bluuebunny/crossref_metadata_2025_split huggingface dataset:
Monometallic, Bimetallic, and Trimetallic Oxyphosphides for OER Catalysis in Alkaline Electrolyte
Authors: Onajah Sammy , Lalley Marja , Kreider Melissa E , Alia Shaun M , Yu Haoran , Myers Deborah J. , Farghaly Ahmed A. 
Published: December 2024

The development of efficient and durable catalysts for the kinetically sluggish oxygen evolution reaction (OER) is paramount for advancing various electrochemical processes including water splitting, CO2 electroreduction, and metal air batteries. In this presentation, the synthesis, characterization, and electrochemical evaluation of monometallic, bimetallic, and trimetallic transition metal OER catalysts will be discussed. We employed a colloidal synthesis approach to fabricate mesoporous oxyphosphide catalysts with varying compositions. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterization revealed the formation of a distinct core@shell structure comprising a zero-valent metallic core enveloped by a porous oxygen-rich shell. An OER potential of <1.5 V versus RHE at 10 mA cm-2 and a low Tafel slope of 32 mV decade-1 were measured, surpassing other catalyst configurations including commercial platinum-group-metal-free (PGM-free) catalysts in alkaline media. Furthermore, excellent OER durability at 10 mA cm-2 was demonstrated, with a potential increase of <0.5 mV/h after 100 hours of testing. These findings underscore the potential of TM oxyphosphide catalysts as promising candidates for efficient and durable OER electrocatalysts, paving the way for sustainable energy conversion and storage technologies.
Acknowledgments
This work was supported by the U.S. Department of Energy (DOE), Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office (HFTO) under the auspices of the Electrocatalysis Consortium (ElectroCat 2.0). Argonne is managed for the U.S Department of Energy by the University of Chicago Argonne, LLC, under Contract DE-AC-02-06CH11357.

Khalafallah D, Farghaly AA, Ouyang C, Huang W, Hong Z. Atomically dispersed Pt single sites and nanoengineered structural defects enable a high electrocatalytic activity and durability for hydrogen evolution reaction and overall urea electrolysis. Journal of Power Sources. 2023, 558, 232563.

Onajah S, Sarkar R, Islam MS, Lalley M, Khan K, Demir M, Abdelhamid HN, Farghaly AA. Silica‐Derived Nanostructured Electrode Materials for ORR, OER, HER, CO2RR Electrocatalysis, and Energy Storage Applications: A Review. The Chemical Record. 2024, e202300234.

Sarkar R, Farghaly AA, Arachchige IU. Oxidative Self-Assembly of Au/Ag/Pt Alloy Nanoparticles into High-Surface Area, Mesoporous, and Conductive Aerogels for Methanol Electro-oxidation. Chemistry of Materials. 2022, 34(13), 5874-87.
Multiscale Modeling of Heterogeneous Interfaces for Hydrogen Production
Authors: Pham Anh Tuan , Kwon Hyuna , Zagalskaya Alexandra , Calegari Marcos , Ogitsu Tadashi 
Published: December 2024

Improving performance of hydrogen production devices requires a detailed understanding of physicochemical processes at solid-gas and solid-liquid interfaces. However, probing behavior of these interfaces under working conditions remain a significant challenge for both simulations and experimental probes. In this talk, I will provide an overview of our strategy for simulating heterogeneous interfaces within the HydroGEN Advanced Water Splitting Materials Consortium, ranging from first-principles calculations of chemical reactivity to machine learning approaches for accelerating theory-experiment integration and continuum methods for understanding microstructure effects. In particular, I will discuss how computational models can be used to elucidate mechanisms of interface chemical reactions and mass transport, as well as the formation of new phases and their impacts on materials stability and performance. I will also show how simulations have been integrated with experimental probes, such as X-ray spectroscopy, to obtain new understanding of materials interfaces under operating conditions. Finally, I will discuss how this understanding is being used to guide new strategies for improving materials functionality for hydrogen production.
This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
Engineered Porous Transport Electrode for Proton Exchange Membrane Water Electrolysers
Authors: Sidney Santana Cássia , Bens Frennie , Shen Jie , Dijk Bas , Diaz-Morales Oscar 
Published: December 2024

