Binuclear ruthenium complexes bearing the2,2'‐bipyridine‐6,6'‐dicarboxylate(bda)ligand have been demonstrated to be highly active catalysts towards water oxidation with CeIV as an oxidant.However,the cataly...Binuclear ruthenium complexes bearing the2,2'‐bipyridine‐6,6'‐dicarboxylate(bda)ligand have been demonstrated to be highly active catalysts towards water oxidation with CeIV as an oxidant.However,the catalytic properties of ruthenium dimers have not yet been explored for visible light‐driven water oxidation.Herein,the photocatalytic performance of a dipyridyl propane‐bridged ruthenium dimer2was investigated in comparison with its monomeric precursor,[Ru(bda)(pic)2](1),in CH3CN/phosphate buffer mixed solvent in a three‐component system including a photosensitizer and a sacrificial electron acceptor.Experimental results showed that the activity of each catalyst was strongly dependent on the content of CH3CN in the phosphate buffer,which not only affected the driving force for water oxidation,but also altered the kinetics of the reaction,probably through different mechanisms associated with the O–O bond formation.As a result,dimer2showedsignificantly higher activity than monomer1in the solvent containing a low content of CH3CN,and comparable activities were attained with a high content of CH3CN in the solvent.Under the optimal conditions,complex2achieved a turnover number of638for photocatalytic O2evolution.展开更多
基金supported by the National Basic Research Program of China (973 Program, 2014CB239402)the National Natural Science Foundation of China (21476043)+1 种基金the Fundamental Research Funds for the Central Universities (DUT17ZD204)the Swedish Energy Agency and K&A Wallenberg Foundation~~
文摘Binuclear ruthenium complexes bearing the2,2'‐bipyridine‐6,6'‐dicarboxylate(bda)ligand have been demonstrated to be highly active catalysts towards water oxidation with CeIV as an oxidant.However,the catalytic properties of ruthenium dimers have not yet been explored for visible light‐driven water oxidation.Herein,the photocatalytic performance of a dipyridyl propane‐bridged ruthenium dimer2was investigated in comparison with its monomeric precursor,[Ru(bda)(pic)2](1),in CH3CN/phosphate buffer mixed solvent in a three‐component system including a photosensitizer and a sacrificial electron acceptor.Experimental results showed that the activity of each catalyst was strongly dependent on the content of CH3CN in the phosphate buffer,which not only affected the driving force for water oxidation,but also altered the kinetics of the reaction,probably through different mechanisms associated with the O–O bond formation.As a result,dimer2showedsignificantly higher activity than monomer1in the solvent containing a low content of CH3CN,and comparable activities were attained with a high content of CH3CN in the solvent.Under the optimal conditions,complex2achieved a turnover number of638for photocatalytic O2evolution.
