Carbon Vacancies Steer the Activity in Dual Ni Carbon Nitride Photocatalysis

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 C—X (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.