A visible-light driven H2 evolution system comprising of a RuII dye (RuP) and CoIII proton reduction catalysts (CoP) immobilised on TiO2 nanoparticles and mesoporous films is presented. The heterogeneous system evolves H2 efficiently during visible-light irradiation in a pH-neutral aqueous solution at 25 °C in the presence of a hole scavenger. Photodegradation of the self-assembled system occurs at the ligand framework of CoP, which can be readily repaired by addition of fresh ligand, resulting in turnover numbers above 300 mol H2 (mol CoP)−1 and above 200,000 mol H2 (mol TiO2 nanoparticles)−1 in water. Our studies support that a molecular Co species, rather than metallic Co or a Co-oxide precipitate, is responsible for H2 formation on TiO2. Electron transfer in this system was studied by transient absorption spectroscopy and time-correlated single photon counting techniques. Essentially quantitative electron injection takes place from RuP into TiO2 in approximately 180 ps. Thereby, upon dye regeneration by the sacrificial electron donor, a long-lived TiO2 conduction band electron is formed with a half-lifetime of approximately 0.8 s. Electron transfer from the TiO2 conduction band to the CoP catalysts occurs quantitatively on a 10 μs timescale and is about a hundred times faster than charge-recombination with the oxidised RuP. This study provides a benchmark for future investigations in photocatalytic fuel generation with molecular catalysts integrated in semiconductors.
If you can't find a tool you're looking for, please click the link at the top of the page to "Go to old article view". Alternatively, view our Knowledge Base articles for additional help. Your feedback is important to us, so please let us know if you have comments or ideas for improvement.