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Molecular Speciation of Isopolyoxomolybdates and Isopolyoxotungstates with Silicic Acid in Aqueous Solution Using ESI–MS

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Abstract

There have been few reports on the characterization of molybdate and tungstate species in pure water using ESI–MS. Hexameric molybdate anions were reported to be unstable in neutral solution, but to exist in acidic solutions. The monomolybdate anion was found to be stable in pure aqueous solution in the form of [HMoO4]−. Monomeric tungstate was observed as [WO4]2− and [HWO4]− in acidic solution. At low pH, [Mo4O13]2−, [HMo4O13]− and [HW3O10]− were the main molecular species observed. At high pH, hydrolyzed [HMoO4]− and [HWO4]− were detected by mass spectometer. When silicic acid was added to the molybdate solution, [SiMo12O40]4− and [HSiMo12O40]3− were formed from the tetrameric molybdate anion. In addition, monomeric, trimeric, hexameric, heptameric, undecameric and dodecameric polyoxomolybdates were detected in the supernatant solution by ESI mass spectrometry. When silicic acid was added to a tungstate solution, [HSiW12O40]3−, composed of the trimeric tungstate anion was detected. In addition, two pentameric polyoxotungstates as well as tetrameric, hexameric and heptameric polyoxotungstates were present in the supernatant solution, while no monomer or dimer was detected.

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Acknowledgements

This study was partly supported by THE TOYO SUISAN FOUNDATION.

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Authors and Affiliations

  1. Graduate School of Marine Science and Technology, Tokyo University of Marine Science and Technology, 4-5-7, Konan, Minato-ku, Tokyo, 108-8277, Japan

    Yuri Osuka, Kyota Ii, Kotaro Tsuchiya, Masao Nemoto & Miho Tanaka

  2. RIKEN, Hirosawa 2-1, Wako-shi, Saitama, 351-0198, Japan

    Yu Vin Sahoo & Kazuya Takahashi

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Contributions

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by MT, YO, KI and RU and discussed by KT, MN, YVS, KT and MT. The first draft of the manuscript was written by TM and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Miho Tanaka.

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Osuka, Y., Ii, K., Tsuchiya, K. et al. Molecular Speciation of Isopolyoxomolybdates and Isopolyoxotungstates with Silicic Acid in Aqueous Solution Using ESI–MS. J Solution Chem 53, 642–654 (2024). https://doi.org/10.1007/s10953-023-01255-6

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