Surface-Controlled TiO2 Nanocrystals with Catalytically Active Single-Site Co Incorporation for the Oxygen Evolution Reaction

Liu, Chang; Kwon, Soonho; Godbold, Perrin; Johnson, Grayson; Hwang, Sooyeon; Sun, Chengjun; Zhou, Hua; Goddard, William A.; Zhang, Sen

doi:10.1021/jacs.5c05795

Title: Surface-Controlled TiO₂ Nanocrystals with Catalytically Active Single-Site Co Incorporation for the Oxygen Evolution Reaction

Journal Article · Tue May 27 00:00:00 UTC 2025 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.5c05795 · OSTI ID:2570592

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University of Virginia, Charlottesville, VA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
California Institute of Technology, Pasadena, CA (United States)
University of Virginia, Charlottesville, VA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

The design of advanced electrocatalysts is often hindered by uncertainties in identifying and controlling the active surfaces and catalytic centers within heterogeneous materials. Here we present the synthesis of single-site Co catalysts, substitutionally doped into surface-controlled TiO₂ anatase nanocrystals, aimed at enhancing the oxygen evolution reaction (OER). Grand canonical quantum mechanics calculations reveal that the kinetics of the OER, following an adsorbate evolution mechanism, is markedly influenced by the coordination environment of Co. The simulations suggest significantly higher turnover frequencies when Co is doped into the (001) surface of TiO₂ compared to the (101) surface. Consistent with the computational findings, experimental results show that Co-doped TiO₂ (Co-TiO₂) nanoplates with selectively exposed {001} surfaces exhibit enhanced current densities and turnover frequencies compared to Co-TiO₂ nanobipyramids with {101} surfaces. This study highlights the synergy between theoretical calculations and precision synthesis in the development of more effective catalysts.

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Research Organization:: Brookhaven National Lab; Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: US National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

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

OSTI ID:: 2570592

Report Number(s):: BNL-228321-2025-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 22 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Surface-Controlled TiO2 Nanocrystals with Catalytically Active Single-Site Co Incorporation for the Oxygen Evolution Reaction

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