Highly Selective Photocatalytic CO2 Methanation with Water Vapor on Single‐Atom Platinum‐Decorated Defective Carbon Nitride

Abstract Solar‐driven CO 2 methanation with water is an important route to simultaneously address carbon neutrality and produce fuels. It is challenging to achieve high selectivity in CO 2 methanation due to competing reactions. Nonetheless, aspects of the catalyst design can be controlled with meaningful effects on the catalytic outcomes. We report highly selective CO 2 methanation with water vapor using a photocatalyst that integrates polymeric carbon nitride (CN) with single Pt atoms. As revealed by experimental characterization and theoretical simulations, the widely explored Pt−CN catalyst is adapted for selective CO 2 methanation with our rationally designed synthetic method. The synthesis creates defects in CN along with formation of hydroxyl groups proximal to the coordinated Pt atoms. The photocatalyst exhibits high activity and carbon selectivity (99 %) for CH 4 production in photocatalytic CO 2 reduction with pure water. This work provides atomic scale insight into the design of photocatalysts for selective CO 2 methanation.