Carbon nitride based materials: more than just a support for single-atom catalysis

Autor(es)

Rocha, Guilherme F. S. R. ; da Silva, Marcos A. R. ; Rogolino, Andrea ; Diab, Gabriel A. A. ; Noleto, Luis F. G. ; Antonietti, Markus ; Teixeira, Ivo F.

• Tipo de documento: Artigo Científico
• Fonte: CHEMICAL SOCIETY REVIEWS; v. 52, n. 15, p. 56-pg., 2023-07-06.

Resumo

Recently, the missing link between homogeneous and heterogeneous catalysis has been found and it was named single-atom catalysis (SAC). However, the SAC field still faces important challenges, one of which is controlling the bonding/coordination between the single atoms and the support in order to compensate for the increase in surface energy when the particle size is reduced due to atomic dispersion. Excellent candidates to meet this requirement are carbon nitride (CN)-based materials. Metal atoms can be firmly trapped in nitrogen-rich coordination sites in CN materials, which makes them a unique class of hosts for preparing single-atom catalysts (SACs). As one of the most promising two-dimensional supports to stabilize isolated metal atoms, CN materials have been increasingly employed for preparing SACs. Herein, we will cover the most recent advances in single-atoms supported by CN materials. In this review, the most important characterization techniques and the challenges faced in this topic will be discussed, and the commonly employed synthetic methods will be delineated for different CN materials. Finally, the catalytic performance of SACs based on carbon nitrides will be reviewed with a special focus on their photocatalytic applications. In particular, we will prove CN as a non-innocent support. The relationship between single-atoms and carbon nitride supports is two-way, where the single-atoms can change the electronic properties of the CN support, while the electronic features of the CN matrix can tune the catalytic activity of the single sites in photocatalytic reactions. Finally, we highlight the frontiers in the field, including analytical method development, truly controlled synthetic methods, allowing the fine control of loading and multi-element synthesis, and how understanding the two-way exchange behind single-atoms and CN supports can push this topic to the next level. (AU)

• Processo FAPESP: 21/14006-7 - Síntese controlada de single-atoms em PHI/PTI e suas aplicações em energia
• Beneficiário: Gabriel Ali Atta Diab
• Modalidade de apoio: Bolsas no Brasil - Doutorado Direto
• Processo FAPESP: 21/11162-8 - EMU concedido no processo 2020/14741-6: GC-MS/FID/TCD (2 injetores+Loop+Sistema valvulado)
• Beneficiário: Ivo Freitas Teixeira
• Modalidade de apoio: Auxílio à Pesquisa - Programa Equipamentos Multiusuários
• Processo FAPESP: 22/04748-9 - Nitretos de carbono grafítico como catalisadores sólidos ácidos aplicados à conversão de biomassa
• Beneficiário: Guilherme de Freitas Silva Rodrigues Rocha
• Modalidade de apoio: Bolsas no Brasil - Mestrado
• Processo FAPESP: 20/14741-6 - Nitretos de carbono grafítico como plataformas para single-atom fotocatálise: usando princípios de design para melhores desempenhos
• Beneficiário: Ivo Freitas Teixeira
• Modalidade de apoio: Auxílio à Pesquisa - Jovens Pesquisadores
• Processo FAPESP: 21/13271-9 - Single-atoms coordenados em nitretos de carbono grafítico para conversão fotocatalítica de metano
• Beneficiário: Marcos Augusto Ribeiro da Silva
• Modalidade de apoio: Bolsas no Brasil - Doutorado