Photothermal catalysis for CO₂ hydrogenation to C₂⁺ products: Mechanisms, catalytic system, and selectivity control

The selective hydrogenation of carbon dioxide (CO₂) into multi-carbon (C₂⁺) products offers a promising approach to mitigate greenhouse gas emissions while producing high-energy-density fuels compatible with existing petrochemical infrastructure. Photothermal catalysis, which couples photonic excitation with thermal activation, has emerged as an efficient strategy to overcome the kinetic and thermodynamic barriers associated with CO₂ activation and C-C bond formation. This review summarizes recent advances in photothermal CO₂ hydrogenation, emphasizing the CO₂ Fischer Tropsch mechanism, key surface intermediates, and structure–function relationships governing C-C coupling efficiency. Representative catalyst systems, including LDH derived bimetallic alloys, plasmonic nanostructures, metal/metal oxide interfaces, and promoter-modified hybrids, are critically evaluated in terms of their performance, design strategies, and mechanistic insights. Remaining challenges, such as active-site stabilization, selectivity control, and integration into scalable solar-driven reactors, are discussed to identify pathways toward efficient, selective, and industrially viable photothermal CO₂ hydrogenation to C₂⁺ products. This review contributes to photothermal catalysis research by establishing a comprehensive mechanistic and design framework that correlates light matter interactions with catalytic performance, thereby providing guidance for the rational development of next generation solar driven CO₂ conversion systems.