Dynamically modulated synthesis of hollow metal-organic frameworks for selective hydrogenation reactions  

作　　者：Liyun Xiao Chuanqi Cheng Zhixi Li Chaoyang Zheng Jing Du Meina Song Yue Wan Shaopeng Li Guo Jun Meiting Zhao 

机构地区：[1]Department of Chemistry,Institute of Molecular Aggregation Science,Tianjin Key Laboratory of Molecular Optoelectronic Sciences,Tianjin University,Tianjin 300072,China [2]Institute of New Energy Materials,School of Materials Science and Engineering,Tianjin University,Tianjin 300072,China [3]State Key Laboratory of Separation Membranes and Membrane Processes,School of Chemistry,Tiangong University,Tianjin 300387,China

出　　处：《Nano Research》2023年第8期11334-11341,共8页纳米研究（英文版）

基　　金：The authors acknowledge financial support from the National Natural Science Foundation of China(Nos.21905195,M.T.Z.and 22103055,J.G.);Natural Science Foundation of Tianjin City(No.20JCYBJC00800,M.T.Z.);Science and Technology Plans of Tianjin(No.21ZYJDJC00050,J.G.);PEIYANG Young Scholars Program of Tianjin University(No.2020XRX-0023,M.T.Z.).

摘　　要：Hollow metal-organic frameworks(MOFs)have attracted increasing attention in the field of catalysis in recent years due to their unique cavity structure with fast mass-diffusion rates and easily accessible active sites.Here,we report the use of dynamic modulators,which are formed by the in-situ imine condensation reaction of 4-aminobenzoic acid and 4-formylbenzoic acid,to regulate the growth of MOFs to synthesize well-defined hollow thioether functionalized UiO-67(denoted as H-UiO-67-S)single crystals.After supporting Pd nanoparticles,the designed catalysts Pd@H-UiO-67-S show excellent conversion(>99.9%),selectivity(>99.9%),and stability(10 cycles)in the selective hydrogenation of nitrobenzenes with other reducible groups.Density functional theory calculations and the experimental results reveal that Pd nanoparticles not only selectively adsorb the nitro-groups on nitrobenzene,but also restrict the adsorption of the aniline product,due to the interaction of thioether with Pd in the confined pores of H-UiO-67-S,finally result in a significant increase in selectivity of nitro-hydrogenation.

关 键 词：hollow structure metal-organic frameworks(MOFs) dynamically modulated synthesis selective hydrogenation NITROBENZENE 

分 类 号：O64[理学—物理化学]