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

Author(s)

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.

• Document type: Journal article
• Source: CHEMICAL SOCIETY REVIEWS; v. 52, n. 15, p. 56-pg., 2023-07-06.

Abstract

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)

• FAPESP's process: 21/14006-7 - PHI/PTI-single-atoms controlled synthesis and energy applications
• Grantee: Gabriel Ali Atta Diab
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• FAPESP's process: 21/11162-8 - Multi-user equipment approved in grant 2020/14741-6: GC-MS/FID/TCD (2 injetores+Loop+Sistema valvulado)
• Grantee: Ivo Freitas Teixeira
• Support Opportunities: Multi-user Equipment Program
• FAPESP's process: 22/04748-9 - Graphitic carbon nitrides as acid solid catalysts applied to biomass conversion
• Grantee: Guilherme de Freitas Silva Rodrigues Rocha
• Support Opportunities: Scholarships in Brazil - Master
• FAPESP's process: 20/14741-6 - Graphitic carbon nitrides as platforms for single-atom photocatalysis: moving towards design principles for improved performance
• Grantee: Ivo Freitas Teixeira
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 21/13271-9 - Single atoms coordinated on graphitic carbon nitrides to photocatalytic conversion of methane
• Grantee: Marcos Augusto Ribeiro da Silva
• Support Opportunities: Scholarships in Brazil - Doctorate