Direct Z-scheme MgIn ₂ S ₄ /TiO ₂ heterojunction for enhanced photocathodic protection of metals under visible light

Abstract

To improve the photocathodic protection performance of traditional TiO₂photoanodes for metals, constructing a Z-scheme heterojunction is one of the most promising and creative strategies. Herein, we fabricated a novel Z-scheme MgIn₂S₄nanosheets/TiO₂nanotube nanocomposite through anodization and hydrothermal method. The optimized Z-scheme MgIn₂S₄/TiO₂nanocomposites exhibited stronger visible light absorption, higher separation efficiency of photoelectrons and photocathodic protection performances in comparison to pure TiO₂. The theoretical analysis and experimental results show that the Z-scheme heterojunction and oxygen vacancies jointly improved the separation efficiency of photogenerated electron-hole pairs and visible light absorption capacity, thereby improving the photoelectric conversion performance of the MgIn₂S₄/TiO₂nanocomposites. Furthermore, the influence of the precursor solution concentration on the photocathodic protection performances of the composites was investigated. As a result, when the concentration of magnesium source in the precursor solution was 0.06 mmol, the prepared MgIn₂S₄/TiO₂-0.06 displayed the best photocathodic protection performance. In addition, the hydroxyl radicals (·OH) generated in the electron spin resonance (ESR) experiment verified the Z-scheme heterojunction mechanism of the MgIn₂S₄/TiO₂composite, and also demonstrated the excellent redox performance of the composite. This work provides valuable reference for the construction of high-performance Z-scheme heterojunctions for photocathode protection of metals.