Advanced Science ( IF 15.1 ) Pub Date : 2023-07-06 , DOI:
10.1002/advs.202303781
MiriamMarchi,EdoardoRaciti,SaiManojGali,FedericaPiccirilli,HendrikVondracek,AriannaActis,EnricoSalvadori,CristianRosso,AlejandroCriado,CarmineD'Agostino,LukeForster,DanielLee,AlexandreCFoucher,RajeevKumarRai,DavidBeljonne,EricAStach,MarioChiesa,RobertoLazzaroni,GiacomoFilippini,MaurizioPrato,MicheleMelchionna,PaoloFornasiero
The manipulation of carbon nitride (CN) structures is one main avenue to enhance the activity of CN-based photocatalysts. Increasing the efficiency of photocatalytic heterogeneous materials is a critical step toward the realistic implementation of sustainable schemes for organic synthesis. However, limited knowledge of the structure/activity relationship in relation to subtle structural variations prevents a fully rational design of new photocatalytic materials, limiting practical applications. Here, the CN structure is engineered by means of a microwave treatment, and the structure of the material is shaped around its suitable functionality for Ni dual photocatalysis, with a resulting boosting of the reaction efficiency toward many CX (X = N, S, O) couplings. The combination of advanced characterization techniques and first-principle simulations reveals that this enhanced reactivity is due to the formation of carbon vacancies that evolve into triazole and imine N species able to suitably bind Ni complexes and harness highly efficient dual catalysis. The cost-effective microwave treatment proposed here appears as a versatile and sustainable approach to the design of CN-based photocatalysts for a wide range of industrially relevant organic synthetic reactions.