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Design and synthesis of phosphomolybdate coordination compounds based on {P4Mo6} structural units and their proton conductivity

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Abstract

Developing new low-cost and efficient proton-conducting materials remains an attractive and challenging task. Herein, sodium molybdate dihydrate is used as the source of molybdenum, mixed with transition metal chloride and 2-methylimidazole (2-MI), using the "one-pot method" to synthesize two crystalline proton conducting materials based on {P4Mo6} units: H14[C4H6N2]2[M(H2O)5] [M(H2O)2]2{M[(PO3)3(PO4)Mo6O15]2}·4H2O (M=Co and Fe) (1–2). Different from the common {P4Mo6}, we use H3PO3 to adjust the pH value, resulting in two different coordination modes of P atoms in the crystal structure. The structure is expanded into three-dimensional network by metal ions. At 75 °C and 98% relative humidity, the proton conductivity of compounds 1 and 2 are 1.33 × 10–2 S·cm−1 and 1.03 × 10–2 S·cm−1, respectively. The high proton conductivity is mainly attributed to the free state of 2-methylimidazole as the proton carrier, which has a fast migration rate. At the same time, 2-methylimidazole, coordination water, and {P4Mo6} anion form a hydrogen bond network to provide multiple pathways for the transmission of protons.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 21871042, 21471028, 21673098, and 21671036), Natural Science Foundation of Jilin Province (Grant No. 20200201083JC), Jilin Provincial Education Department (Grant No. JJKH20201169KJ), the Fundamental Research Funds for the Central Universities (Grant Nos. 2412015KJ012, 2412017BJ004), and the support of the Jilin Provincial Department of Education.

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  1. Zhi-Xin Gao and Sai Sun contributed equally to this work.

Authors and Affiliations

  1. 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

    Zhi-Xin Gao, Sai Sun, Bo Li, Dong-Ming Cheng, Yong-Hui Wang, Hong-Ying Zang & Yang-Guang Li

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  1. Zhi-Xin Gao
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ZG and SS designed and wrote the draft; BL and DC collected the data; ZG and SS contributed equally to this work. All authors contributed to the writing and revisions.

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Correspondence to Hong-Ying Zang.

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Gao, ZX., Sun, S., Li, B. et al. Design and synthesis of phosphomolybdate coordination compounds based on {P4Mo6} structural units and their proton conductivity. Tungsten 5, 67–74 (2023). https://doi.org/10.1007/s42864-021-00122-5

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  • DOI: https://doi.org/10.1007/s42864-021-00122-5

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