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

Hongqiang Jin,Xiaohu Yu,Peixin Cui,Jinan Shi,Wu Zhou,Weiguo Song,Changyan Cao,Peipei Li

doi:10.1038/s41467-022-28367-9

Abstract

Transition 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.

Highlights

Transition metal single atom catalysts (SACs) with M1-Nx coordination configuration have shown outstanding activity and selectivity for hydrogenation of nitroarenes
We report an N/P dual-coordinated Co single-atom catalysts (SACs) with Co1-N3P1 coordination structure and investigate its catalytic performance for chemoselective hydrogenation of nitroarenes
The unprecedentedly high activity of Co1-N3P1 SAC can be ascribed to the upshift d-band center of Co single atoms, which is more favorable for H2 dissociation as verified by the kinetic isotope effect and density functional theory calculation results

Summary

Introduction

Transition metal single atom catalysts (SACs) with M1-Nx coordination configuration have shown outstanding activity and selectivity for hydrogenation of nitroarenes. Transition metal single-atom catalysts (SACs) with M1-Nx-C (M = Fe, Co, Ni, x = 2–6) coordination configuration exhibited much better activities than their counterpart nanoparticles while maintaining high selectivity, owing to their maximum atom efficiency and particular electronic structure[13–18]. Ni-N coordination numbers (CN), and the capability of Ni single sites to dissociate H2 was greatly enhanced, leading to higher catalytic activity in chemoselective hydrogenation of functionalized nitroarenes[19]. This result suggests that the catalytic activity of

Methods

Results

Conclusion