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Methanol Dehydrogenation via Rutile TiO2-Based Single-Atom Catalysts: Structure, Stability, and Selectivity

  • CHEMICAL KINETICS AND CATALYSIS
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Abstract

Single-atom catalysts possessing distinct geometric and electronic structures have permitted the highly efficient performance and tunable catalytic property for methanol dehydrogenation. The structure and stability of rutile TiO2-based single-atom catalyst, and the selectivity for methanol dehydrogenation were addressed via DFT + U calculations. The stable single-atom catalysts: rutile Co1@TiO2 and Ru1/TiO2, have been identified from all the possible terminations. Their interface structures, stabilities in thermodynamics, and selectivity for methanol dehydrogenation are determined by the two important parameters: metal-atom doping site and surficial oxygen stoichiometry. In particular, the substitutional rutile Co1@TiO2(110) facet can boost direct methanol dehydrogenation, activate O–H and C–H bonds, and then release formaldehyde, H2, and CO. The rutile Ru1/TiO\(_{{2 + x}}\)(110) one, a supported neutral Ru atom with additional oxygen on the stoichiometric rutile TiO2(110) facet, prefers to facilitate partial oxidation of methanol.

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Funding

This work was supported by National Natural Science Foundation of China (grant no. 21703194).

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Authors and Affiliations

  1. School of Materials and Chemical Engineering, Xuzhou University of Technology, 221018, Xuzhou, China

    Ju Wang, Yusheng Liu, Wenyou Zhu, Wenchang Zhuang & Lin Tian

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  1. Ju Wang
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Correspondence to Ju Wang or Lin Tian.

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Supplementary Information

The supporting information includes computational details for chemical potentials of single-atom catalysts, structure and stability for all the terminations of single-atom Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au catalysts at the exposed rutile TiO2(110) facets, the key intermediates of direct methanol dehydrogenation at the substitutional rutile Co1@TiO2(110) facet, and the key intermediates of methanol partial oxidation at the supported rutile Ru1/TiO2(110) facet.

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Wang, J., Liu, Y., Zhu, W. et al. Methanol Dehydrogenation via Rutile TiO2-Based Single-Atom Catalysts: Structure, Stability, and Selectivity. Russ. J. Phys. Chem. 97, 2958–2965 (2023). https://doi.org/10.1134/S0036024423130125

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