Photoinduced Biomimetic Room‐Temperature C−O Bond Cleavage over Mn Doped CdS

Abstract

Selective C−O bond cleavage is an efficient way for the biomass valorization to value‐added chemicals, but is challenged to be operated at room temperature via conventional thermal catalysis. Herein, inspired from the DNA biosynthesis which involves a radical‐mediated spin‐center shift (SCS) C−O bond cleavage process, we report a biomimetic room‐temperature C−O bond cleavage of vicinal diol (HOCHCH‐OH). We construct a Mn doped CdS (Mn/CdS) as a photocatalyst to mimic the biologic SCS process. The Mn site plays pivotal role: (1) accelerates the photo‐induced carrier separation, promoting the hole‐mediated C−H bond cleavage to generate carbon‐centered radicals, and (2) serves as the binding site for −OH groups, making it to be an easier leaving group. Mn/CdS achieves 0.28 mmol g_cat⁻¹ h⁻¹ of hydroxyacetone (HA) from glycerol dehydration at room temperature under visible light irradiation, which is 3.5‐fold that over pristine CdS and 40‐fold that over bulk MnS/CdS. This study provides a new biomimetic room‐temperature C−O bond cleavage process, which is promising for the biomass valorization.