A highly reduced Mo_(74) polyoxometalate featuring high proton conductivity accessed by building block strategy  

作　　者：Shi-Yi Liu Xue-Xin Li Wei-Chao Chen Kui-Zhan Shao Xin-Long Wang Chao Qin Zhong-Min Su 

机构地区：[1]Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education,Department of Chemistry,Northeast Normal University,Changchun 130024,China [2]State Key Laboratory of Supramolecular Structure and Materials,Institute of Theoretical Chemistry,College of Chemistry,Jilin University,Changchun 130021,China

出　　处：《Science China Chemistry》2024年第3期862-868,共7页中国科学（化学英文版）

基　　金：supported by the Natural Science Foundation of Jilin Province-Free Exploration General Project(YDZJ202201ZYTS331);the National Natural Science Foundation of China(21801038);the Science and Technology Research Foundation of Jilin Educational Committee(JJKH20221158KJ);the Fundamental Research Funds for the Central Universities(2412022ZD002,2412022ZD009)。

摘　　要：Highly reduced polyoxometalates(POMs) are predicted to be used as rather high energy density materials;however,it still suffers from the limited cluster species and reduction ratio.Here we demonstrate that it is possible to employ the building block strategy to generate a highly reduced polyoxomolybdate(C_(2)H_(8)N)_(14)(NH_(4))_(4)H_(14)[Mo_(48)-ⅤMo_(26)ⅥO_(202)(OH)_(12)(SO_(4))_(6)]·46H_(2)O(Mo_(74)).The fundamental Mo-based{Mo_x}(x=4,5,and 6) building blocks,which are templated by tetra-coordinated anions{MoO_(4)}or{SO_(4)},not only lay foundation for the formation of Mo_(74) featuring an unprecedented reduction ratio of 65%,but also give rise to SBBs-mediated(secondary building blocks) supramolecular dense packing interactions among the isolated Mo_(74) clusters that are favorable for proton conduction.Remarkably,high proton conductivity(2.04×10^(-2)S cm^(-1)) had been realized at 50℃ and 90% relative humidity,revealing one of the well-known POMs-based crystalline proton conducting materials.This result highlights that this building block approach possesses great potential in producing highly reduced POM systems that can achieve controllable reduced ratio and desirable properties.

关 键 词：POLYOXOMETALATE building block MOLYBDENUM highly reduced state proton conduction 

分 类 号：TB34[一般工业技术—材料科学与工程]