Liao Hui, Weng Peiqi, Huang Haigen, Tan Ruoxia, Zhu Rui, Liu Yao, Wang Zhijun
Key Laboratory of Coordination Chemistry of Jiangxi Province, School of Chemistry and Chemical Engineering, Jinggangshan University Ji'an Jiangxi 343009 China
RSC Adv. 2023 Jul 12;13(30):20876-20888. doi: 10.1039/d3ra03643j. eCollection 2023 Jul 7.
The hydrogenation of nitroarenes to aromatic amines with H under solvent-free conditions in place of organic solvents is a crucial process for the synthesis of fine chemicals. However, the catalysts that have been identified so far are relatively inactive with primary nitroarenes under solvent-free conditions. Herein, ordered mesoporous carbon (OMC)-supported highly dispersed Ru nanoparticles (Ru NPs) were easily prepared by using a coordination-assisted solvent evaporation induced co-assembly method, where 8-hydroxyquinoline exerts a significant influence on the mesostructure ordering and specific surface area of the Ru/OMC composites. The ultrasmall-sized Ru NPs (∼2.0 nm) supported on ordered mesoporous carbon were then applied in the hydrogenation of nitroarenes, exhibiting high activity and selectivity for numerous structurally diverse nitroarenes under solvent-free conditions. Compared with Ru/OMC-imp and Ru/AC-imp, Ru/OMC-800 exhibited a much higher activity and selectivity for hydrogenation of nitroarenes, suggesting its overwhelmingly better performance than OMC or AC supporting noble NPs by simple impregnation method. The strong metal-support interaction is capable of stabilizing the Ru NPs and achieving good recyclability as well as high selectivity.
在无溶剂条件下用氢气将硝基芳烃氢化为芳香胺以取代有机溶剂，是精细化学品合成的关键过程。然而，迄今为止所确定的催化剂在无溶剂条件下对伯硝基芳烃的活性相对较低。在此，通过配位辅助溶剂蒸发诱导共组装法轻松制备了有序介孔碳（OMC）负载的高度分散钌纳米颗粒（Ru NPs），其中8-羟基喹啉对Ru/OMC复合材料的介观结构有序性和比表面积有显著影响。然后将负载在有序介孔碳上的超小尺寸Ru NPs（约2.0 nm）应用于硝基芳烃的氢化反应，在无溶剂条件下对多种结构各异的硝基芳烃表现出高活性和选择性。与Ru/OMC-imp和Ru/AC-imp相比，Ru/OMC-800在硝基芳烃氢化反应中表现出更高的活性和选择性，表明其性能远优于通过简单浸渍法负载贵金属纳米颗粒的OMC或AC。强金属-载体相互作用能够稳定Ru NPs，并实现良好的可回收性以及高选择性。
