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High-valence metals improve oxygen evolution reaction performance by modulating 3d metal oxidation cycle energetics

Journal Article · · Nature Catalysis
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  1. Fudan Univ., Shanghai (China). State Key Lab. of Molecular Engineering of Polymers, Lab. of Advanced Materials
  2. King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia). KAUST Catalysis Center
  3. Univ. of Toronto, ON (Canada)
  4. Ecole Polytechnique Federale Lausanne (Switzerland). Inst. of Chemical Sciences and Engineering
  5. Canadian Light Sources, Inc., Saskatoon, SK (Canada)
  6. Univ. of Alabama, Birmingham, AL (United States)
  7. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  8. National Synchrotron Radiation Research Center, Hsinchu (Taiwan)
  9. Chinese Academy of Sciences (CAS), Beijing (China). Beijing Synchrotron Radiation Facility, Inst. of High Energy Physics
  10. Soochow Univ., Suzhou (China). Inst. of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Lab. for Carbon-Based Functional Materials & Devices
  11. Nanjing Univ. (China)
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Multimetal oxyhydroxides have recently been reported that outperform noble metal catalysts for oxygen evolution reaction (OER). In such 3d-metal-based catalysts, the oxidation cycle of 3d metals has been posited to act as the OER thermodynamic-limiting process; however, further tuning its energetics is challenging due to similarities among the electronic structures of neighboring 3d metal modulators. Here we report a strategy to reprogram the Fe, Co, and Ni oxidation cycles by incorporating high-valence transition-metal modulators X (X=W, Mo, Nb, Ta, Re, and MoW). Furthermore, we use in-situ/ex-situ soft and hard X-ray absorption spectroscopies to characterize the oxidation transition in modulated NiFeX and FeCoX oxyhydroxide catalysts, and conclude that the lower OER overpotential is facilitated by the readier oxidation transition of 3d metals enabled by high-valence modulators. We report a ~ 17 fold mass activity enhancement compared with OER catalysts widely employed in industrial water-splitting electrolyzers.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NSFC); Ministry of Science and Technology of the Republic of China (MOST); USDOE Office of Science (SC), Basic Energy Sciences (BES); STCSM; SHMEC
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1780685
Journal Information:
Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 12 Vol. 3; ISSN 2520-1158
Publisher:
Springer NatureCopyright Statement
Country of Publication:
United States
Language:
English

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Raw data for "High-valence metals improve OER performance by modulating 3d metal oxidation cycle energetics" text January 2020

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