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

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

doi:10.1073/pnas.2101817118

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

Journal Article · Tue Aug 31 00:00:00 EDT 2021 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2101817118· OSTI ID:1827344

Zheng, Xueli ^[1]; ^[2]; ^[3]; Garrido Torres, Jose A. ^[3]; Yu, Xiaoyun ^[1]; ^[1]; Been, Emily May ^[1]; Ercius, Peter ^[4]; Mao, Haiyan ^[5]; Fakra, Sirine C. ^[6]; Song, Chengyu ^[4]; ^[7]; ^[5]; ^[8]; ^[3]; Cui, Yi ^[2]

Stanford Univ., CA (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

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 (Ir^5.3+) 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 (Ir_0.1/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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; SC0008685

OSTI ID:: 1827344

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 36 Vol. 118; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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

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