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.

Carbon Vacancies Steer the Activity in Dual Ni Carbon Nitride Photocatalysis

Actis, Arianna;Salvadori, Enrico;Chiesa, Mario;
2023-01-01

Abstract

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.
2023
10
26
1
12
https://onlinelibrary.wiley.com/doi/epdf/10.1002/advs.202303781
carbon nitride; dual photocatalysis; nickel; organic synthesis
Marchi, Miriam; Raciti, Edoardo; Gali, Sai Manoj; Piccirilli, Federica; Vondracek, Hendrik; Actis, Arianna; Salvadori, Enrico; Rosso, Cristian; Criado, Alejandro; D'Agostino, Carmine; Forster, Luke; Lee, Daniel; Foucher, Alexandre C; Rai, Rajeev Kumar; Beljonne, David; Stach, Eric A; Chiesa, Mario; Lazzaroni, Roberto; Filippini, Giacomo; Prato, Maurizio; Melchionna, Michele; Fornasiero, Paolo
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/1945855
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