Nanostructured Ni-MoCx:An efficient non-noble metal catalyst for the chemoselective hydrogenation of nitroaromatics  

作　　者：Yifei Zhang Zhiwen Li Jingjing Zhang Liangliang Xu Zhong-Kang Han Alfons Baiker Gao Li 

机构地区：[1]Institute of Catalysis for Energy and Environment,College of Chemistry and Chemical Engineering,Shenyang Normal University,Shenyang 110034,China [2]State Key Laboratory of Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China [3]Department of Chemical and Biomolecular Engineering,Korea Advanced Institute of Science and Technology(KAIST),Daejeon 34141,Republic of Korea [4]School of Materials Science and Engineering,Zhejiang University,Hangzhou 310027,China [5]Department of Chemistry and Applied Biosciences,Institute for Chemical and Bioengineering,ETH Zurich,Hönggerberg,HCl,Zurich CH-8093,Switzerland [6]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Nano Research》2023年第7期8919-8928,共10页纳米研究（英文版）

基　　金：We thank the National Natural Science Foundation of China for supporting this work(No.22172167);The 1W1B beamline of Beijing Synchrotron Radiation Facility and BL14W1 beamline of Shanghai Synchrotron Radiation Facility are acknowledged for providing the beam time.

摘　　要：Catalysts for chemoselective hydrogenation are of vital importance for the synthesis of various important chemicals and intermediates.Herein we developed a simple method for preparing a highly efficient Ni-MoC_(x)nanocomposite catalyst via temperature-programmed carburization of a polyoxometalate precursor.X-ray diffraction(XRD),scanning transmission electron microscopy(STEM),X-ray photoelectron spectroscopy(XPS),and X-ray absorption spectroscopy(XAS)analyses indicate that the resulting mesoporous nanocomposite catalyst is made up of well-dispersed metallic nickel particles embedded in a MoC_(x)matrix.This catalyst exhibits high activity and selectivity(>99%)in the hydrogenation of various substituted nitroaromatics to corresponding anilines.The high efficiency is attributed to the intimate contact of the constituents favoring electron transfer and hydrogen adsorption.Dihydrogen is physisorbed on the carbide support and dissociates on the nickel particles,as evidenced by Mo K-edge X-ray absorption near-edge structure(XANES)spectra,density functional theory(DFT),and hydrogen-deuterium exchange.The remarkable catalytic performance of the catalyst could be traced back to the synergistic interaction between the Ni particles and the carbide support.In-situ infrared spectroscopy and DFT simulations indicated that the adsorption/activation of the nitro group is favored compared to that of other substituents at the aromatic ring.In recyclability tests,the Ni-MoC_(x)nanocomposite showed no significant loss of catalytic performance in seven consecutive runs,indicating its robust nature.

关 键 词：Ni-MoC_(x)nanocomposite carburization of polyoxometalate HYDROGENATION NITROAROMATICS synergistic effect 

分 类 号：O64[理学—物理化学]