Photoenzyme Coupling System: Covalent Organic Frameworks In Situ Production of Hydrogen Peroxide Cascaded with Unspecific Peroxygenase to Achieve C–H Bonds Selective Activation

As an efficient, sustainable, and environmentally friendly semiconductor material, covalent organic frameworks (COFs) can generate hydrogen peroxide (H 2 O 2 ) by photocatalysis, attracting wide attention in recent years. Herein, the effects of hydroxyl, methoxyl, and vinyl groups of imide-linked two-dimensional (2D) COFs on the photocatalytic production of H 2 O 2 were studied theoretically and experimentally. The introduction of vinyl groups greatly promotes the photogenerated charge separation and migration of COFs, providing more oxygen adsorption sites, stronger proton affinity, and lower intermediate binding energy, which effectively facilitates the rapid conversion of oxygen to H 2 O 2 . Further, we have integrated the properties of the photocatalytic in situ generation of H 2 O 2 by COFs and the continuous consumption of H 2 O 2 by unspecific peroxygenases (UPOs) to construct a mild and simple photoenzyme coupling system that can achieve selective activation of C–H bonds without the need of any external oxidants or sacrificial agents. This simple, stable, and compatible photoenzyme system avoids irreversible enzyme damage caused by excessive exogenous H 2 O 2 and the utilization of sacrificial agents, thus providing an efficient and green pathway for fine chemical synthesis. This system not only breaks the restriction of continuous exogenous H 2 O 2 supplementation on the UPO catalytic system but also provides a new practical application direction for semiconductor photocatalytic H 2 O 2 production.