Abstract
Developing sustainable catalytic systems for biomass valorization is vital to replace energy-intensive oxidation processes. In this study, a hybrid enzyme-photocatalyst platform integrating horseradish peroxidase (HRP) and unspecific peroxygenase (UPO) with TiO(2) nanoparticles was designed for the selective oxidation of Biomass-derived furanic precursor to Bio-aromatic diacid monomer under mild, aqueous, and light-driven conditions. The hybrid catalyst achieved a maximum Bio-aromatic diacid monomer yield of 98% at 30 °C, significantly surpassing conventional enzymatic and photocatalytic routes. Mechanistic investigations combining EPR, fluorescence, in situ FTIR, and DFT analyses confirmed a strong electron-transfer coupling between enzyme active centers and TiO(2), establishing a direct photo-biocatalytic communication channel. The immobilized system retained over 85% catalytic efficiency during 120 h of continuous packed-bed operation with a negligible pressure drop, demonstrating excellent stability and scalability. Economic evaluation revealed a 35-50% reduction in overall production cost compared with noble-metal catalysts. This work provides a rationally engineered, sustainable hybrid catalytic strategy that unites enzymatic selectivity with photocatalytic durability for green oxidation chemistry and renewable monomer synthesis.