Oxygen evolution reaction over catalytic single-site Co in a well-defined brookite TiO2 nanorod surface

Liu, Chang; Qian, Jin; Ye, Yifan; Zhou, Hua; Sun, Cheng-Jun; Sheehan, Colton; Zhang, Zhiyong; Wan, Gang; Liu, Yi-Sheng; Guo, Jinghua; Li, Shuang; Shin, Hyeyoung; Hwang, Sooyeon; Gunnoe, T. Brent; Goddard, William A.; Zhang, Sen

doi:10.1038/s41929-020-00550-5

Oxygen evolution reaction over catalytic single-site Co in a well-defined brookite TiO₂ nanorod surface

Journal Article · Mon Dec 14 00:00:00 EST 2020 · Nature Catalysis

DOI:https://doi.org/10.1038/s41929-020-00550-5· OSTI ID:1760638

^[1]; Qian, Jin ^[2]; Ye, Yifan ^[3]; ^[4]; Sun, Cheng-Jun ^[4]; Sheehan, Colton ^[1]; Zhang, Zhiyong ^[1]; Wan, Gang ^[5]; ^[3]; ^[3]; Li, Shuang ^[6]; ^[2]; Hwang, Sooyeon ^[6]; Gunnoe, T. Brent ^[1]; ^[2]; ^[1]

Univ. of Virginia, Charlottesville, VA (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Argonne National Lab. (ANL), Argonne, IL (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Efficient electrocatalysts for the oxygen evolution reaction (OER) are paramount to the development of electrochemical devices for clean energy and fuel conversion. However, the structural complexity of heterogeneous electrocatalysts makes it a great challenge to elucidate the surface catalytic sites and OER mechanisms. Here, we report that catalytic single-site Co in a well-defined brookite TiO₂ nanorod (210) surface (Co-TiO₂) presents turnover frequencies that are among the highest for Co-based heterogeneous catalysts reported to date, reaching 6.6 ± 1.2 and 181.4 ± 28 s^-1 at 300 and 400 mV overpotentials, respectively. Based on grand canonical quantum mechanics calculations and the single-site Co atomic structure validated by in situ and ex situ spectroscopic probes, we have established a full description of the catalytic reaction kinetics for Co-TiO₂ as a function of applied potential, revealing an adsorbate evolution mechanism for the OER. The computationally predicted Tafel slope and turnover frequencies exhibit exceedingly good agreement with experiment.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: Canadian Light Source, Inc.; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 1760638

Alternate ID(s):: OSTI ID: 1775495

Report Number(s):: BNL--220799-2021-JAAM

Journal Information:: Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 1 Vol. 4; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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