Platinum Carbonyl Chini Clusters as Catalysts for Photocatalytic H₂ Generation

Platinum Chini clusters with a general formula [Pt₃(CO)₆]_n^2– are formed by stacked Pt₃ units. They have fascinating electronic and optical properties that can be tuned with n. 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 n. 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 (n = 4) are more effective than larger ones (n = 7–8), and that composites having lower Pt content perform better.