Monovalent to Trivalent Materials: Catalyst Development in Electrolysis through Manipulation of the Complex Interface

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Electrocatalysis presents a challenging frontier for our physico-chemical understanding of the surface morphology and catalytic properties of a material: synthesis methods eschew the typical thermodynamically stable facets of (111) in metals and (110) in rutile MO 2 , often featuring a mixture of facet families and core-shell architectures; in addition, reactions are mediated by surface environments related to the varying potentials of OER, pH, and electrolyte ions. 1-4 Catalysts expose a range of surface, heterogeneous morphologies due to the experimental processes of dissolution in the electrolyte, synthesis techniques, and passivation at higher potentials leading to a corresponding need to understand the catalytic changes at atomic and electronic levels of theory. Here, we show-case how understanding of the mechanisms available to pure materials e.g. Pt, IrO 2 , NiO can inform our manipulation of mixed-metal, -metal oxide materials to activate specific steps of electrolysis (hydrogen evolution, oxygen evolution). 5-7 Catalyst architectures such as core-shell and doped-surfaces will be considered with particular attention paid to how different mechanisms and binding trends may change due to the complex, heterogeneous interface as compared to a pure material. In reality, electrolysis may involve many different pathways and a consideration of low-coverage and higher-coverage pathways involving adsorbate-adsorbate interactions may empower theoretical predictions to discover more active catalysts. 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. This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36–08GO28308. (1) Stamenkovic, V. R.; Fowler, B.; Mun, B. S.; Wang, G.; Ross, P. N.; Lucas, C. A.; Marković, N. M. Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability. Science 2007 , 315 (5811), 493-497. DOI: doi:10.1126/science.1135941. (2) Stamenkovic, V. R.; Mun, B. S.; Arenz, M.; Mayrhofer, K. J. J.; Lucas, C. A.; Wang, G.; Ross, P. N.; Markovic, N. M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nature Materials 2007 , 6 (3), 241-247. DOI: 10.1038/nmat1840. (3) Alia, S. M.; Anderson, G. C. Iridium Oxygen Evolution Activity and Durability Baselines in Rotating Disk Electrode Half-Cells. Journal of The Electrochemical Society 2019 , 166 (4), F282-F294. (4) Alia, S. M.; Ha, M.-A.; Anderson, G. C.; Ngo, C.; Pylypenko, S.; Larsen, R. E. The Roles of Oxide Growth and Sub-Surface Facets in Oxygen Evolution Activity of Iridium and Its Impact on Electrolysis. Journal of The Electrochemical Society 2019 , 166 (15), F1243-F1252. DOI: 10.1149/2.0771915jes. (5) Ha, M.-A.; Alia, S. M.; Norman, A. G.; Miller, E. M. Fe-Doped Ni-Based Catalysts Surpass Ir-Baselines for Oxygen Evolution Due to Optimal Charge-Transfer Characteristics. ACS Cat. 2024 , 17347-17359. DOI: 10.1021/acscatal.4c04489. (6) Ha, M.-A.; Larsen, R. E. Multiple Reaction Pathways for the Oxygen Evolution Reaction May Contribute to IrO2 (110)’s High Activity. Journal of The Electrochemical Society 2021 , 168 (2), 024506. (7) Alia, S. M.; Ha, M.-A.; Ngo, C.; Anderson, G. C.; Ghoshal, S.; Pylypenko, S. Platinum–Nickel Nanowires with Improved Hydrogen Evolution Performance in Anion Exchange Membrane-Based Electrolysis. ACS Cat. 2020 , 10 (17), 9953-9966. DOI: 10.1021/acscatal.0c01568. Figure 1. Schematic of the multitude of reaction networks that may be available to a system moving from a pure metal or oxide to a mixed-metal, -metal oxide interface. Figure 1

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