Mechanistic insights into the formation of surface oxygen vacancies with controllable concentration and long-term stability in small-molecule bonded bismuth-based semiconductor hybrid photocatalyst

Abstract

Constructing oxygen vacancies (OVs) with desired concentration and stability on the surfaces of semiconductors has been demonstrated to be a powerful tactic to enhance their photocatalytic performances. Nevertheless, forming OVs usually requires rigorous conditions, and OVs harshly suffer from deactivation during photoreaction. Herein, a facile strategy is developed to introduce surface OVs with tunable concentrations and long-term stability in bismuth-based semiconductors (BBS) through organic small-molecule surface-bonding. Taking I-doped BiOCl (I-BiOCl) as a model photocatalyst and catechol and its derivatives as ligands, a series of organic/I-BiOCl bonded hybrid photocatalysts are successfully synthesized. Compared with I-BiOCl, hybrid photocatalysts exhibited substantially enhanced catalytic activity toward multiple contaminants removal. Experimental characterizations and DFT calculations reveal a strong interfacial interaction between organic ligands and BBS through the formation of BiOC bonds, which lengthen Bi-O bonds within [Bi2O2]2+ structural units and reduce the formation energy of OVs, facilitating the escape of lattice O atoms and thus producing abundant surface OVs. More importantly, the concentration of OVs can be easily regulated by controlling the number of organic ligands, and the OVs exhibit high stability during photoreaction, attributing to the existence of high-valence-state Bi(3+x)+ that is near the OVs, which would not be re-oxidized by oxidative species like the low-valence-state Bi(3-x)+, that is, they would not be reset to original Bi3+. As a verification of its universality, the surface bonded strategy has been successfully extended to other BBS.