Proton Exchange Membrane Water Electrolysers (PEMWEs) is among the most promising approaches for green hydrogen production due to its rapid response times and high-power density operation, which make this electrolysis technology well-suited to harvest the intermittent power from wind and solar plants. Nevertheless, the commercial breakthrough of PEMWE technology continues to face barriers due to its costs [1]. The porous transport layer (PTL) is one of the PEMWE components that facilitates the transport of incoming water to the catalyst layer and the removal of the product gases, hence it is very important for good electrolyser performance. The state-of-the-art PTLs are manufactured by high temperature sintering of titanium fibers or powders, which can generate oxidized surfaces that will reduce PEMWE performance. Furthermore, titanium is listed by the European Union as a critical raw material since 2020 [2], so it is advisable to reduce the amounts of its use to produce PTLs. Additionally, the (micro)structure of state-of-the-art PTLs is not optimized for efficient liquid and gas transport in electrolysis. The manufacturing process plays a key role in achieving PTLs with optimized liquid and gas transport as well as reducing the usage of titanium.
In this work, we used lithography to manufacture PTLs in which the (micro-)structure can be optimized and the usage of titanium metal can be significantly reduced. The lithography manufactured PTLs were used as substrates to produce catalyst-coated electrodes (CCE) with (ultra-)low loadings of iridium and the PEMWE performance was evaluated, respect to CCEs manufactured on commercial PTLs. We demonstrate similar performance of the CCEs manufactured with the engineered PTL, with the advantage of using less titanium and being able to tune the (micro-)structure of the component.
References:
[1] Babic, U., Suermann, M., Büchi, F. N., Gubler, L., & Schmidt, T. J. (2017). Critical review - identifying critical gaps for polymer electrolyte water electrolysis development. Journal of The Electrochemical Society, 164(4), F387.
[2] European Commission, Directorate-General for Internal Market, Industry, Entrepreneurship and SMEs, Blengini, G., El Latunussa, C., Eynard, U. et al., Study on the EU's list of critical raw materials (2020) – Final report, Publications Office of the European Union, 2020, https://data.europa.eu/doi/10.2873/11619

Figure 1
Design of Highly Dispersed Pt Entities on Mesoporous N-Doped Carbon Nanospheres – Improving Pt Utilization for Hydrogen Evolution
Authors: Küspert Sven , Campbell Ian E. , Zeng Zhiqiang , Balaghi S. Esmael , Ortlieb Niklas , Thomann Ralf , Knäbbeler-Buß Markus , Allen Christopher S. , Mohney Suzanne E. , Fischer Anna 
Published: December 2024

Considering the global and growing technological demand for platinum, increasing its utilization is key in the context of green hydrogen production by proton exchange membrane water electrolysis. An effective strategy to increase Platinum utilization in Pt/C hydrogen evolution electrocatalysts is to increase the Pt dispersion on the conductive carbon support and to reduce the Pt nanoparticle size down to Pt clusters or even Pt single sites. In that context utilization of 3D porous N-doped carbon supports is helpful to form and stabilize highly dispersed Pt species and achieve high mass activities.
In here we present two approaches for the synthesis of such electrocatalysts with high Pt dispersion for hydrogen evolution: one based on a simple wet impregnation with subsequent thermal reduction, the other based on a vapor phase CVD deposition. We use N-doped mesoporous carbon nanospheres as supports, with high surface area and surface functionality to build Pt nanoparticles, clusters, and single sites.
The Pt speciation, depending on the synthesis approach, was thereby investigated a. o. by XRD, XPS, ac-STEM, XAS and electrochemical CO stripping. In all cases, when high Pt dispersion was achieved in form of Pt clusters and single sites, ultra-high mass activity was demonstrated at the RDE level [1,2].
Literature:
[1] Zeng, Z.; Küspert, S.; Balaghi, S. E.; Hussein, H. E. M.; Ortlieb, N.; Knäbbeler‐Buß, M.; Hügenell, P.; Pollitt, S.; Hug, N.; Melke, J.; Fischer, A. Small
2023, 2205885.
[2] Küspert, S.; Campbell, I. E.; Zeng, Z.; Balaghi, S. E.; Ortlieb, N.; Thomann, R.; Knäbbeler‐Buß, M.; Allen, C. S.; Mohney, S. E.; Fischer, A. Small
2024, 2311260.
Highly Gas Permeable and Dimensionally Stable Anion Exchange Ionomers for Anion Exchange Membrane Water Electrolyzers
Authors: Liu Fanghua , Liu Fanghua , Iwataki Toshio , Uchida Makoto , Kakinuma Katsuyoshi , Miyatake Kenji 
Published: December 2024

