Direct Z-Scheme Heterojunction α-MnO₂/BiOI with Oxygen-Rich Vacancies Enhanced Photoelectrocatalytic Degradation of Organic Pollutants under Visible Light

The degradation efficiency of photoelectrocatalytic (PEC) processes for the removal of organic pollutants is highly dependent on the performance of the photoelectroanode catalyst. The design of PEC systems with a direct Z-scheme charge transfer mechanism and visible light excitation is essential to enhance the degradation efficiency of organic compounds. Here, a α-MnO2/BiOI direct Z-scheme heterojunction photocatalyst was successfully synthesized through a convenient and feasible method. It is remarkable that the photoanode exhibited excellent PEC performance under visible light irradiation; a 95% removal rate of tetracycline (TC) pollutants was achieved within 2 h, and it had excellent stability and reusability, which was expected to degrade antibiotics efficiently and environmentally in harsh environments. The presence of oxygen vacancies (OVs) in the α-MnO2/BiOI heterojunction was confirmed by electron spin resonance technique, and the OVs acted as electron traps that contributed substantially to the separation efficiency of photogenerated carriers. ESR characterization showed that the main reactive radicals during TC degradation were •OH and •O2−. By analyzing the intermediates, the possible degradation pathways of TC were further analyzed and a suitable degradation mechanism was proposed. The toxicity changes in the degradation process were explored by evaluating the toxicity of the intermediates. This study provides a new way to enhance the performance of Bi-based semiconductor photocatalysts for the effective degradation of TC in water.