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A highly reduced Mo74 polyoxometalate featuring high proton conductivity accessed by building block strategy

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Abstract

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 (C2H8N)14(NH4)4H14[MoV48MoVI26O202(OH)12(SO4)6]·46H2O (Mo74). The fundamental Mo-based {Mox} (x = 4, 5, and 6) building blocks, which are templated by tetra-coordinated anions {MoO4} or, not only lay foundation for the formation of Mo74 featuring an unprecedented reduction ratio of 65%, but also give rise to SBBs-mediated (secondary building blocks) supramolecular dense packing interactions among the isolated Mo74 clusters that are favorable for proton conduction. Remarkably, high proton conductivity (2.04 × 10−2 S cm−1) had been realized at 50 °C 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.

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Acknowledgements

This work was 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), and the Fundamental Research Funds for the Central Universities (2412022ZD002, 2412022ZD009).

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Authors and Affiliations

  1. Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, 130024, China

    Shi-Yi Liu, Xue-**n Li, Wei-Chao Chen, Kui-Zhan Shao, **n-Long Wang, Chao Qin & Zhong-Min Su

  2. State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun, 130021, China

    Zhong-Min Su

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  1. Shi-Yi Liu
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  2. Xue-**n Li
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Correspondence to Wei-Chao Chen, **n-Long Wang or Zhong-Min Su.

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Supporting information The supporting information is available online at chem.scichina.com and springer.longhoe.net/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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11426_2023_1776_MOESM1_ESM.pdf

Development of the Building Block Strategy To Access a Highly Reduced Mo74 Polyoxometalate Featuring High Proton Conductivity

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Liu, SY., Li, XX., Chen, WC. et al. A highly reduced Mo74 polyoxometalate featuring high proton conductivity accessed by building block strategy. Sci. China Chem. 67, 862–868 (2024). https://doi.org/10.1007/s11426-023-1776-0

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  • DOI: https://doi.org/10.1007/s11426-023-1776-0

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