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

Author:

Jin Hongqiang,Li Peipei,Cui PeixinORCID,Shi Jinan,Zhou WuORCID,Yu XiaohuORCID,Song Weiguo,Cao ChangyanORCID

Abstract

AbstractTransition metal single atom catalysts (SACs) with M1-Nx 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 Co1/NPC catalyst with unsymmetrical single Co1-N3P1 sites that displays unprecedentedly high activity and chemoselectivity for hydrogenation of functionalized nitroarenes. Compared to the most popular Co1-N4 coordination, the electron density of Co atom in Co1-N3P1 is increased, which is more favorable for H2 dissociation as verified by kinetic isotope effect and density functional theory calculation results. In nitrobenzene hydrogenation reaction, the as-synthesized Co1-N3P1 SAC exhibits a turnover frequency of 6560 h−1, which is 60-fold higher than that of Co1-N4 SAC and one order of magnitude higher than the state-of-the-art M1-Nx-C SACs in literatures. Furthermore, Co1-N3P1 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.

Funder

National Natural Science Foundation of China

Youth Innovation Promotion Association of the Chinese Academy of Sciences

Publisher

Springer Science and Business Media LLC

Subject

General Physics and Astronomy,General Biochemistry, Genetics and Molecular Biology,General Chemistry,Multidisciplinary

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