Granum-Inspired Photoenzyme-Coupled Catalytic System via Stacked Polymeric Carbon Nitride

Photoenzyme-coupled catalysis has become a powerful platform for chemical manufacturing, in which energy-bearing intermediates are often shuttled between a photocatalytic module and an enzymatic module. A photoenzyme-coupled catalytic system (PECCS) to realize the generation of intermediates by the photocatalytic module and utilization of intermediates by the enzymatic module is highly desired. Inspired by the structure and function of a granum, stacked tubular polymeric carbon nitride (st-PCN*) is designed as both a photocatalyst and a carrier for chlorperoxidase (CPO), constructing the st-PCN*@CPO PECCS to implement the cascade chlorination reaction. st-PCN* ensures oriented electron transfer, achieving the H2O2 evolution rate of 150 mu mol h(-1) g(-1) (st-PCN*), over 55- and 2-fold that of bulky PCN (b-PCN) and bulky PCN* (b-PCN*). Meanwhile, st-PCN* shortens the diffusion distance of H2O2 from st-PCN* to CPO. Under simulated sunlight irradiation, our st-PCN*@CPO PECCS realizes in situ, continuous, and controllable supply of H2O2 to CPO, followed by converting monochlorodimedone (MCD) into dichlordimedone (DCD) with a final conversion ratio of similar to 39.5%. The initial reaction rate could reach 0.29 mM h(-1), over 20-fold that of its counterpart PECCS with a nonstacked structured photocatalyst. Our study unveils the potential of exploring the stacked structure to coordinate cascade catalytic processes.

Automated summary

The study presents a photoenzyme-coupled catalytic system for efficient energy intermediate transfer and utilization in chemical manufacturing. By using stacked tubular polymeric carbon nitride as a photocatalyst and carrier, the system achieves continuous, effective, and controllable chlorination reaction with high reaction rates and conversion ratios.