Platinum Carbonyl Chini Clusters as Catalysts for Photocatalytic H ₂ Generation

Platinum Chini clusters with a general formula [Pt₃(CO)₆] _<i>n</i> ^2- are formed by stacked Pt₃ units. They have fascinating electronic and optical properties that can be tuned with <i>n</i>. In the current manuscript, the electronic, photochemical, and charge transport properties of the platinum Chini clusters are studied with the density functional theory (PBE and CAM-B3LYP/6-31G(d,p)+LANL2DZ) as a function of their nuclearity number <i>n</i>. Our theoretical predictions are supported by experimental proof of concept, in which synthesized Chini clusters are deposited as cocatalysts on TiO₂ for photocatalytic hydrogen generation. We demonstrate that smaller clusters (<i>n</i> = 4) are more effective than larger ones (<i>n</i> = 7-8), and that composites having lower Pt content perform better.