Chen, J.-J. et al. (2022) Effective storage of electrons in water by the formation of highly reduced polyoxometalate clusters. Journal of the American Chemical Society, 144(20), pp. 8951-8960. (doi: 10.1021/jacs.1c10584) (PMID:35536652)
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Abstract
Aqueous solutions of polyoxometalates (POMs) have been shown to have potential as high-capacity energy storage materials due to their potential for multi-electron redox processes, yet the mechanism of reduction and practical limits are currently unknown. Herein, we explore the mechanism of multi-electron redox processes that allow the highly reduced POM clusters of the form {MO3}y to absorb y electrons in aqueous solution, focusing mechanistically on the Wells–Dawson structure X6[P2W18O62], which comprises 18 metal centers and can uptake up to 18 electrons reversibly (y = 18) per cluster in aqueous solution when the countercations are lithium. This unconventional redox activity is rationalized by density functional theory, molecular dynamics simulations, UV–vis, electron paramagnetic resonance spectroscopy, and small-angle X-ray scattering spectra. These data point to a new phenomenon showing that cluster protonation and aggregation allow the formation of highly electron-rich meta-stable systems in aqueous solution, which produce H2 when the solution is diluted. Finally, we show that this understanding is transferrable to other salts of [P5W30O110]15– and [P8W48O184]40– anions, which can be charged to 23 and 27 electrons per cluster, respectively.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Busche, Dr Christopher and Ganin, Dr Alexey and Vila-Nadal, Dr Laia and Chisholm, Dr Greig and Zhao, Dr Tingting and Minato, Dr Takuo and Kandasamy, Dr Balamurugan and Cronin, Professor Lee and Chen, Dr Jiajia |
| Authors: | Chen, J.-J., Vilà-Nadal, L., Solé-Daura, A., Chisholm, G., Minato, T., Busche, C., Zhao, T., Kandasamy, B., Ganin, A. Y., Smith, R. M., Colliard, I., Carbó, J. J., Poblet, J. M., Nyman, M., and Cronin, L. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Journal of the American Chemical Society |
| Publisher: | American Chemical Society |
| ISSN: | 0002-7863 |
| ISSN (Online): | 1520-5126 |
| Published Online: | 10 May 2022 |
| Copyright Holders: | Copyright © 2022 American Chemical Society |
| First Published: | First published in Journal of the American Chemical Society 144(20): 8951-8960 |
| Publisher Policy: | Reproduced under a Creative Commons License |
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