Reduction-Assisted Calcination Enhances the Photocatalytic Activity of ZnO and WO₃ Nanoparticles in Biomass Conversion

Rising energy needs and environmental issues have prompted the creation of effective and affordable photocatalysts for converting biomass. Utilizing abundant biomass, oxidation of 5-hydroxymethylfurfural (HMF) emerges as a method for generating high-value chemicals from biomass, offering an alternative to fossil fuels. We synthesized defect-engineered metal oxides (ZnO and WO₃) by calcination with NaBH₄ as a reducing agent. Atomic-level analyses identified oxygen vacancy defects induced by the reduction of metal ions within the metal oxide nanoparticles. Further analysis showed an unchanged band gap but an up to 4-fold increase in current density. This enhancement is attributed to the trapping of electrons in defect sites created during the calcination process. The formation of new electron donor states hindered photogenerated electron-hole recombination, enhancing the photocatalytic efficiency of the metal oxide. The photocatalytic degradation yield of HMF was over 95%, and the selective organic products 2,5-diformylfuran (DFF) and 2,5-furandicarboxylic acid (FDCA) were obtained without byproducts. Kinetic studies demonstrated that the photocatalytic conversion reaction rates were accelerated by up to 3.5-fold. Improved photocatalytic activity for HMF oxidation was achieved by introducing oxygen vacancy defects upon the reduction of metal ions within the metal oxides. Our results provide a promising approach for designing efficient photocatalysts.