A Specific Review of CO2 Catalytic Conversion Reactions Based on the Concept of Catalytic Sites Contiguity

Thermocatalytic conversions of carbon dioxide (CO₂) to value‐added products offer promising approaches to achieving net negative emissions. The catalysts for CO₂ conversions, particularly for CO₂ hydrogenation reactions, usually involve more than one catalytic sites working together. In this review, we first introduce the advanced characterization techniques used to identify the catalytic sites in CO₂ hydrogenation catalysts, sites for hydrogen (H₂) activation and CO₂ adsorption/activation. We then discuss how the dual or multiple‐site configurations influence the catalytic activity and selectivity in reactions such as reverse water‐gas shift (RWGS), CO₂ methanation, and CO₂ hydrogenation for methanol (MeOH). We finally explain the Catalytic Sites Contiguity (CSC) concept that our research group developed from the work in CO₂ reforming of methane and use it to understand the relationship between the spatial arrangement of catalytic sites and the efficiency of reactant activation and conversion in recent publications on MeOH synthesis from CO₂ hydrogenation. We hope our insights into the impact of CSC on catalytic performance lead to a potential top‐down design method in optimizing the CO₂ hydrogenation catalysts.