CaltechAUTHORS
Published June 4, 2025 | Published
Journal Article Metadata-only

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

Liu, Chang1 ORCID icon
Kwon, Soonho2 ORCID icon
Godbold, Perrin1
Johnson, Grayson1 ORCID icon
Hwang, Sooyeon3 ORCID icon
Sun, Chengjun4
Zhou, Hua4 ORCID icon
Goddard, William A., III2 ORCID icon
Zhang, Sen1 ORCID icon
  • 1. ROR icon University of Virginia
  • 2. ROR icon California Institute of Technology
  • 3. ROR icon Brookhaven National Laboratory
  • 4. ROR icon Argonne National Laboratory

Abstract

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.

Copyright and License

Copyright © 2025 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0 .

Supplemental Material

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.5c05795.

  • Experimental section, Figures S1–S34, and Tables S1–S4 (PDF)

  • Geometry files with header information with energy, electrochemical potential, and total number of electrons (ZIP)

Contributions

C.L. and S.K. contributed equally.

Conflict of Interest

The authors declare no competing financial interest.

Acknowledgement

The electrochemical study and computational work were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division (DE-SC00234430). Support for the catalyst synthesis and structural characterization was provided by US National Science Foundation (CBET-2004808). This work used Stampede3 at Texas Advanced Computing Center through allocation DMR160114 from the Advanced Cyberinfrastructure Coordination Ecosystem: Services & Support (ACCESS) program, which is supported by National Science Foundation grants #2138259, #2138286, #2138307, #2137603, and #2138296. S.K. acknowledges support from the Resnick Sustainability Institute at Caltech. This research used Electron Microscopy facilities of the Center for Functional Nanomaterials (CFN), which is a U.S. Department of Energy Office of Science User Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Additional details

Funding Dates Caltech Custom Metadata
Created:
July 23, 2025
Modified:
July 23, 2025