Enhanced catalytic activity of N-heterocyclic carbene stabilized surface adatoms for CO reduction reaction

• Published in: Communications chemistry Vol. 6; no. 1; p. 270
• Main Authors: Gao, Yuxiang, Tao, Lei, Zhang, Yu-Yang, Du, Shixuan
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 11.12.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 639/301/1034; 639/4077/4057; 639/638/542; 639/638/563/606; 639/638/77/886; Adatoms; Carbenes; Carbon monoxide; Catalytic activity; Chemical reduction; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Coupling; Decoration; Density functional theory; Hydrogenation; Mathematical analysis; Quantum mechanics; Single atom catalysts
• ISSN: 2399-3669; 2399-3669
• DOI: 10.1038/s42004-023-01066-2

Adatom engineering represents a highly promising opportunity for enhancing electrochemical CO reduction reaction (CORR). However, the aggregation of adatoms under typical reaction conditions often leads to a decline in catalyst activity. Recent studies have revealed that N-heterocyclic carbene (NHC) can stabilize surface adatoms. Herein, based on density functional theory calculations, we reveal a significant enhancement in the catalytic activity of Cu adatoms decorated with NHC molecules for CORR. The NHC decoration strengthens the interaction between the d xy orbital of the Cu adatom and the p x orbital of the C atom, reducing the energy barriers in both CO hydrogenation and C-C coupling steps. Moreover, the CORR catalytic activity of the NHC decorated adatom can be further improved by tuning the side groups of NHC molecules. These results provide insights for the design of efficient CORR catalysts and offer a theoretical framework that can be extended to other hydrogenation reactions. Single atom catalysts dispersed on a surface demonstrate great promise for a variety of catalytic reactions, but their aggregation leads to a degradation of catalytic activity. Here, the authors use quantum mechanical calculations to study the catalytic activity of Cu adatoms stabilized with N-heterocyclic carbenes (NHCs) on a Cu(100) surface, finding that NHC-decoration significantly reduces the energy barriers to electrocatalytic CO hydrogenation and C–C coupling.