Architecting Cobalt-Centered 2D Sandwich-Type Polyoxometalate Frameworks for Selective Electrocatalytic Nitrate Reduction to Ammonia

Developing efficient electrocatalysts for neutral-media nitrate reduction (NO<sub>3</sub><sup>-</sup>RR) is crucial for simultaneous nitrate remediation and sustainable ammonia (NH<sub>3</sub>) synthesis, yet hindered by sluggish reaction kinetics. Herein, we designed and synthesized four novel two-dimensional (2D) cobalt-centered hourglass-shaped [P<sub>4</sub>Mo<sub>6</sub><sup>V</sup>O<sub>31</sub>]<sup>12-</sup>-based crystalline materials via the hydrothermal method: (H<sub>2</sub>bimb)<sub>2</sub>[Co<sub>3</sub>{Mo<sub>6</sub>O<sub>15</sub>(HPO<sub>4</sub>)<sub>3</sub>(PO<sub>4</sub>)}<sub>2</sub>]·7H<sub>2</sub>O (1), (H<sub>2</sub>bimb)<sub>2</sub>[Co<sub>3</sub>{Mo<sub>6</sub>O<sub>15</sub>(HPO<sub>4</sub>)<sub>3</sub>(PO<sub>4</sub>)}<sub>2</sub>]·16H<sub>2</sub>O (2), [{Co(Hbimb)<sub>2</sub>}<sub>2</sub>][{Co(H<sub>2</sub>O)<sub>2</sub>}Co{Mo<sub>6</sub>O<sub>15</sub>(HPO<sub>4</sub>)<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>}<sub>2</sub>]·10H<sub>2</sub>O (3), and (H<sub>2</sub>bimb)<sub>2</sub>[Co(Hbimb)<sub>2</sub>][{Co(H<sub>2</sub>O)<sub>2</sub>}<sub>2</sub>Co{Mo<sub>6</sub>O<sub>15</sub>(HPO<sub>4</sub>)<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>}<sub>2</sub>]·18H<sub>2</sub>O (4) (bimb = 1,3-bis(1H-imidazol-1-yl)benzene), featuring tunable hourglass-type [P<sub>4</sub>Mo<sub>6</sub><sup>V</sup>O<sub>31</sub>]<sup>12-</sup> clusters. The experimental results showed that compounds 1-4 all exhibited better NO<sub>3</sub><sup>-</sup>RR performance, among which compound 4 exhibited excellent stability and outstanding redox activity performance with a Faradaic efficiency of 89.65% at -0.7 V (versus reversible hydrogen electrode) and an ammonia synthesis rate of 8.97 mg h<sup>-1</sup> mg<sub>cat</sub><sup>-1</sup>. This work extends the application of e-NO<sub>3</sub><sup>-</sup>RR catalysts based on polymetallic oxides and opens up innovative pathways for sustainable ammonia synthesis through molecular-level structure modulation.

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Publication Details

Journal
Inorganic Chemistry
Published
2025-10-17
DOI
https://doi.org/10.1021/acs.inorgchem.5c03275
Citations
2
Primary Topic
Ammonia Synthesis and Nitrogen Reduction
Type
article
Field-Weighted Citation Impact
0.78
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article

Architecting Cobalt-Centered 2D Sandwich-Type Polyoxometalate Frameworks for Selective Electrocatalytic Nitrate Reduction to Ammonia

Xiaoming Ren, Qiushuang Jiang, Haijun Pang, Gang Li et al.
2 citations
Inorganic Chemistry
Ammonia Synthesis and Nitrogen Reduction
0.78
article

Architecting Cobalt-Centered 2D Sandwich-Type Polyoxometalate Frameworks for Selective Electrocatalytic Nitrate Reduction to Ammonia

Xiaoming Ren, Qiushuang Jiang, Haijun Pang, Gang Li, Xinming Wang, Hui Luo, Huiyuan Ma
article en
2 citations

Abstract

Developing efficient electrocatalysts for neutral-media nitrate reduction (NO<sub>3</sub><sup>-</sup>RR) is crucial for simultaneous nitrate remediation and sustainable ammonia (NH<sub>3</sub>) synthesis, yet hindered by sluggish reaction kinetics. Herein, we designed and synthesized four novel two-dimensional (2D) cobalt-centered hourglass-shaped [P<sub>4</sub>Mo<sub>6</sub><sup>V</sup>O<sub>31</sub>]<sup>12-</sup>-based crystalline materials via the hydrothermal method: (H<sub>2</sub>bimb)<sub>2</sub>[Co<sub>3</sub>{Mo<sub>6</sub>O<sub>15</sub>(HPO<sub>4</sub>)<sub>3</sub>(PO<sub>4</sub>)}<sub>2</sub>]·7H<sub>2</sub>O (1), (H<sub>2</sub>bimb)<sub>2</sub>[Co<sub>3</sub>{Mo<sub>6</sub>O<sub>15</sub>(HPO<sub>4</sub>)<sub>3</sub>(PO<sub>4</sub>)}<sub>2</sub>]·16H<sub>2</sub>O (2), [{Co(Hbimb)<sub>2</sub>}<sub>2</sub>][{Co(H<sub>2</sub>O)<sub>2</sub>}Co{Mo<sub>6</sub>O<sub>15</sub>(HPO<sub>4</sub>)<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>}<sub>2</sub>]·10H<sub>2</sub>O (3), and (H<sub>2</sub>bimb)<sub>2</sub>[Co(Hbimb)<sub>2</sub>][{Co(H<sub>2</sub>O)<sub>2</sub>}<sub>2</sub>Co{Mo<sub>6</sub>O<sub>15</sub>(HPO<sub>4</sub>)<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>}<sub>2</sub>]·18H<sub>2</sub>O (4) (bimb = 1,3-bis(1H-imidazol-1-yl)benzene), featuring tunable hourglass-type [P<sub>4</sub>Mo<sub>6</sub><sup>V</sup>O<sub>31</sub>]<sup>12-</sup> clusters. The experimental results showed that compounds 1-4 all exhibited better NO<sub>3</sub><sup>-</sup>RR performance, among which compound 4 exhibited excellent stability and outstanding redox activity performance with a Faradaic efficiency of 89.65% at -0.7 V (versus reversible hydrogen electrode) and an ammonia synthesis rate of 8.97 mg h<sup>-1</sup> mg<sub>cat</sub><sup>-1</sup>. This work extends the application of e-NO<sub>3</sub><sup>-</sup>RR catalysts based on polymetallic oxides and opens up innovative pathways for sustainable ammonia synthesis through molecular-level structure modulation.

Inorganic ChemistryVol. 64(42)
Harbin University of Science and Technology (CN), Green Chemistry (PL)
Openalex Percentile: Top 27%
Ammonia Synthesis and Nitrogen Reduction
0.78
DOISourceOpenAlex
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