Metal-organic polyhedra(MOPs)have emerged as novel porous platforms for proton conduc-tion,however,the concerted employment of both linker and metal cluster vertex is rarely applied for the fabrication of MOPs-based high conducting materials.Herein we report the synthesis of sulfonate-functiona-lized polyoxovanadate-based MOPs for enhanced proton conduction via the synergistic effect from linker and metal cluster node.MOPs 1 and 2 exhibit octahedral cage configuration constructed from{V5O9Cl}vertex and 5-sulfoisophthalate linker.Owing to the ordered packing of octahedral cages along three axes,3D interpenetrated open channels that are lined with high-density sulfonates are thus formed within 2.Cou-pled with the proton-conductive{V5O9Cl}vertexs as well as protonated counterions,an extensive H-bonded network is therefore generated for facile proton transfer.2 exhibits high proton conductivity of 3.02×10-2 S cm-1 at 65℃under 90％RH,recording the highest value for MOPs pellet sample.This value is enhanced～1 order of magnitude compared with that of carboxylate-functionalized analogue 3,clearly illustrating the ad-vantage of combining linker and metal cluster node for enhanced proton conduction.This work will further promote the exploitation of high proton conductive MOPs-based materials by the synergy design strategy.

Yu Zhang;Shan-Shan Liu;Bo Li;Hanqi You;Longxi Zhang;Zhenyi Zhang;Hong-Ying Zang;Qi Zheng;Weimin Xuan

College of Chemistry,Chemical Engineering and Biotechnology&State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,Donghua University,Shanghai 201620,China;Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education at Universities of Jilin Province,Faculty of Chemistry,Northeast Normal University,Changchun 130024,China;Bruker(Beijing)Scientific Technology Co.,Ltd 9F,Building No.1,Lane 2570,Hechuan Rd,Minhang District,Shanghai 200233,China;State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,College of Materials Science and Engineering,Donghua University,Shanghai 201620,China

结构化学

[1]Yu Zhang;Shan-Shan Liu;Bo Li;Hanqi You;Longxi Zhang;Zhenyi Zhang;Hong-Ying Zang;Qi Zheng;Weimin Xuan-.Sulfonate-Functionalized Polyoxovanadate-Based Metal-Organic Polyhedra for Enhanced Proton Conduction via the Synergy of Linker and Metal Cluster Vertex)[J].结构化学,2022(08):12-17

Sulfonate,Polyoxovanadate,Polyhedra,functiona,polyoxovanadate,V5O9Cl,sulfoisophthalate,sulfonates,vertexs

Functionalized,Based,Metal,Organic,Enhanced,Proton,Conduction,via,Synergy,Linker,Cluster,Vertex,organic,polyhedra,MOPs,have,emerged,novel,porous,platforms,however,concerted,employment,both,linker,metal,cluster,rarely,applied,fabrication,conducting,materials,Herein,report,synthesis,enhanced,conduction,synergistic,effect,from,node,octahedral,configuration,constructed,Owing,ordered,packing,cages,along,three,axes,interpenetrated,open,channels,that,lined,density,thus,formed,within,Cou,pled,conductive,well,protonated,counterions,extensive,bonded,network,therefore,generated,facile,transfer,exhibits,conductivity,under,RH,recording,highest,value,pellet,sample,This,magnitude,compared,carboxylate,functionalized,analogue,clearly,illustrating,vantage,combining,will,further,promote,exploitation,by,synergy,design,strategy

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