Mechanochemical synthesis of ternary heterojunctions TiO2(A)/TiO2(R)/ZnO and TiO2(A)/TiO2(R)/SnO2 for effective charge separation in semiconductor photocatalysis: A comparative study

Abstract

TiO₂, ZnO, and SnO₂ metal oxides were synthesized by the sol-gel method and heterojunctions were fabricated by combining TiO₂ with either ZnO or SnO₂ in a 1:1 ratio using mechanochemical ball milling process. The ball milling process promotes phase transition of TiO₂ from anatase to rutile and yields ternary heterojunction of the type TiO₂(A)/TiO₂(R)/ZnO and TiO₂(A)/TiO₂(R)/SnO₂ (A-anatase and R-rutile). These ternary heterojunctions were characterized by various analytical techniques and its photocatalytic efficiency is evaluated using 4-Chloro Phenol as a model compound under UV and solar light. The enhanced catalytic activity of TiO₂(A)/TiO₂(R)/ZnO heterojunction is attributed to the formation of Ti³⁺-V_o defect states which leads to the efficient charge carrier separation. During the ball milling process severe crystal deformation takes place in TiO₂ and ZnO lattices by creating crystal lattice distortion which leads to the formation of defects due to valency mismatch between Ti⁴⁺ and Zn²⁺. A mechanistic pathway is proposed for the enhanced photocatalytic activity of the ternary heterojunctions.

Keywords: Crystal structure; Defects; Heterojunctions; Oxides; Phase transitions.