Origin of enhanced water oxidation activity in an iridium single atom anchored on NiFe oxyhydroxide catalyst

Published

August 31, 2021

Author(s)

Xueli Zheng, Jing Tang, Allesandro Gallo, Jose A. Garrido Torres, Xiaoyun Yu, Peter Ercius, Haiyan Mao, Emily Been, Constantine J. Athanitis, Sirine C. Fakra, Chengyu Song, Ryan Davis, Jeffrey A. Reimer, John Vinson, Michal Bajdich, Yi Cui

Abstract

The efficiency of the synthesis of renewable fuels and feedstocks from electrical sources is limited, at present, by the sluggish water oxidation reaction. Single-atom catalysts (SACs) with a controllable coordination environment and exceptional atom utilization efficiency open new paradigms toward designing high-performance water oxidation catalysts. Here, using operando X-ray absorption spectroscopy measurements with calculations of spectra and electrochemical activity, we demonstrate that the origin of water oxidation activity of IrNiFe SACs is the presence of highly oxidized Ir single atom (Ir5.3+) in the NiFe oxyhydroxide under operating conditions. We show that the optimal water oxidation catalyst could be achieved by systematically increasing the oxidation state and modulating the coordination environment of the Ir active sites anchored atop the NiFe oxyhydroxide layers. Based on the proposed mechanism, we have successfully anchored Ir single-atom sites on NiFe oxyhydroxides (Ir0.1/Ni9Fe SAC) via a unique in situ cryogenic–photochemical reduction method that delivers an overpotential of 183 mV at 10 mA ⋅ cm−2 and retains its performance following 100 h of operation in 1 M KOH electrolyte, outperforming the reported catalysts and the commercial IrO2 catalysts. These findings open the avenue toward an atomic-level understanding of the oxygen evolution of catalytic centers under in operando conditions.

Citation

Proceedings of the National Academy of Sciences

Volume

118

Pub Type

Journals

Download Paper

https://doi.org/10.1073/pnas.2101817118

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Citation

Zheng, X. , Tang, J. , Gallo, A. , Garrido Torres, J. , Yu, X. , Ercius, P. , Mao, H. , Been, E. , Athanitis, C. , Fakra, S. , Song, C. , Davis, R. , Reimer, J. , Vinson, J. , Bajdich, M. and Cui, Y. (2021), Origin of enhanced water oxidation activity in an iridium single atom anchored on NiFe oxyhydroxide catalyst, Proceedings of the National Academy of Sciences, [online], https://doi.org/10.1073/pnas.2101817118, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=929178 (Accessed April 18, 2024)