I. Ozoemena, Acs Catal, 12, (2022) 10938.
[5] H. A. Miller, M. V. Pagliaro, M. Bellini, F. Bartoli, L. Q. Wang, I. Salam, J. R. Varcoe and F. Vizza, ACS Appl Energ Mater, 3, (2020) 10209.
[6] Horizon Europe funded project FRESH, Formate for Renewable Energy Storage, GA 101069605 July 2022 - June 2025.

Figure 1
Atomically Dispersed Ru on Ni Catalyst-Integrated Porous Transport Electrode for Proton Exchange Membrane Water Electrolyzer
Authors: Yeo Kyeong-Rim , Kim Soo Kil 
Published: December 2024

Water electrolysis is an eco-friendly technology that does not emit pollutants when connected to renewable energy and can obtain high purity hydrogen (>99.9%) through the process of electrochemically splitting water molecules into hydrogen and oxygen. Among them, proton exchange membrane water electrolysis (PEMWE) has the advantage of high current density, low gas crossover, high gas purity, and high pressure operation compared to existing alkaline water electrolysis.[1] The material that shows the best catalytic activity in the hydrogen evolution reaction (HER) is platinum (Pt), which has a low overpotential and high exchange current density. Therefore, it has been the subject of various studies in the fields of catalysis and electrochemistry to investigate the effect of the size and structure of Pt nanoparticles and nanostructures on electrocatalytic activity.[2,3] However, due to the limited resources and high cost of platinum, the use of platinum acts as an obstacle to commercialization of PEMWE. Accordingly, many studies have been conducted on the development of low-platinum hydrogen generation catalysts to reduce platinum usage and increase activity. has been in progress.
In this study, a porous transport electrode incorporating a Ni catalyst in which Ru was atomically dispersed was fabricated through simple electrodeposition. The Ni98.1Ru1.9 catalyst doped with trace amounts of Ru showed a low overpotential of 35 mV at –10 mA cm-2 for hydrogen evolution and a low Tafel slope of 31 mV with excellent stability. It was found that optimized hydrogen adsorption strength and improved mobility of hydrogen adsorbates on the catalyst surface contributed to high performance through density functional theory calculations. As a result of further verifying the performance and durability by applying Ni98.1Ru1.9 to the hydrogen electrode of the PEMWE cell, it showed excellent performance of 6.0 A cm-2 at 2.25Vcell and high stability operating at 1 A cm-2 for 50 hours.[4]

[References]
[1] M. F. Kaya, N. Demir., Fuel Cells, 17 (2017) 37–47
[2] J. Solla-Gullón, R. Gómez, A. Aldaz, J.M. Pérezet., Electrochemistry Communications, 10 (2008) 319–322
[3] Maryam Bayati, Jose M. Abad, Craig A. Bridges, Matthew J. Rosseinsky, David J. Schiffrin, Journal of Electroanalytical Chemistry, 623 (2008) 19–28
[4] K-R. Yeo, H. Kim, K-S Lee, S. Kim, J. Lee, H. Park, S-K Kim, Applied Catalysis B: Environment and Energy, 346 (2024), 123738