Construction of metal-organic frameworks with unsaturated Cu sites for efficient and fast reduction of nitroaromatics:A combined experimental and theoretical study  

作　　者：Longlong Geng Huiling Liu Wenfeng Zhou Yong-Zheng Zhang Hongliang Huang Da-Shuai Zhang Hui Hu Chao Lv Xiuling Zhang Suijun Liu 

机构地区：[1]Shandong Provincial Key Laboratory of Monocrystalline Silicon Semiconductor Materials and Technology,College of Chemistry and Chemical Engineering,Dezhou University,Dezhou 253023,China [2]School of Chemistry and Chemical Engineering,Shandong University of Technology,Zibo 255000,China [3]State Key Laboratory of Separation Membranes and Membrane Processes,School of Chemical Engineering and Technology,Tiangong University,Tianjin 300387,China [4]School of Chemistry and Chemical Engineering,Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry,Jiangxi University of Science and Technology,Ganzhou 341000,China

出　　处：《Chinese Chemical Letters》2024年第8期514-519,共6页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.21902022,81903501,21601028);Qingchuang Science and Technology Plan of Shandong Province(No.2021KJ054);the Natural Science Foundation of Shandong Province(Nos.ZR2018LB018,ZR2019QB026,ZR2022QB058,ZR2020KB014);Scientific Research Foundation of Dezhou University(Nos.30101905,30102708,30102701).

摘　　要：Metal-organic frameworks(MOFs)functionalized with open metal sites(OMSs)have received widespread attention in various applications due to their fascinating electronic properties and unique interactions with guest molecules.However,rational tailoring of the coordination environment of metal nodes dur-ing the synthesis of MOFs remains a great challenge due to their tendency of saturated coordination with linkers.Herein,we reported the construction of three new MOFs featuring unsaturated Cu(Ⅱ)sites,namely[Cu(HCOO)(pzta)]_(n)(HL-1),{[Cu(PTA)0.5(pzta)(H_(2)O)]·2H_(2)O}_(n)(HL-2)and[Cu(NA)0.5(pzta)]_(n)(HL-3)(Hpzta=3-pyrazinyl-1,2,4-triazole;PTA=terephthalic acid;NA=1,4-naphthalene dicarboxylic acid),based on the mixed-linker strategy via specific selection of versatile Hpzta ligand and carboxylate ligands.Re-markably,the obtained MOFs exhibited excellent activity and good recyclability for the catalytic reduction of nitroaromatics under mild conditions(25℃and 1 atm).In particular,the complete conversion of 4-nitrophenol(4-NP)took only 30 s on HL-2,reaching a record-high TOF value compared with previously reported metal catalysts.The combined experimental and theoretical studies on HL-2 revealed that the open Cu site with positive-charged nature could improve the adsorption and subsequent electron trans-port between the substrates,and was responsible for the outstanding performance.This work shined lights on the further enhancement of performance for MOFs through rational OMSs construction.

关 键 词：Metal-organic frameworks Open metal sites CATALYSIS Copper node 4-NITROPHENOL 

分 类 号：O643.36[理学—物理化学] O621.251[理学—化学]