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Systematic Approach to the Synthesis of Cobalt-Containing Polyoxometalates for Their Application as Energy Storage Materials

New energy storage materials are an object of study within the framework of the global energy transition. The development of renewable sources is being boosted thanks to stationary energy storage systems such as redox flow batteries (RFBs). This work reports the synthesis of the cobalt-containing Ke...

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Autores principales: Barros, Ángela, Artetxe, Beñat, Eletxigerra, Unai, Aranzabe, Estibaliz, Gutiérrez-Zorrilla, Juan M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10384885/
https://www.ncbi.nlm.nih.gov/pubmed/37512329
http://dx.doi.org/10.3390/ma16145054
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author Barros, Ángela
Artetxe, Beñat
Eletxigerra, Unai
Aranzabe, Estibaliz
Gutiérrez-Zorrilla, Juan M.
author_facet Barros, Ángela
Artetxe, Beñat
Eletxigerra, Unai
Aranzabe, Estibaliz
Gutiérrez-Zorrilla, Juan M.
author_sort Barros, Ángela
collection PubMed
description New energy storage materials are an object of study within the framework of the global energy transition. The development of renewable sources is being boosted thanks to stationary energy storage systems such as redox flow batteries (RFBs). This work reports the synthesis of the cobalt-containing Keggin-type polyoxometalates [CoW(12)O(40)](6−) (CoW(12)) and [Co(H(2)O)SiW(11)O(39)](6−) (CoSiW(11)), which have previously been shown to have applicability in RFBs. These procedures were reassessed to meet the strict requirements associated with the further implementation of RFBs, including fast and affordable synthetic procedures with high reaction yields. In contrast to the lengthy and complicated synthetic approaches published to date, the optimized synthesis reported in this work enables the isolation of the pure crystalline salt of the CoW(12) anion with a 75% reduction of the time of the whole reaction procedure, eliminating tedious steps such as the recrystallization and including a 20% increased yield. The control of the stoichiometry, fine-tuning of reaction conditions, and the identification of intermediate species, as well as the acidic equilibria taking place during the process, were monitored via thermal, spectroscopic, and structural analyses. In the case of the CoSiW(11) anion, its preparation was based on a simple and highly efficient procedure. Moreover, promising electrochemical properties were observed with the use of the one-pot synthetic approach, in which the stoichiometric amounts of the starting reagents are dissolved in the supporting electrolyte to be directly implemented as the electrolyte for a RFB.
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spelling pubmed-103848852023-07-30 Systematic Approach to the Synthesis of Cobalt-Containing Polyoxometalates for Their Application as Energy Storage Materials Barros, Ángela Artetxe, Beñat Eletxigerra, Unai Aranzabe, Estibaliz Gutiérrez-Zorrilla, Juan M. Materials (Basel) Article New energy storage materials are an object of study within the framework of the global energy transition. The development of renewable sources is being boosted thanks to stationary energy storage systems such as redox flow batteries (RFBs). This work reports the synthesis of the cobalt-containing Keggin-type polyoxometalates [CoW(12)O(40)](6−) (CoW(12)) and [Co(H(2)O)SiW(11)O(39)](6−) (CoSiW(11)), which have previously been shown to have applicability in RFBs. These procedures were reassessed to meet the strict requirements associated with the further implementation of RFBs, including fast and affordable synthetic procedures with high reaction yields. In contrast to the lengthy and complicated synthetic approaches published to date, the optimized synthesis reported in this work enables the isolation of the pure crystalline salt of the CoW(12) anion with a 75% reduction of the time of the whole reaction procedure, eliminating tedious steps such as the recrystallization and including a 20% increased yield. The control of the stoichiometry, fine-tuning of reaction conditions, and the identification of intermediate species, as well as the acidic equilibria taking place during the process, were monitored via thermal, spectroscopic, and structural analyses. In the case of the CoSiW(11) anion, its preparation was based on a simple and highly efficient procedure. Moreover, promising electrochemical properties were observed with the use of the one-pot synthetic approach, in which the stoichiometric amounts of the starting reagents are dissolved in the supporting electrolyte to be directly implemented as the electrolyte for a RFB. MDPI 2023-07-17 /pmc/articles/PMC10384885/ /pubmed/37512329 http://dx.doi.org/10.3390/ma16145054 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Barros, Ángela
Artetxe, Beñat
Eletxigerra, Unai
Aranzabe, Estibaliz
Gutiérrez-Zorrilla, Juan M.
Systematic Approach to the Synthesis of Cobalt-Containing Polyoxometalates for Their Application as Energy Storage Materials
title Systematic Approach to the Synthesis of Cobalt-Containing Polyoxometalates for Their Application as Energy Storage Materials
title_full Systematic Approach to the Synthesis of Cobalt-Containing Polyoxometalates for Their Application as Energy Storage Materials
title_fullStr Systematic Approach to the Synthesis of Cobalt-Containing Polyoxometalates for Their Application as Energy Storage Materials
title_full_unstemmed Systematic Approach to the Synthesis of Cobalt-Containing Polyoxometalates for Their Application as Energy Storage Materials
title_short Systematic Approach to the Synthesis of Cobalt-Containing Polyoxometalates for Their Application as Energy Storage Materials
title_sort systematic approach to the synthesis of cobalt-containing polyoxometalates for their application as energy storage materials
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10384885/
https://www.ncbi.nlm.nih.gov/pubmed/37512329
http://dx.doi.org/10.3390/ma16145054
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