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.

开发非贵金属催化剂以高效选择性地还原官能化硝基芳烃是生产增值胺的迫切需要。在此，我们报道了一种新型、高效、抗中毒的单原子钴催化剂 (Co-NAC)，用于将具有各种官能团（包括乙烯基、氰基和卤素）的硝基芳烃的硝基高选择性氢化为氨基。使用结构表征技术的组合，我们已经证实钴物种主要以四配位 Co 单点的形式存在，其锚定在作为有序介孔载体的氮组装碳 (NAC) 上。Co-NAC 催化剂在温和条件下（80 °C， ₂ MPa H₂ )。对于 3-硝基苯乙烯的选择性加氢，Co-NAC 催化剂具有高催化产率（19.7 h ^-1），优于钴纳米颗粒（NPs）催化剂和大多数最近报道的钴基催化剂。这归因于高度可及的原子分散的 Co 活性位点、具有有序中孔形态的高表面积和显着的高氮掺杂剂含量。值得注意的是，Co-NAC催化剂表现出对含硫毒物（20当量）和强非氧化性酸（8 M）的抵抗力，显示出在化学工业中持续应用的巨大潜力。