Mn-Based Polyoxometalates with Organic–Inorganic Large-Spaced Layers as the Highly Efficient Electrocatalysts for Acidic and Alkaline Hydrogen Evolution Reaction

Polyoxometalates are promising options for electrocatalysts due to electronic sponges properties. Organic-inorganic hybridized polyoxometalates are the focus of research in the field of electrocatalytic hydrogen evolution through substitution by transition metal ions or modification by organic ligands. Using a one-step solution method, two new Mn-based polyoxometalates were successfully created, Na<sub>4</sub>(C<sub>4</sub>H<sub>7</sub>N<sub>2</sub>)[{Mn<sub>3</sub>WO<sub>3</sub>}[BiW<sub>9</sub>O<sub>33</sub>]<sub>2</sub>(H<sub>3</sub>O)<sub>8</sub>]·7H<sub>2</sub>O (1), Na<sub>7</sub>(C<sub>3</sub>H<sub>3</sub>N<sub>2</sub>)[{MnWO<sub>3</sub>}{BiW<sub>9</sub>O<sub>33</sub>}]·14H<sub>2</sub>O (2). Both compounds, 1 and 2 are made up of two {BiW<sub>9</sub>O<sub>33</sub>}<sup>9-</sup> polyoxyanions encapsulated in 10-nuclear high-nuclear clusters containing Mn ions and further connected to organic ligands through hydrogen bonding. It is worth noting that compound 1 forms large-spaced organic-inorganic layered three-dimensional structures with two {BiW<sub>9</sub>O<sub>33</sub>}<sup>9-</sup> polyoxyanions encapsulating 10-nuclear high-nuclear clusters containing Mn ions as the inorganic layer and 2-methylimidazole ligand as the organic layer eventually. However, compound 2 forms a three-dimensional structure with an imidazole ligand organic layer wrapped in an inorganic layer. The two compounds were used in the electrocatalytic hydrogen evolution reaction (HER) in acidic solutions (0.5 M H<sub>2</sub>SO<sub>4</sub>) and alkaline solutions (1 M KOH). Compound 1 has exceptional catalytic activity, with overpotential values of 30 and 140 mV, respectively, which were significantly lower than compound 2 (74 mV/328 mV), Na<sub>12</sub>[(Na(H<sub>2</sub>O)<sub>2</sub>)<sub>6</sub>(BiW<sub>9</sub>O<sub>33</sub>)<sub>2</sub>]·27H<sub>2</sub>O (abbreviated as {BiW<sub>9</sub>}) (369 mV/534 mV), [{NaO<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>}<sub>2</sub>{(Mn(H<sub>2</sub>O)<sub>2</sub>)<sub>2</sub>(WO<sub>2</sub>)<sub>2</sub> (BiW<sub>9</sub>O<sub>33</sub>)<sub>2</sub>}]·16H<sub>3</sub>O<sup>+</sup>·XH<sub>2</sub>O (abbreviated as {BiW<sub>9</sub>-Mn})(285 mV/435 mV) at 10 mA cm<sup>-2</sup> in 0.5 M H<sub>2</sub>SO<sub>4</sub> and 1 M KOH electrolyte solution. Meanwhile, compound 1 showed excellent durability (1000 cycles) and stability (24 h) under both conditions. This study provides a new and convenient way to design organic-inorganic layered polyoxometalates for electrocatalytic hydrogen evolution reactions.

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Journal
Langmuir
Published
2025-11-03
DOI
https://doi.org/10.1021/acs.langmuir.5c04803
Citations
1
Primary Topic
Polyoxometalates: Synthesis and Applications
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article
Field-Weighted Citation Impact
0.52
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article

Mn-Based Polyoxometalates with Organic–Inorganic Large-Spaced Layers as the Highly Efficient Electrocatalysts for Acidic and Alkaline Hydrogen Evolution Reaction

Meijia Wang, Lige Gong, Limin Dong, Jihua Wang
1 citations
Langmuir
Polyoxometalates: Synthesis and Applications
0.52
article

Mn-Based Polyoxometalates with Organic–Inorganic Large-Spaced Layers as the Highly Efficient Electrocatalysts for Acidic and Alkaline Hydrogen Evolution Reaction

Meijia Wang, Lige Gong, Limin Dong, Jihua Wang
article en
1 citations

Abstract

Polyoxometalates are promising options for electrocatalysts due to electronic sponges properties. Organic-inorganic hybridized polyoxometalates are the focus of research in the field of electrocatalytic hydrogen evolution through substitution by transition metal ions or modification by organic ligands. Using a one-step solution method, two new Mn-based polyoxometalates were successfully created, Na<sub>4</sub>(C<sub>4</sub>H<sub>7</sub>N<sub>2</sub>)[{Mn<sub>3</sub>WO<sub>3</sub>}[BiW<sub>9</sub>O<sub>33</sub>]<sub>2</sub>(H<sub>3</sub>O)<sub>8</sub>]·7H<sub>2</sub>O (1), Na<sub>7</sub>(C<sub>3</sub>H<sub>3</sub>N<sub>2</sub>)[{MnWO<sub>3</sub>}{BiW<sub>9</sub>O<sub>33</sub>}]·14H<sub>2</sub>O (2). Both compounds, 1 and 2 are made up of two {BiW<sub>9</sub>O<sub>33</sub>}<sup>9-</sup> polyoxyanions encapsulated in 10-nuclear high-nuclear clusters containing Mn ions and further connected to organic ligands through hydrogen bonding. It is worth noting that compound 1 forms large-spaced organic-inorganic layered three-dimensional structures with two {BiW<sub>9</sub>O<sub>33</sub>}<sup>9-</sup> polyoxyanions encapsulating 10-nuclear high-nuclear clusters containing Mn ions as the inorganic layer and 2-methylimidazole ligand as the organic layer eventually. However, compound 2 forms a three-dimensional structure with an imidazole ligand organic layer wrapped in an inorganic layer. The two compounds were used in the electrocatalytic hydrogen evolution reaction (HER) in acidic solutions (0.5 M H<sub>2</sub>SO<sub>4</sub>) and alkaline solutions (1 M KOH). Compound 1 has exceptional catalytic activity, with overpotential values of 30 and 140 mV, respectively, which were significantly lower than compound 2 (74 mV/328 mV), Na<sub>12</sub>[(Na(H<sub>2</sub>O)<sub>2</sub>)<sub>6</sub>(BiW<sub>9</sub>O<sub>33</sub>)<sub>2</sub>]·27H<sub>2</sub>O (abbreviated as {BiW<sub>9</sub>}) (369 mV/534 mV), [{NaO<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>}<sub>2</sub>{(Mn(H<sub>2</sub>O)<sub>2</sub>)<sub>2</sub>(WO<sub>2</sub>)<sub>2</sub> (BiW<sub>9</sub>O<sub>33</sub>)<sub>2</sub>}]·16H<sub>3</sub>O<sup>+</sup>·XH<sub>2</sub>O (abbreviated as {BiW<sub>9</sub>-Mn})(285 mV/435 mV) at 10 mA cm<sup>-2</sup> in 0.5 M H<sub>2</sub>SO<sub>4</sub> and 1 M KOH electrolyte solution. Meanwhile, compound 1 showed excellent durability (1000 cycles) and stability (24 h) under both conditions. This study provides a new and convenient way to design organic-inorganic layered polyoxometalates for electrocatalytic hydrogen evolution reactions.

LangmuirVol. 41(45)
Harbin University of Science and Technology (CN)
Openalex Percentile: Top 31%
Polyoxometalates: Synthesis and Applications
0.52
DOISourceOpenAlex
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