Hydrogen, as a clean energy carrier, is promising to alleviate the dependence on fossil fuels and contributing to carbon-neutrality. Alkaline water electrolyzers (AEMs) and proton exchange membrane water electrolyzers (PEMWEs) have realized commercialization to produce pure hydrogen, while high corrosiveness resulting from concentrated KOH aqueous solution and low hydrogen production efficiency of AWEs, as well as high cost resulting from platinum group metal (PGM) catalysts of PEMWEs enforced to develop the alternatives. Anion exchange membrane water electrolyzers (AEMWEs) which combine the advantages of AWEs and PEMWEs have been regarded as attractive and effective electrochemical devices as emerging water electrolyzers. Over the decades, the catalysts and AEMs have been widely studied to improve the performance and durability of AEMWEs. However, ionomers in the catalyst layers, has been largely overlooked, while ionomers play roles in binding catalyst particles and permeating produced hydrogen and oxygen.
Herein, we developed anion exchange ionomers (QC6xBA and QC6xPA) with high gas permeability and dimensional stability by introducing bulky cyclohexyl (C6) groups into polymer backbones. Among synthesized polymers, QC650BA-2.1 (target ion exchange capacity, IEC: 2.1 mmol g-1) with 50 mol% C6 composition was the most gas permeable, having 16.6-fold higher H2 permeability and 22.3-fold higher O2 permeability than QC60BA-2.1 without C6 groups. Meanwhile, QC650BA-2.1 was also more dimensionally stable, the through-plane swelling ratio decreased to 12.5% (QC650BA-2.1) from 31.1% (QC60BA-2.1). Applying QC650BA-2.1 as the anode ionomer and PGM-free Ni0.8Co0.2O1) as anode catalyst, the water electrolysis cell showed 2 times higher performance (2 A cm-2 at 1.69 V) than the cell using our previous QPAF-4-2.02) ionomer. During 1000 h durability test at 1.0 A cm-2, the QC650BA-2.1 cell showed ignorable change of cell voltage with decay rate of 1.1 μV h-1 after initial voltage increase. These results indicated using high gas permeable and dimensionally stable ionomer is significantly effective to enhance the performance and durability of AEMWE.
Reference
1) Ono, T. Kimura, A. Takano, K. Asazawa, J. Miyake, J. Inukai, K. Miyatake, J. Mater. Chem. A
2017,5, 24804.
2) Shi, T. Tano, D. A. Tryk, M. Yamaguchi, A. Iiyama, M. Uchida, K. Iida, C. Arata, S. Watanabe, K. Kakinuma, ACS Catal.
2022, 12, 14209.
A Non-Ideal Transport Model of Bipolar Membranes to Understand and Manage Multi-Ion Interactions in Water Electrolysis
Authors: Galang Francisco Javier Ubongen , Bui Justin C. , Goyal Priyamvada , Weber Adam Z. , Bell Alexis T. 
Published: December 2024

