Unprecedentedly high activity and selectivity for hydrogenation of nitroarenes with single atomic Co1-N3P1 sites

• Published in: Nature communications Vol. 13; no. 1; pp. 723 - 9
• Main Authors: Jin, Hongqiang, Li, Peipei, Cui, Peixin, Shi, Jinan, Zhou, Wu, Yu, Xiaohu, Song, Weiguo, Cao, Changyan
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 07.02.2022; Nature Publishing Group; Nature Portfolio
• Subjects: 639/301/357/537; 639/638/77/884; 639/638/77/887; Atomic structure; Catalysts; Chemical synthesis; Coordination; Density functional theory; Displays; Electron density; Humanities and Social Sciences; Hydrogenation; Isotope effect; multidisciplinary; Nitrobenzene; Science; Science (multidisciplinary); Selectivity; Single atom catalysts; Transition metals
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-28367-9

Transition metal single atom catalysts (SACs) with M 1 -N x coordination configuration have shown outstanding activity and selectivity for hydrogenation of nitroarenes. Modulating the atomic coordination structure has emerged as a promising strategy to further improve the catalytic performance. Herein, we report an atomic Co 1 /NPC catalyst with unsymmetrical single Co 1 -N 3 P 1 sites that displays unprecedentedly high activity and chemoselectivity for hydrogenation of functionalized nitroarenes. Compared to the most popular Co 1 -N 4 coordination, the electron density of Co atom in Co 1 -N 3 P 1 is increased, which is more favorable for H 2 dissociation as verified by kinetic isotope effect and density functional theory calculation results. In nitrobenzene hydrogenation reaction, the as-synthesized Co 1 -N 3 P 1 SAC exhibits a turnover frequency of 6560 h −1 , which is 60-fold higher than that of Co 1 -N 4 SAC and one order of magnitude higher than the state-of-the-art M 1 -N x -C SACs in literatures. Furthermore, Co 1 -N 3 P 1 SAC shows superior selectivity (>99%) toward many substituted nitroarenes with co-existence of other sensitive reducible groups. This work is an excellent example of relationship between catalytic performance and the coordination environment of SACs, and offers a potential practical catalyst for aromatic amine synthesis by hydrogenation of nitroarenes. Modulating the atomic coordination structure has emerged as a promising strategy to further improve catalytic performance. Here, the authors report an atomic Co1/NPC catalyst with unsymmetrical single Co1N3P1 sites that displays high activity and chemoselectivity for hydrogenation of functionalized nitroarenes.