Highly efficient and anti-poisoning single-atom cobalt catalyst for selective hydrogenation of nitroarenes
Yuemin Lin, Renfeng Nie, Yuting Li, Xun Wu, Jiaqi Yu, Shaohua Xie, Yajing Shen, Shanjun Mao, Yuzhuo Chen, Dan Lu, Zongbi Bao, Qiwei Yang, Qilong Ren, Yiwen Yang, Fudong Liu, Long Qi, Wenyu Huang, Zhiguo Zhang
Abstract
Developing non-precious metal catalysts to selectively reduce functionalized nitroarenes with high efficiency is urgently desirable for the production of value-added amines. Herein, we report a novel, efficient, anti-poisoning single-atom cobalt catalyst (Co-NAC) for the highly selective hydrogenation of the nitro to amino group for nitroarenes baring various functional groups, including vinyl, cyano, and halogen. Using a combination of structure characterization techniques, we have confirmed that the cobalt species are predominantly present in the form of four-coordinated Co single sites anchored on nitrogen-assembly carbon (NAC) as the ordered mesoporous support. Co-NAC catalysts enable the full conversion and > 99% selectivity with molecular H2 as a green reductant under mild conditions (80 °C, 2 MPa H2). As for the selective hydrogenation of 3-nitrostyrene, Co-NAC catalyst affords high catalytic productivity (19.7 h−1), which is superior to the cobalt nanoparticles (NPs) catalysts and most of the recently reported Co-based catalysts. This is attributed to the highly accessible atomically-dispersed Co active sites, the high surface area with ordered-mesoporous morphology and the prominent high content of nitrogen dopants. Notably, Co-NAC catalyst displays resistance towards sulfur-containing poisons (20 equivalents) and strong non-oxidizing acid (8 M), showing great potential for continuous application in the chemical industry.