Thermo-photodynamic perspective of the simultaneous S-Scheme ternary heterostructure through Ag3VO4 shuttle for the increased photo-redox ability

Abstract

A binary heterostructure bearing Ag3VO4 and InVO4 is deposited over a 2D gC3N4 nano-bed through a multistep hydrothermal technique. Though the synthesis is non-directional, the formation of the junction is governed through Ag3VO4 acting as a shuttle for charge transfer between InVO4 and gC3N4. Vacant d-orbital in the Ag3VO4 accommodated the incoming ⊡ electrons from gC3N4 forming a covalent bond through Agostic interactions and was as exhibited through DFT calculation. The chosen materials possessed dielectric, absorption, and extinction coefficient in both the low to high energy domain. Hence their amalgamation inserted robust light-harvesting properties. A 3D-2D Vandarwall junction among the binary material and the gC3N4 nano-bed has created a hierarchical attachment that resulted in a strong interfacial double layer in each junction with an internal electric field and has prevented the exciton recombination. The holistic S-scheme configuration responsible for the charge transfer was revealed. A thermo-chemodynamical understanding of photocatalysis during the MB degradation has shown the superiority of the diffusion control during the removal. The enhanced reduction potential of the Ag3VO4 center and the catalytic center has imparted higher stabilization of the transition state that resulted in lower activation energy for MB removal.