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Titanium dioxide is the only known material that can enable gas-phase CO 2  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 CO 2  hydrogenation photocatalyst for the production of CH 3 OH and CO. Significantly, the rhombohedral polymorph exhibits higher activity, superior stability and improved selectivity towards CH 3 OH over CO. These gains in catalyst performance originate in the enhanced acidity and basicity of surface frustrated Lewis pairs in the rhombohedral form.

Polymorph selection towards photocatalytic gaseous CO2 hydrogenation