Characterization of Pt/g-C₃N₄-Catalyzed Methanol Oxidation to Drive Peroxygenase-Catalyzed Oxyfunctionalization of Hydrocarbons

The photobiocatalysis combining photocatalysts and enzymes provides new strategies for organic synthesis and energy conversion. However, the available photocatalysts used in photobiocatalysis are still limited. Herein, highly dispersed Pt nanoparticles supported on graphitic carbon nitride (Pt/g-C3N4) were designed and applied for the light-driven in situ generation of H2O2, which was subsequently supplied to peroxygenase for selective oxyfunctionalization of C-H bonds. Substrates with activated and non-activated C-H bonds were hydroxylated into the corresponding alcohols with an enantiomeric excess of up to 99% and a turnover number of 133,000, which was about four times higher than that of unsupported g-C3N4 catalysts. Further mechanistic study by UV-vis, static photoluminescence spectroscopy, and DFT calculations revealed that the effective absorption of visible light by Pt nanoparticles on the surface of g-C3N4 and the strong interaction between O2 and the g-C3N4 surface were advantageous to improve the performance of photobiocatalysis. This research provides new insights into the fabrication of efficient photocatalysts compatible with peroxyzymes, paving the way for synergistic photobiocatalysis for selective oxyfunctionalization of hydrocarbons.