journal article·2023-09Open access

Carbon Vacancies Steer the Activity in Dual Ni Carbon Nitride Photocatalysis

Miriam Marchi, Edoardo Raciti, Sai Manoj Gali, Federica Piccirilli, Hendrik Vondracek, Arianna Actis, Enrico Salvadori, Cristian Rosso, Alejandro Criado, Carmine D'Agostino, Luke Forster, Daniel Lee, Alexandre C. Foucher, Rajeev Kumar Rai, David Beljonne, Eric A. Stach, Mario Chiesa, Roberto Lazzaroni, Giacomo Filippini, Maurizio Prato, Michele Melchionna, Paolo Fornasiero

Advanced Science· Volume 10· Issue 26

Abstract

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.
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Research context

OpenAlex topics: Advanced Photocatalysis Techniques · Perovskite Materials and Applications · MXene and MAX Phase Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Chemical and Pharmaceutical Sciences, Center for Energy, Environment and Transport “Giacomo Ciamician” INSTM UdR Trieste University of Trieste Via Licio Giorgieri 1 Trieste 34127 Italy

Laboratory for Chemistry of Novel Materials Materials Research Institute University of Mons‐UMONS Mons 7000 Belgium

Elettra Sincrotrone Trieste Strada Statale 14 km 163.5 in Area Science Park Basovizza Trieste 34149 Italy

Department of Chemistry and NIS Centre University of Torino Via Pietro Giuria 7 Torino 10125 Italy

Centro Interdisciplinar de Química e Bioloxía–CICA Universidade da Coruña Rúa As Carballeiras A Coruña 15071 Spain

Department of Chemical Engineering The University of Manchester Oxford Road Manchester M13 9PL UK

Department of Civil, Chemical, Environmental and Material Engineering (DICAM) Alma Mater Studiorum University of Bologna Via Terracini, 28 Bologna 40131 Italy

Department of Materials Science and Engineering University of Pennsylvania Philadelphia PA 19104‐6272 USA

Center for Cooperative Research in Biomaterials (CIC biomaGUNE) Basque Research and Technology Alliance (BRTA) Paseo de Miramón 194 Donostia‐San Sebastián 20014 Spain

Ikerbasque Basque Foundation for Science Bilbao 48013 Spain

ICCOM‐CNR Unit of Trieste via L. Giorgieri 1 Trieste 34127 Italy

Funding

Engineering and Physical Sciences Research Council · Biotechnology and Biological Sciences Research Council · National Science Foundation

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