Water electrolysis provides a means of producing H2 gas without carbon emissions. However, H2 production through water electrolysis is more costly compared to methods using fossil fuels. A key element to the cost of water electrolysis is the need to purify the water fed to the electrolyzer. Impure feeds can lead to corroding electrodes (e.g. chloride oxidation) and fouling of commonly-used monopolar membranes (i.e., cation and anion exchange membranes). Bipolar Membranes (BPMs), consisting of a cation and anion exchange membranes with a water dissociation catalyst at the interface, pose unique advantages. Because each layer can be tuned independently, BPMs enable higher control of co-ion transport and impurities, unlike monopolar membranes. However, challenges arise in rationally-designing BPMs for impure water electrolysis due to a lack of fundamental understanding of the coupled interactions between water, mobile ions, and fixed charge groups.
In this study, we develop a continuum model to systematically investigate the use of BPMs for water electrolysis with impure feedstocks (e.g. seawater). The model defines the flux of each species using a modified Nernst-Planck-Poisson framework while explicitly considering non-ideal contributions to chemical potential from ion-ion, ion-membrane, swelling, electrostatic, steric, and solvation interactions to the electrochemical potential. The simulations quantify the effect of these interactions and membrane properties on ion transport, and how they could be modulated to mitigate the deleterious effects of impurities and co-ions. Our analysis shows that simple dilute-solution theory is not capable of predicting the effect of impurities on BPM water electrolysis and identifies the dominant interactions that dictate transport in BPMs. This study provides guidelines for modelling water electrolysis and materials design strategies for water electrolysis in non-ideal conditions.
Cellulose-Based Crosslinked and Reinforced Sulfonated Poly(ether ether ketone) Membranes for Robust Proton Exchange Membranes in Fuel Cells
Authors: Lee Dongjun , Kim Daeun , Kim Seungbin , Bae Insung 
Published: December 2024

Proton exchange membrane fuel cells (PEMFCs) are a promising clean energy solution due to their high efficiency and eco-friendly operation. Central to their function is the proton exchange membrane (PEM), typically composed of perfluorosulfonic acid (PFSA) ionomers like Nafion and Aquivion. However, challenges such as cost, gas crossover, and limited temperature range persist. To address these, researchers explore hydrocarbon (HC)-based polymers like sulfonated poly(ether ether ketone) (SPEEK), prized for cost-effectiveness and stability. However, HC-based polymers suffer from issues like unstable mechanical behavior and reduced proton conductivity under low humidity, necessitating further development for practical application.
In this study, we propose two approaches to overcome these drawbacks of HC-based PEMs. Firstly, we prepare crosslinked SPEEK membranes with cellulose acetate to enhance proton conduction under low RH conditions and stabilize membrane properties. The crosslinked structure of SPEEK/cellulose membranes is investigated using small-angle X-ray scattering, atomic force microscopy, and transmission electron microscopy. Additionally, we incorporate cellulose-based nanofibers obtained by electrospinning as a reinforcing substrate, enhancing the interaction between the SPEEK matrix and cellulose nanofiber filler. This results in a dense membrane without voids, effectively preventing gas crossover and improving membrane robustness. These investigations using cellulose-containing SPEEK membranes lead to enhanced power density and durable operation of fuel cells, particularly at low RH conditions.
Porphyrin-Based Antioxidant for Proton Exchange Membrane Fuel Cells
Authors: de Wild Tym , Gubler Lorenz , Nauser Thomas , Nemeth Tamas 
Published: December 2024

