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https://doi.org/10.53941/mi.2025.100002
Wei, X., Chen, Y., Zhang, Y., Zhang, L., Ma, L., Yung, M. M., & Zhang, S. Constructing Co Cluster Sites for Selective CO<sub>2</sub> Hydrogenation via Phase Segregation from Co-Doped TiO<sub>2</sub> Nanocrystals. Materials and Interfaces. 2025. doi: https://doi.org/10.53941/mi.2025.100002
Volume 2, Issue 1, 2025
Copyright (c) 2025 by the authors.
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This work is licensed under a Creative Commons Attribution 4.0 International License.

Article

Constructing Co Cluster Sites for Selective CO2 Hydrogenation via Phase Segregation from Co-Doped TiO2 Nanocrystals

Xiangru Wei 1, Yizhen Chen 1, Yulu Zhang 1, Liyue Zhang 1, Lu Ma 2, Matthew M. Yung 3 and Sen Zhang 1,*

1 Department of Chemistry, University of Virginia, Charlottesville, VA 22904, USA

2 National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY 11973, USA

3 Bioenergy Science and Technology Directorate, National Renewable Energy Laboratory, Denver West Parkway,
Golden, CO 80401, USA

* Correspondence: sz3t@virginia.edu

Received: 7 November 2024; Revised: 2 January 2025; Accepted: 3 January 2025; Published: 23 January 2025

Abstract: This article presents a Co phase segregation strategy for creating stable Co cluster catalytic sites on TiO2, enabling selective CO2 hydrogenation to CO. Through oxidative calcination, pre-synthesized Co-doped brookite TiO2 nanorods transform into a mixed TiO2 phase, leading to the phase segregation of Co species. The resulting Co clusters, stabilized by strong Co-TiO2 interactions during reductive CO2 hydrogenation, effectively suppress the formation of larger nanoparticles. The undercoordinated sites of these clusters promote a high CO production rate with near-unit selectivity, contrasting with Co nanoparticles, which favor CH4 formation under identical conditions. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis indicates that the weakened CO adsorption on Co clusters is key to their enhanced CO selectivity, highlighting this method as a promising approach for efficient CO2 utilization.

Keywords:

CO2 hydrogenation heterogeneous catalysis cluster sites selectivity phase segregation

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