Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO2 single-atom catalyst

Zheng Chen; Zhangyun Liu; Xin Xu

doi:10.1038/s41467-023-38307-w

Dynamic evolution of the active center driven by hemilabile coordination in Cu/CeO₂ single-atom catalyst

Nat Commun. 2023 May 2;14(1):2512. doi: 10.1038/s41467-023-38307-w.

Authors

Zheng Chen¹, Zhangyun Liu¹, Xin Xu^{2

3}

Affiliations

¹ Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, MOE Key Laboratory of Computational Physical Sciences, Department of Chemistry, Fudan University, Shanghai, 200433, P. R. China.
² Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, MOE Key Laboratory of Computational Physical Sciences, Department of Chemistry, Fudan University, Shanghai, 200433, P. R. China. xxchem@fudan.edu.cn.
³ Hefei National Laboratory, Hefei, 230088, P. R. China. xxchem@fudan.edu.cn.

Abstract

Hemilability is an important concept in homogeneous catalysis where both the reactant activation and the product formation can occur simultaneously through a reversible opening and closing of the metal-ligand coordination sphere. However, this effect has rarely been discussed in heterogeneous catalysis. Here, by employing a theoretical study on CO oxidation over substituted Cu₁/CeO₂ single atom catalysts, we show that dynamic evolution of metal-support coordination can significantly change the electronic structure of the active center. The evolution of the active center is shown to either strengthen or weaken the metal-adsorbate bonding as the reaction proceeds from reactants, through intermediates, to products. As a result, the activity of the catalyst can be increased. We explain our observations by extending hemilability effects to single atom heterogenous catalysts and anticipate that introducing this concept can offer a new insight into the important role active site dynamics have in catalysis toward the rational design of more sophisticated single atom catalyst materials.