Origin of enhanced water oxidation activity in an iridium single atom anchored on NiFe oxyhydroxide catalyst
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 operandomore »
- Authors:
-
[2];
[3];
[1];
[7];
[5];
[8];
[3];
- 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)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1827344
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515; SC0008685
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Volume: 118; Journal Issue: 36; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; highly oxidized Ir sites; water oxidation; operando X-ray absorption spectroscopy; DPT calculations
Citation Formats
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, and Cui, Yi. Origin of enhanced water oxidation activity in an iridium single atom anchored on NiFe oxyhydroxide catalyst. United States: N. p., 2021.
Web. doi:10.1073/pnas.2101817118.
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. Origin of enhanced water oxidation activity in an iridium single atom anchored on NiFe oxyhydroxide catalyst. United States. https://doi.org/10.1073/pnas.2101817118
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, and Cui, Yi. Tue .
"Origin of enhanced water oxidation activity in an iridium single atom anchored on NiFe oxyhydroxide catalyst". United States. https://doi.org/10.1073/pnas.2101817118. https://www.osti.gov/servlets/purl/1827344.
@article{osti_1827344,
title = {Origin of enhanced water oxidation activity in an iridium single atom anchored on NiFe oxyhydroxide catalyst},
author = {Zheng, Xueli and Tang, Jing and Gallo, Alessandro and Garrido Torres, Jose A. and Yu, Xiaoyun and Athanitis, Constantine J. and Been, Emily May and Ercius, Peter and Mao, Haiyan and Fakra, Sirine C. and Song, Chengyu and Davis, Ryan C. and Reimer, Jeffrey A. and Vinson, John and Bajdich, Michal and Cui, Yi},
abstractNote = {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.},
doi = {10.1073/pnas.2101817118},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 36,
volume = 118,
place = {United States},
year = {Tue Aug 31 00:00:00 EDT 2021},
month = {Tue Aug 31 00:00:00 EDT 2021}
}
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