The increase in regulations on per- and polyfluoroalkyl substances (PFAS) due to health and environmental concerns,1 has resulted in an increasing need for alternatives to polyfluoroalkylsulfonic acid (PFSA) based proton exchange membranes (PEMs). An alternate class of polymers are functionalized polyarylenes, such as sulfonated polyphenylenesulfone (sPPS)2, sulfonated phenylated polyphenylenes (sPPP)3, and the co-polymer sulfonated polyphenylene quinquephenylene (SPP-QP)4.
Despite good progress made in reaching comparable performance to Nafion, radical induced degradation of phenyl(sulfonate) rings during fuel cell operation remains prevalent. In a recently published study,5 we investigated the potential of using a Cu(II)-porphyrin complex as an antioxidant for aromatic sulfonate compounds. First, γ-radiolysis was used on aqueous solutions containing the model aromatic compound potassium 4-(tert-butyl)-2-methoxyphenylsulfonate with varying amounts of antioxidant. The exposure of water-based solutions to high-energy radiation results in the formation of hydroxyl radicals, which in turn react with the model compound. Resulting degradation of the compounds was analyzed using high performance liquid chromatography (HPLC). In the second part of the study, we incorporated the Cu(II)-porphyrin into PEMs to test membrane stability during fuel cell operation using an accelerated degradation protocol. The measurements combined with post-mortem analysis show that membranes containing antioxidants have a five-fold increased stability compared to reference non-stabilized membranes.

References:

(1) Ackerman Grunfeld, D.; Gilbert, D.; Hou, J.; Jones, A. M.; Lee, M. J.; Kibbey, T. C. G.; O’Carroll, D. M. Underestimated Burden of Per- and Polyfluoroalkyl Substances in Global Surface Waters and Groundwaters. Nat. Geosci.
2024, 17 (4), 340–346. https://doi.org/10.1038/s41561-024-01402-8.
(2) Araujo, C. C. de; Kreuer, K. D.; Schuster, M.; Portale, G.; Mendil-Jakani, H.; Gebel, G.; Maier, J. Poly(p-Phenylene Sulfone)s with High Ion Exchange Capacity: Ionomers with Unique Microstructural and Transport Features. Phys. Chem. Chem. Phys.
2009, 11 (17), 3305–3312. https://doi.org/10.1039/B822069G.
(3) Adamski, M.; Skalski, T. J. G.; Britton, B.; Peckham, T. J.; Metzler, L.; Holdcroft, S. Highly Stable, Low Gas Crossover, Proton-Conducting Phenylated Polyphenylenes. Angew. Chem. Int. Ed.
2017, 56 (31), 9058–9061. https://doi.org/10.1002/anie.201703916.
(4) Miyake, J.; Taki, R.; Mochizuki, T.; Shimizu, R.; Akiyama, R.; Uchida, M.; Miyatake, K. Design of Flexible Polyphenylene Proton-Conducting Membrane for next-Generation Fuel Cells. Sci. Adv.
2017, 3 (10), eaao0476. https://doi.org/10.1126/sciadv.aao0476.
(5) de Wild, T.; Wurm, J.; Becker, P.; Günther, D.; Nauser, T.; Schmidt, T. J.; Gubler, L.; Nemeth, T. A Nature-Inspired Antioxidant Strategy Based on Porphyrin for Aromatic Hydrocarbon Containing Fuel Cell Membranes**. ChemSusChem
2023, 16 (21), e202300775. https://doi.org/10.1002/cssc.202300775.
Operando Quantification of Dynamic Lithium Active Area Growth in Zero-Excess-Lithium Solid-State Batteries
Authors: Fan Austin , Li Zhuo , Hatzell Kelsey 
Published: December 2024

Growing demands for electric vehicles motivate the need for energy-dense battery technologies that can enable enhanced driving ranges on a single charge [1]. Zero-excess-lithium solid-state batteries operate with no excess lithium at the anode, instead fully cycling all the lithium within the cell during each cycle. Removing excess lithium significantly increases the specific and volumetric energy density, improves battery safety, and reduces manufacturing costs [2]. However, zero-excess-lithium solid-state batteries suffer from poor coulombic efficiency and lithium dendrite formation [3] resulting from non-uniform lithium deposition onto the anodic current collector [4]. Optical microscopy is a promising operando technique for examining the electro-chemo-mechanics of lithium nucleation and growth during lithium deposition in a zero-excess-lithium solid-state battery [4]. In this work, we investigate the lithium nucleation and growth behavior on a current collector substrate using a custom cell conducive to operando optical microscopy. The transparent components of the cell allow for direct, real-time observation of lithium plating behavior. In particular, quantifying the dynamic in-plane lithium growth as a function of operating conditions such as current density, temperature, and thermal gradients provides crucial insight into the lithium growth mechanism. Optical data is complemented with mapped synchrotron diffraction data that elucidate the vertical growth of lithium into the solid electrolyte pellet by measuring the relative intensities of lithium. These results enable comprehensive characterization of lithium growth regimes, including in-plane-growth dominant and vertical-growth dominant regimes, at successive capacities of lithium plated. Understanding these lithium growth regimes guides strategies to attain more lateral, uniform lithium deposition, with long-term implications in achieving stable, high-capacity zero-excess-lithium solid-state battery operation.

