Facile fabrication of B-rGO/ZnFe2O4 p–n heterojunction-based S-scheme exciton engineering for photocatalytic Cr(vi) reduction: kinetics, influencing parameters and detailed mechanism

Abstract

The fabrication of p–n heterostructures was found to be an effective strategy to stimulate the interfacial exciton shipment and photocatalytic reactions. Herein, we report a p–n junction synthesized by combining p-type boron-doped reduced graphene oxide (B-rGO) with an n-type ZnFe₂O₄ semiconducting material for Cr(VI) reduction under LED light irradiation. The band structures of ZnFe₂O₄ and B-rGO were evaluated using UV-vis spectroscopy, Mott–Schottky (M–S) plots and photocurrent studies. The results indicated that ZnFe₂O₄ and B-rGO exhibit a conventional type-II charge transfer, and the Fermi-level (E_F) of ZnFe₂O₄ was found to be much lower than that of the B-rGO material. Based on these investigations, an S-scheme charge-migration pathway was suggested and demonstrated by the photocatalytic activity and nitroblue tetrazolium (NBT) chloride experiments. The optimal 2 wt% B-rGO/ZnFe₂O₄ heterojunction exhibits the highest photocatalytic performance, i.e. 84% of Cr(VI) reduction in 90 min under 20 W LED light irradiation with a rate constant of 0.0207 min⁻¹, which was 4.6- and 2.15-fold greater than that of ZnFe₂O₄ (ZnF) and B-rGO, respectively. The intimate interfacial contact, excellent photon-harvesting properties, effective exciton segregation and availability of active electrons are some factors responsible for enhanced photocatalytic Cr(VI) reduction. In order to fulfill the demand of applied waste-water management, the influences of various photocatalyst amounts, pH values and co-exiting ions on photocatalytic activities were evaluated. Finally, this work provides a way to fabricate S-scheme-based p–n-heterostructures for photocatalytic wastewater treatment.