Intramolecular modulation of iron-based metal organic framework with energy level adjusting for efficient photocatalytic activity

Abstract Efficient photocatalytic activity is always pressingly expected for photocatalytic technology on removing organic water contaminations. Modulating the intrinsic electronic properties is one of the most effective approaches to improve photocatalytic efficiency. Herein, we developed a promising photocatalyst through modulation electronic properties of iron-based metal organic framework by sulfur (S-MIL-53(Fe)), in which the sulfur particles were intramolecularly in-suite inserted into MIL-53(Fe) through annealing treatment process. The constructed S3-MIL-53(Fe) crystal with regular spindle-shaped polyhedron morphology exhibited superior higher apparent quantum efficiency (AQE) of 27.82% which was over 30 times than that of pure MIL-53(Fe) (0.903%) indicating the significantly enhanced photoactivity. A computational study was conducted to reveal the electronic structure changes and the resulted charge transfer induced by the sulfur modulation. The experimental and computational analyses suggest that intramolecular modulation MIL-53(Fe) with sulfur to engineer band structure for promoting charge transfer is a promising approach to improve the photocatalytic efficiency.