Nanoparticulate Perovskites for Photocatalytic Water Reduction

SrTiO₃ and BaTiO₃ nanoparticles (NPs) were activated using H₂O₂ or aqueous HNO₃, and pristine and activated NPs were functionalized with a 2,2'-bipyridine phosphonic acid anchoring ligand (1), followed by reaction with RuCl₃^.3H₂O and bpy, RhCl₃^.3H₂O and bpy, or RuCl₃^.3H₂O. The surface-bound metal complex functionalized NPs were used for the photogeneration of H₂ from water, and their activity was compared to related systems using TiO₂ NPs. The role of pH during surface complexation was found to be important. The NPs were characterized using Fourier transform infrared (FTIR) and solid-state absorption spectroscopies, thermogravimetric analysis mass spectrometry (TGA-MS), and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), and the dihydrogen generation was analyzed using gas chromatography-mass spectrometry (GC-MS). Our findings indicate that extensively functionalized SrTiO₃ or BaTiO₃ NPs may perform better than TiO₂ NPs for water reduction.