无溶剂合成以Co-N物种为活性位点的Co@NC催化剂用于芳香硝基化合物选择加氢  

Solvent-free synthesis of Co@NC catalyst with Co–N species as active sites for chemoselective hydrogenation of nitro compounds

作　　者：魏海生 宋华兴 任煜京 颜晓瑞 方葛钱 王文华 任万忠 朱明远 林坚 Haisheng Wei;Huaxing Song;Yujing Ren;Xiaorui Yan;Geqian Fang;Wenhua Wang;Wanzhong Ren;Mingyuan Zhu;Jian Lin(College of Chemistry and Chemical Engineering,Yantai University,Yantai 264005,China;CAS Key Laboratory of Science and Technology on Applied Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China;Interdisciplinary Research Center of Biology&Catalysis,School of Life Sciences,Northwestern Polytechnical University,Xi’an 710072,China)

机构地区：[1]College of Chemistry and Chemical Engineering,Yantai University,Yantai 264005,China [2]CAS Key Laboratory of Science and Technology on Applied Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China [3]Interdisciplinary Research Center of Biology&Catalysis,School of Life Sciences,Northwestern Polytechnical University,Xi’an 710072,China

出　　处：《Science China Materials》2023年第1期169-178,共10页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(21808193,21878283,22022814,and 22002118);China Postdoctoral Science Foundation(2020TQ0245);the Science and Technology Innovation Development Plan of Yantai(2021XDHZ069);the Youth Innovation Promotion Association CAS(Y2021057);Dalian Science Foundation for Distinguished Young Scholars(2021RJ10);Taishan Scholars Program of Shandong province(tsqn202103051)。

摘　　要：金属有机骨架(MOFs)衍生的Co基催化剂用于芳香硝基化合物选择加氢引起了广泛的关注,但催化剂合成过程中使用大量溶剂,且对催化剂中活性中心的认识存在争议.本文开发了一种固相合成策略,在不使用任何溶剂的情况下获得MOF前体材料,经发泡和热解处理获得Co@NC催化剂.研究发现,800℃热解所得的催化剂中Co纳米颗粒被氮掺杂石墨烯壳层包裹,在3-硝基苯乙烯的加氢过程中表现出~100%的转化率,3-乙烯基苯胺的选择性大于99%,同时,该催化剂具有良好的循环稳定性和底物普适性.表征和实验结果证明该催化剂中Co–N物种为活性中心,其含量可通过热解温度进行调变,且催化性能与Co–N物种的含量存在正相关关系.本工作为设计用于选择加氢反应的高效Co基催化剂提供了一种新的绿色合成策略.Metal-organic frameworks(MOFs)derived Cobased catalysts have received extensive attention in the chemoselective hydrogenation of nitroarenes,while they usually require a lot of solvent during the synthesis and identification of active species.This study explores a solid-phase synthesis strategy to obtain MOF precursors without using any solvent,which is then foamed and pyrolyzed to synthesize the Co@NCX catalyst.It was found that a nitrogen-doped graphene shell can well encapsulate the Co nanoparticles.The resulting catalyst,which was pyrolyzed at 800℃,exhibited~100%conversion for the hydrogenation of 3-nitrostyrene and>99%selectivity to 3-vinylaniline.This catalyst also showed excellent stability and good substrate universality for the hydrogenation of extensive substituted nitroarenes.Various characterizations revealed a positive relationship between the catalytic performance and the content of Co±N species tuned by pyrolysis temperature.This work provides a novel and green strategy to design an efficient Co-based catalyst for chemoselective hydrogenation.

关 键 词：芳香硝基化合物 金属有机骨架 氮掺杂石墨烯 活性中心 合成策略 选择加氢 加氢过程 固相合成 

分 类 号：TQ426[化学工程]