Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 34, Pages 10710-10720Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b02719
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Funding
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DOE BES)
- UChicago Argonne, LLC [DE-AC02-06CH11357]
- Argonne Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center - DOE BES [DE-SC0001059]
- DOE BES Chemical Sciences, Geosciences and Biosciences Division [DE-AC02-06CH11357]
- DOE BES, Materials Sciences and Engineering Division [DE-AC02-76SF00515]
- U.S. DOE BES [DE-AC02-06CH11357, DE-FG02-03-ER15457]
- R&D Convergence Program of MSIP (Ministry of Science, ICT and Future Planning)
- NST (National Research Council of Science & Technology) of Republic of Korea [CRC-14-1-KRICT]
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Non-noble-metal, thin-film oxides are widely investigated as promising catalysts for oxygen evolution reactions (OER). Amorphous cobalt oxide films electrochemically formed in the presence of borate (CoBi) and phosphate (CoPi) share a common cobaltate domain building block, but differ significantly in OER performance that derives from different electron proton charge transport properties. Here, we use a combination of L edge synchrotron X-ray absorption (XAS), resonant X-ray emission (RXES), resonant inelastic X-ray scattering (RIXS), resonant Raman (RR) scattering, and high-energy X-ray pair distribution function (PDF) analyses that identify electronic and structural factors correlated to the charge transport differences for CoPi and CoBi. The analyses show that CoBi is composed primarily of cobalt in octahedral coordination, whereas CoPi contains approximately 17% tetrahedral Co(II), with the remainder in octahedral coordination. Oxygen-mediated 4p-3d hybridization through Co-O-Co bonding was detected by RXES and the intersite dd excitation was observed by RIXS in CoBi, but not in CoPi. RR shows that CoBi resembles a disordered layered LiCoO2-like structure, whereas CoPi is amorphous. Distinct domain models in the nanometer range for CoBi and CoPi have been proposed on the basis of the PDF analysis coupled to XAS data. The observed differences provide information on electronic and structural factors that enhance oxygen evolving catalysis performance.
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