Surface-Controlled TiO₂ Nanocrystals with Catalytically Active Single-Site Co Incorporation for the Oxygen Evolution Reaction
Creators
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1.
University of Virginia
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2.
California Institute of Technology
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3.
Brookhaven National Laboratory
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4.
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.
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Experimental section, Figures S1–S34, and Tables S1–S4 (PDF)
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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
- Office of Basic Energy Sciences
- DE-SC00234430
- Resnick Sustainability Institute
- Division of Chemical, Bioengineering, Environmental, and Transport Systems
- 2004808
- Advanced Cyberinfrastructure Coordination Ecosystem: Services & Support
- Stampede3 at Texas Advanced Computing Center DMR160114
- National Science Foundation
- 2138259
- National Science Foundation
- 2138286
- National Science Foundation
- 2138307
- National Science Foundation
- 2137603
- National Science Foundation
- 2138296
- Office of Science
- Center for Functional Nanomaterials (CFN) DE-SC0012704
- Office of Science
- Advanced Photon Source DE-AC02-06CH11357
Dates
- Available
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2025-05-27