Resolution of Electronic and Structural Factors Underlying Oxygen-Evolving Performance in Amorphous Cobalt Oxide Catalysts

Kwon, Gihan; Jang, Hoyoung; Lee, Jun -Sik; Mane, Anil; Mandia, David J.; Soltau, Sarah R.; Utschig, Lisa M.; Martinson, Alex B. F.; Tiede, David M.; Kim, Hacksung; Kim, Jungho

doi:10.1021/jacs.8b02719

Title: Resolution of Electronic and Structural Factors Underlying Oxygen-Evolving Performance in Amorphous Cobalt Oxide Catalysts

Journal Article · Fri Jul 20 00:00:00 EDT 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b02719· OSTI ID:1472118

^[1]; Jang, Hoyoung ^[2]; Lee, Jun -Sik ^[3]; Mane, Anil ^[4]; Mandia, David J. ^[4];

^[5];

^[6];

^[1];

^[4]

Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Pohang Accelerator Lab., Gyeongbuk (Republic of Korea)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Bridgewater State Univ., Bridgewater, MA (United States)
Argonne National Lab. (ANL),Lemont, IL (United States)

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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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-03ER15457; AC02-06CH11357; SC0001059; CRC-14-1-KRICT

OSTI ID:: 1472118

Alternate ID(s):: OSTI ID: 1870993

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 34; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 42 works

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Cobalt oxide
Cobalt borate
Cobalt phosphate
Water oxidation
Water splitting
Resonant X-ray emission spectroscopy (RXES)
Resonant inelastic X-ray scattering (RIXS)
Resonant Raman spectroscopy
Cobalt L3 edge X-ray absorption spectroscopy