A combined experimental and theoretical study of RuO₂/TiO₂ heterostructures as a photoelectrocatalyst for hydrogen...

We report a joint experimental and theoretical study of RuO₂/TiO₂ heterostructures. In the experimental section, mesoporous RuO₂/TiO₂ heterostructures were prepared by impregnation of mesoporous TiO₂ nanoparticles which were synthesized from a new precursor, Na₂[Ti(C₂O₄)₃], in an aqueous solution of ruthenium(III) chloride followed by calcination at 300 °C. Using various techniques, the prepared TiO₂ and RuO₂/TiO₂ heterostructures were extensively characterized. The photoelectocatalytic application of the as-prepared heterostructures was then investigated toward the hydrogen evolution reaction (HER). The results illustrated that RuO₂ is dispersed uniformly on the TiO₂ surface. The loading of RuO₂ on TiO₂ decreases the band gap energy and extends the absorption edge to the visible light region. This wide absorption extends the photoelectrocatalytic activity of RuO₂/TiO₂ heterostructures. To obtain a deeper understanding of the increase of the photoelectrocatalytic activity of RuO₂/TiO₂ heterostructures compared to pure TiO₂, theoretical calculations at the density functional theory (DFT) level were performed on some model clusters of pure TiO₂ and the RuO₂/TiO₂ heterostructure. The theoretical results elucidated that the recombination ratio of electron-hole pairs decreases effectively for RuO₂/TiO₂ compared to pure TiO₂.