Design and in-situ construct BiOI/Bi/TiO_(2)photocatalysts with metal-mediated heterostructures employing oxygen vacancies in TiO_(2)nanosheets

The conventional p-n heterojunction photocatalysts suffer from the incompatibility between the interfacial charge transfer efficiency and the redox ability of charge carriers.To optimize the interfacial charge transfer of the conventional BiOI/TiO_(2) p-n photocatalyst,we synthesized the BiOI/Bi/TiO_(2) ternary photocatalyst with sandwiched metallic bismuth(Bi~0)by the oxygen-vacancy assisted method.The DFT calculation and structural characterizations confirmed the reaction of the electron-rich oxygen vacancies in the 2D-TiO_(2) nanosheets(TiO_(2)-NS)with the adsorbed BiO~+species.This reaction broke the Bi-O bonds to form Bi^(0) nanoparticles in-situ at the interface but still maintained the p-n heterojunction well.The NO-TPD and XRD analyses for samples correlated the Bi~0 formation with the oxygen vacancy concentrations well.The sandwiched Bi~0 functioned as an electronic transfer mediator like that in the Z-scheme heterostructure.Comparing with 0.20 BiOI/TiO_(2)-NP(NP,Nanoparticles),0.20 BiOI/Bi/TiO_(2)-NS-a(NS,Nanosheet)showed a much improved catalytic performance,i.e.,duplicated apparent quantum yield(AQY)and triplicated reaction rate constant(k).Also,the formation mechanism and the reaction mechanism were investigated in detail.This work provides a new strategy for the improving of the conventional p-n photocatalysts and new insights into the nature of the photocatalysis.