Polymorph selection towards photocatalytic gaseous CO2 hydrogenation

Titanium dioxide is the only known material that can enable gas-phase CO2 photocatalysis in its anatase and rutile polymorphic forms. Materials engineering of polymorphism provides a useful strategy for optimizing the performance metrics of a photocatalyst. In this paper, it is shown that the less well known rhombohedral polymorph of indium sesquioxide, like its well-documented cubic polymorph, is a CO2 hydrogenation photocatalyst for the production of CH3OH and CO. Significantly, the rhombohedral polymorph exhibits higher activity, superior stability and improved selectivity towards CH3OH over CO. These gains in catalyst performance originate in the enhanced acidity and basicity of surface frustrated Lewis pairs in the rhombohedral form.