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介孔氮稳定的钴锌碳实现硝基化合物高效转移氢化制胺

Efficient Transfer Hydrogenation of Nitro Compounds to Amines Enabled by Mesoporous N-Stabilized Co-Zn/C.

作者信息

Xu Yufei, Long Jingxuan, Zhao Wenfeng, Li Hu, Yang Song

机构信息

State Key Laboratory Breeding Base of Green Pesticide & Agricultural Bioengineering, Key Laboratory of Green Pesticide & Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for Research & Development of Fine Chemicals, Guizhou University, Guiyang, China.

出版信息

Front Chem. 2019 Aug 27;7:590. doi: 10.3389/fchem.2019.00590. eCollection 2019.

Abstract

N-doped metal materials with enhanced stability and abundant porosity have attracted tremendous attention in catalytic reactions. Herein, a simple solvothermal approach was demonstrated to significantly enlarge the pore dimension of conventional microporous zeolitic imidazolate framework (ZIF) incorporated with two kinds of central metals (Co, Zn), while maintaining the original ZIF crystal morphology. Upon further pyrolysis, the resulting mesoporous Co-Zn/N-C material could possess the highly dispersed metal particle on the N-doped carbon, with satisfactory pore volume and surface area. The partial vaporization of Zn and the stabilizing effect of N, illustrated by XRD, HRTEM, HAADF-STEM with mapping, SEM, Raman Spectrum, BET, and TGA, were able to remarkably increase the accessibility of substrate toward active sites and prevent the aggregation of metal particles, respectively. Under mild reaction conditions, the N-stabilized Co-Zn/N-C exhibited good activity and selectivity in transfer hydrogenation of various nitro compounds to corresponding amines, where a synergistic role among Co, Zn, and N was responsible for its superior performance to other tested catalysts. In addition, the N-doped non-noble metal/carbon heterogeneous catalyst was fairly stable and could be reused several times without obvious deactivation.

摘要

具有增强稳定性和丰富孔隙率的氮掺杂金属材料在催化反应中引起了极大关注。在此,展示了一种简单的溶剂热方法,可在保持原始沸石咪唑酯骨架(ZIF)晶体形态的同时,显著扩大与两种中心金属(钴、锌)结合的传统微孔ZIF的孔径。进一步热解后,所得的介孔Co-Zn/N-C材料在氮掺杂碳上可拥有高度分散的金属颗粒,具有令人满意的孔体积和表面积。通过XRD、HRTEM、带图谱的HAADF-STEM、SEM、拉曼光谱、BET和TGA表明,锌的部分汽化和氮的稳定作用分别能够显著提高底物对活性位点的可及性并防止金属颗粒聚集。在温和的反应条件下,氮稳定的Co-Zn/N-C在各种硝基化合物转移加氢生成相应胺的反应中表现出良好的活性和选择性,其中钴、锌和氮之间的协同作用是其性能优于其他测试催化剂的原因。此外,这种氮掺杂的非贵金属/碳多相催化剂相当稳定,可重复使用多次而无明显失活。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7906/6718455/a90912db0d57/fchem-07-00590-g0001.jpg

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