Photothermal Synergistic Effect Induces Bimetallic Cooperation to Modulate Product Selectivity of CO₂ Reduction on...

Product selectivity of solar-driven CO₂ reduction and H₂O oxidation reactions has been successfully controlled by tuning the spatial distance between Pt/Au bimetallic active sites on different crystal facets of CeO₂ catalysts. The replacement depth of Ce atoms by monatomic Pt determines the distance between bimetallic sites, while Au clusters are deposited on the surface. This space configuration creates a favourable microenvironment for the migration of active hydrogen species (*H). The *H is generated via the activation of H₂O on monatomic Pt sites and migrate towards Au clusters with a strong capacity for CO₂ adsorption. Under concentrated solar irradiation, selectivity of the (100) facet towards CO is 100 %, and the selectivity of the (110) and (111) facets towards CH₄ is 33.5 % and 97.6 %, respectively. Notably, the CH₄ yield on the (111) facet is as high as 369.4 μmol/g/h, and the solar-to-chemical energy efficiency of 0.23 % is 33.8 times higher than that under non-concentrated solar irradiation. The impacts of high-density flux photon and thermal effects on carriers and *H migration at the microscale are comprehensively discussed. This study provides a new avenue for tuning the spatial distance between active sites to achieve optimal product selectivity.