Quasi-homogeneous photoelectrochemical organic transformations for tunable products and 100%conversion ratio

产物可调控及100%转化比率的类均相光电化学有机转化

Photoelectrochemical(PEC)organic transformation at the anode coupled with cathodic H_(2) generation is a potentially rewarding strategy for efficient solar energy utilization.Nevertheless,achieving the full conversion of organic substrates with exceptional product selectivity remains a formidable hurdle in the context of heterogeneous catalysis at the solid/liquid interface.Here,we put forward a quasi-homogeneous catalysis concept by using the reactive oxygen species(ROS),such as·OH,H_(2)O_(2) and SO_(4)^(2-),as a charge transfer mediator instead of direct heterogeneous catalysis at the solid/liquid interface.In the context of glycerol oxidation,all ROS exhibited a preference forfirst-order reaction kinetics.These ROS,however,showcased distinct oxidation mechanisms,offering a range of advantages such as100%conversion ratios and theflexibility to tune the resulting products.Glycerol oxidative formic acid with Faradaic efficiency(FE)of 81.2%was realized by the H_(2)O_(2) and·OH,while SO_(4)^(2-)was preferably for glycerol conversion to C3 products like glyceraldehyde and dihydroxyacetone with a total FE of about 80%.Strikingly,the oxidative coupling of methane to ethanol was successfully achieved in our quasi-homogeneous system,yielding a remarkable production rate of 12.27 lmol h^(-1) and an impressive selectivity of 92.7%.This study is anticipated to pave the way for novel approaches in steering solar-driven organic conversions by manipulating ROS to attain desired products and conversion ratios.