Facet-Dependent Oxygen Evolution Reaction Activity of IrO₂ from Quantum Mechanics and Experiments

Creators: Kwon, Soonho; Stoerzinger, Kelsey A.; Rao, Reshma; Qiao, Liang; Goddard, William A., III¹; Shao-Horn, Yang

1. California Institute of Technology

Abstract

The diversity of chemical environments present on unique crystallographic facets can drive dramatic differences in catalytic activity and the reaction mechanism. By coupling experimental investigations of five different IrO₂ facets and theory, we characterize the detailed elemental steps of the surface redox processes and the rate-limiting processes for the oxygen evolution reaction (OER). The predicted complex evolution of surface adsorbates and the associated charge transfer as a function of applied potential matches well with the distinct redox features observed experimentally for the five facets. Our microkinetic model from grand canonical quantum mechanics (GC-QM) calculations demonstrates mechanistic differences between nucleophilic attack and O–O coupling across facets, providing the rates as a function of applied potential. These GC-QM calculations explain the higher OER activity observed on the (100), (001), and (110) facets and the lower activity observed for the (101) and (111) facets. This combined study with theory and experiment brings new insights into the structural features that either promote or hinder the OER activity of IrO₂, which are expected to provide parallels in structural effects on other oxide surfaces.

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Acknowledgement

The computational work was supported by the Liquid Sunlight Alliance, which is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under award no. DE-SC0021266 (W.A.G.), and by an individual fellowship from the Resnick Sustainability Institute at Caltech (S.K.). This work used Stampede3 at Texas Advanced Computing Center through allocation DMR160114 from the Advanced Cyberinfrastructure Coordination Ecosystem: Services & Support (ACCESS) program, which is supported by National Science Foundation grants #2138259, #2138286, #2138307, #2137603, and #2138296. (W.A.G.). K.A.S. acknowledges support from the National Science Foundation under grant no. 2041153.

Contributions

S.K. and K.A.S. contributed equally to this work.

Data Availability

Experimental and computational details, additional experimental results and DFT calculations, supplemental figures and tables, and appendix for microkinetic equations (PDF)

Conflict of Interest

The authors declare no competing financial interest.

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