First Study on Phosphonite-Coordinated Ruthenium Sensitizers for Efficient Photocatalytic Hydrogen Evolution.
For the first time we report the design and syntheses of phosphonite coordinated ruthenium(II) sensitizers bearing ĈN̂N ligand and/or terpyridine derivatives carboxylate anchor (GS11, GS12. and GS13) and its application for hydrogen production over Pt-TiO2 system. These heteroleptic complexes exhibit broad metal-to-ligand charge transfer transition band over the whole visible regime extending up to 900 nm. DFT calculations of these complexes show that the HOMO is distributed over the Ru and Cl atom whereas; LUMO is localized on the polypyridile ligand, which are anchored on TiO2 surface. Among the sensitizers tested for photocatalytic hydrogen evolution, GS12 exhibited a maximum turnover number (TON) 8605 (for 8 h), which is very high compared to the reference sensitizer (N719) with TON 163 under similar evaluation condition. The dependence of the hydrogen evolution rate at different pH using GS11, GS12, GS13, and DX-1-sensitized Pt-TiO2 has been studied and the maximum H2 production yield was obtained at pH 7 for all sensitizers.
Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology , Uppal road, Tarnaka, Hyderabad-500007, India.|Network Institute of Solar Energy, (CSIR-NISE) and Academy of Scientific and Innovative Research (AcSIR) , New Delhi-110001, India.
T
T
Swetha
Network Institute of Solar Energy, (CSIR-NISE) and Academy of Scientific and Innovative Research (AcSIR) , New Delhi-110001, India.|Department of Chemistry and Biomimetics, CSIR-Central Mechanical Engineering Research Institute , M.G Avenue, Durgapur-713209, West Bengal India.
Indranil
I
Mondal
Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology , Uppal road, Tarnaka, Hyderabad-500007, India.|Network Institute of Solar Energy, (CSIR-NISE) and Academy of Scientific and Innovative Research (AcSIR) , New Delhi-110001, India.
K
K
Bhanuprakash
Network Institute of Solar Energy, (CSIR-NISE) and Academy of Scientific and Innovative Research (AcSIR) , New Delhi-110001, India.|Department of Chemistry and Biomimetics, CSIR-Central Mechanical Engineering Research Institute , M.G Avenue, Durgapur-713209, West Bengal India.
Ujjwal
U
Pal
Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology , Uppal road, Tarnaka, Hyderabad-500007, India.|Network Institute of Solar Energy, (CSIR-NISE) and Academy of Scientific and Innovative Research (AcSIR) , New Delhi-110001, India.
Surya Prakash
SP
Singh
DFT studies; carboxylate anchor; high TON; hydrogen evolution; phosphonite-coordinated ruthenium(II) sensitizers