Room-temperature hydrogenation of halogenated nitrobenzenes over metal-organic-framework-derived ultra-dispersed Ni stabilized by N-doped carbon nanoneedles  

作　　者：Yuemin Lin Yuanyuan Zhang Renfeng Nie Kai Zhou Yao Ma Mingjie Liu Dan Lu Zongbi Bao Qiwei Yang Yiwen Yang Qilong Ren Zhiguo Zhang 

机构地区：[1]Key Laboratory of Biomass Chemical Engineering of Ministry of Education,College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310027,China [2]School of Chemical Engineering,Henan Center for Outstanding Overseas Scientists,Zhengzhou University,Zhengzhou 450001,China [3]Institute of Zhejiang University—Quzhou,Quzhou 324000,China

出　　处：《Frontiers of Chemical Science and Engineering》2022年第12期1782-1792,共11页化学科学与工程前沿（英文版）

基　　金：This work was supported by the National Key R&D Program of China(Grant No.2021YFC2103704);the National Natural Science Foundation of China(Grant Nos.21878266 and 22078288);the Science and Technology Research Project of Henan Province(Grant No.222300420527);Program of Processing and Efficient Utilization of Biomass Resources of Henan Center for Outstanding Overseas Scientists(Grant No.GZS2022007).

摘　　要：Ultra-dispersed Ni nanoparticles(7.5 nm)on nitrogen-doped carbon nanoneedles(Ni@NCNs)were prepared by simple pyrolysis of Ni-based metal–organic-framework for selective hydrogenation of halogenated nitrobenzenes to corresponding anilines.Two different crystallization methods(stirring and static)were compared and the optimal pyrolysis temperature was explored.Ni@NCNs were systematically characterized by wide analytical techniques.In the hydrogenation of p-chloronitrobenzene,Ni@NCNs-600(pyrolyzed at 600°C)exhibited extraordinarily high performance with 77.9 h^(–1)catalytic productivity and>99%p-chloroaniline selectivity at full p-chloronitrobenzene conversion under mild conditions(90°C,1.5 MPa H2),showing obvious superiority compared with reported Ni-based catalysts.Notably,the reaction smoothly proceeded at room temperature with full conversion and>99%selectivity.Moreover,Ni@NCNs-600 afforded good tolerance to various nitroarenes substituted by sensitive groups(halogen,nitrile,keto,carboxylic,etc.),and could be easily recycled by magnetic separation and reused for 5 times without deactivation.The adsorption tests showed that the preferential adsorption of–NO2 on the catalyst can restrain the dehalogenation of p-chloronitrobenzene,thus achieving high p-chloroaniline selectivity.While the high activity can be attributed to high Ni dispersion,special morphology,and rich pore structure of the catalyst.

关 键 词：halogenated nitrobenzenes room-temperature hydrogenation Ni nanoparticles nitrogen-doped carbon nanoneedles metal–organic-framework 

分 类 号：O62[理学—有机化学]