Construction of isolated Ni sites on nitrogen-doped hollow carbon spheres with Ni-N_(3) configuration for enhanced reduction of nitroarenes

作     者：Binbin Feng Rou Guo Qiulan Cai Yaping Song Nan Li Yanghe Fu De-Li Chen Jiangwei Zhang Weidong Zhu Fumin Zhang Binbin Feng;Rou Guo;Qiulan Cai;Yaping Song;Nan Li;Yanghe Fu;De-Li Chen;Jiangwei Zhang;Weidong Zhu;Fumin Zhang

作者机构：Key Laboratory of the Ministry of Education for Advanced Catalysis MaterialsInstitute of Physical ChemistryZhejiang Normal UniversityJinhua 321004China Dalian National Laboratory for Clean Energy&State Key Laboratory of CatalysisDalian Institute of Chemical PhysicsChinese Academy of SciencesDalian 116023China 

出 版 物：《Nano Research》 (纳米研究（英文版）)

年 卷 期：2022年第15卷第7期

页      面：6001-6009页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：the National Natural Science Foundation of China(Nos.21576243 and 21701168) Natural Science Foundation of Zhejiang Province(Nos.LY18B060006,LY17B060001,and LY21B030003) the National Key R&D Program of China(No.2020YFA0406101) Dalian high level talent innovation project(No.2019RQ063) Open project Foundation of State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences(No.20200021) 

主　　题：single-atom catalyst chemo-selective reduction nitro compounds aromatic amines 

摘      要：Designing and synthesizing high-efficiency non-precious metal-based catalysts having uniform active sites increases the reactivity and selectivity of materials and provides a platform for an in-depth understanding of their catalytic reaction *** this study,we provided an approach for fabricating isolated nickel single-atom sites(Ni SAs)with high loading(4.9 wt.%)stabilized on nitrogen-doped hollow carbon spheres(NHCS)using a core–shell structured Zn/Ni bimetallic zeolitic imidazolate framework(ZIF)composite as the sacrificial *** as-fabricated Ni SAs/NHCS catalyst shows superior activity,selectivity,and recycling durability for the catalytic transfer hydrogenation of nitrobenzene to aniline,thus achieving 100%yield of aniline with a turn-over frequency(TOF)value as high as 29.9 h^(−1) under mild *** TOF value is considerably superior to the supported Ni nanoparticle *** experiments designed show that the hollow structure feature of NHCS facilitates accessible active sites and mass transfer,which thus contributes to the enhancement of the catalytic performance of Ni SAs/*** functional theory calculations show the high chemo-selectivity and activity of the Ni SAs catalyst,arising from the unique role of the single Ni-N3 site on simultaneously activating the H donor(N_(2)H_(4))and substrate,as well as the hydrogenation of the–NOH group as the rate-determining step.