Synergistic interface engineering in n-p-n type heterojunction Co3O4/MIL/Mn-STO with dual S-scheme multi-charge migration to enhance visible-light photocatalytic degradation of antibiotics

Abstract

Constructing an effective multi-heterojunction photocatalyst with maximum charge carrier separation remains challenging. Herein, a high-efficient Co3O4/MIL-88A/Mn–SrTiO3 (Co3O4/MIL/Mn-STO) n-p-n heterojunction photocatalyst was successfully prepared by a simple hydrothermal method for the photodegradation of sulfamethoxazole (SMX). The combination of MIL and Co3O4/Mn-STO established an internal electric field and heterojunction, accelerating the separation of carriers, and thus improved photocatalytic performance. In the Co3O4/MIL/Mn-STO photocatalytic system, 95.5 % of SMX was degraded in 90 min. The photocatalytic kinetic removal rate of Co3O4/MIL/Mn-STO reached 0.0337 min−1, 8 times of Co3O4 (0.0041 min−1), 5.2 times of Mn-STO (0.0062 min−1), 4.6 times of MIL (0.0078 min−1), and 3.6 times of MIL/Mn-STO (0.0095 min−1). Remarkably, superoxide radicals (•O2−) and holes (h+) have been recognized as the main active species in the degradation process through reactive species elimination experiments and electron spin resonance (ESR) tests. The experimental and theoretical proved the in-built interfacial contact and synergistic effect between the photocatalyst accomplished with low bandgaps, high specific surface area, more reaction sites, high electron-hole pair separation, and maximum solar-light utilization. The molecular structure and possible degradation routes with intermediate products in the photocatalytic system were investigated using a liquid chromatography-mass spectrometer (LC-MS) and DFT calculations. This work provided new insight into the guidelines of rational design/growth of new multicomponent photocatalysts to remove antibiotics and other emerging contaminants in wastewater.