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

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 Cu 1 /CeO 2 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.