Adsorption of Molecules on Defective CeO2 for Advanced Catalysis

Adsorption of molecules on active sites of heterogeneous catalysts significantly affects their catalytic performance, which provides a perspective to understand the catalytic process/mechanism at the atomic level and to establish structure–function relationships. This Perspective illustrates a strong correlation between the adsorption of reactants on CeO2-based catalysts and their improved catalytic activity and/or selectivity for various transformations. Regulating the oxygen defect of CeO2 provides an effective approach to construct two typical active sites of a frustrated Lewis pair (FLP) and dual-active site. Benefiting from the unique spatial and electronic structures, the FLP sites exhibit an "embedded" adsorption configuration of small molecules, promoting their effective activation and transformation. The dual-active sites constructed by metal clusters and oxygen vacancy of CeO2 could break the competitive adsorption of various molecules and thereafter enable highly active and selective hydrogenations. Finally, the possibilities and challenges in the adsorption behaviors of various molecules on CeO2-based catalysts are outlined. The tailorability of adsorption strength and selective configuration of molecules on active sites are anticipated to stimulate and guide the design of high-performing catalysts.