References:

[1] Yang-Kook Sun. Promising All-Solid-State Batteries for Future Electric Vehicles. ACS Energy Lett.
2020, 5, 3221-3223.
[2] Christian Heubner, Sebastian Maletti, Henry Auer, Juliane Hüttl, Karsten Voigt, Oliver Lohrberg, Kristian Nikolowski, Mareike Partsch, and Alexander Michaelis. From Lithium-Metal toward Anode-Free Solid-State Batteries: Current Developments, Issues, and Challenges. Adv. Func. Mater. 2021, 31(51), 2106608.
[3] Yuan Tian, Yongling An, Chuanliang Wei, Huiyu Jiang, Shenglin Xiong, Jinkui Feng, and Yitai Qian. Recently advances and perspectives of anode-free rechargeable batteries. Nano Energy. 2020, 78, 105344.
[4] Eric Kazyak, Michael J. Wang, Kiwoong Lee, Srinivas Yadavalli, Adrian J. Sanchez, M.D. Thouless, Jeff Sakamoto, and Neil P. Dasgupta. Understanding the electro-chemo-mechanics of Li plating in anode-free solid-state batteries with operando 3D microscopy. Matter. 2022, 5(11), 3912-3934.
(Invited) Treated Perfluorosulfonic Acid Ionomer Layer with Dual Oxygen Transport Pathways for PEMFC Cathode Catalyst Layer
Authors: Nguyen Trung Van , Li Yuanchao 
Published: December 2024

A hydrophobic treatment was developed to reduce the liquid water saturation level and increase its removal rate from the cathode catalyst layer (CL) of a PEM fuel cell with the expected outcome to be higher performance in the transport-controlled region. However, test results show improvement (> 200% increase in peak power)[1] in both kinetic and transport-controlled regions. Further investigation by mathematical modeling and neutron reflectometry shows the treatment affects the CL in two ways. First, the ionomer/gas phase interface in the pores of the CL becomes more hydrophobic. This facilitates less liquid water coverage of the ionomer layer surface and faster water drainage from the CL that results in better performance at high current densities, which is as expected. Second, it affects the microstructures of the ionomer phase and causes it to separate into two regions, a larger more hydrophobic (or less hydrophilic) region with fewer sulfonic acid groups and therefore lower water hydration levels and a smaller less hydrophobic (or more hydrophilic) region with more ionic groups with higher hydration levels. The more hydrophobic region, which facilitates faster liquid water removal from its interface with the gas pores and direct access to the oxygen gas at higher current densities, provides a higher oxygen solubility pathway to the catalyst active sites in CL at both low and high current densities leading to higher fuel cell performance over the whole polarization curve. See image. The ratio of these two regions can be controlled by the treatment process. This presentation will discuss the hydrophobic treatment process and the major findings of this study.
References

Regis P. Dowd, Yuanchao Li, Trung Van Nguyen, “Controlling the Ionic Polymer/Gas Interface Property of a PEM Fuel Cell Catalyst Layer During Membrane Electrode Assembly Fabrication,” Appl. Electrochem., 50 (10) 993-1006 (2020).

Yuanchao Li and Trung Van Nguyen, “A One-Dimensional Model of the Cathode Catalyst Layer of a PEM Fuel cell Hydrophobically Treated for Water Management,” J. Electrochemical Society, 169 114505 (2022).

Figure 1