Issue 8, 2024

Six polyoxotungstate-based transition metal compounds for electrochemical capacitor application and a comparative analysis of factors affecting capacitances

Abstract

Six different polyoxotungstate-based transition metal complexes were synthesized, namely [Cu5(2,2′-bpy)52-Cl)2(PO4)2(H2O)2][HPW12O40]·2H2O (1), [Cu1.5(2,2′-bpy)1.5(inic)2(H2O)1.5]3[H1.5PW12O40]2·16.25H2O (2), [Cu(2,2′-bpy)2]2[SiW12O40]·10H2O (3), [Zn(phen)3]2[PWVWVI11O40]·5H2O (4), [Zn(phen)2(H2O)]2[SiW12O40]·2H2O (5), and [Zn(2,2′-bpy)2]2[SiW12O40] (6) (2,2′-bpy = 2,2′-bipyridine, inic = isonicotinic acid, phen = 1,10-phenanthroline). Compound 1 is based on [HPW12O40]2− anions, which are accommodated within the open channels of a supramolecular network formed by novel Cu–P–Cl coordination clusters. Compound 2 is constructed from [H1.5PW12O40]1.5− and novel [Cu1.5(2,2′-bpy)1.5(inic)2(H2O)1.5]+ coordination fragments, and polyoxoanions are encapsulated within the pores created by the copper coordination fragments, resulting in a unique three-dimensional supramolecular architecture. Compound 3 is a two-dimensional structure formed through the covalent linkage between [SiW12O40]4− and [Cu(2,2′-bpy)2]2+. Compound 4 is a supramolecular architecture formed by [PWVWVI11O40]4− and [Zn(phen)3]2+ coordination fragments, while compound 5 is a supramolecular structure based on POM bi-supported Zn coordination complexes. Compound 6 is a two-dimensional framework structure constituted by [SiW12O40]4− and [Zn(2,2′-bpy)2]2+via covalent interactions. In addition, electrochemical measurement results show that the copper-based tungstate compounds 1–3 and zinc-based tungstate compounds 4–6 exhibit different performances and durabilities as electrochemical capacitors (compound 1 shows the highest specific capacitance of 94.0 F g−1 at 1.5 A g−1, whereas compound 6 maintains the best cycling stability with the capacity retention of 80.7% after 1000 cycles at 4 A g−1.). This study contributes to the development of POM-based transition metal complexes with high capacitance by providing insights into the design and synthesis process.

Graphical abstract: Six polyoxotungstate-based transition metal compounds for electrochemical capacitor application and a comparative analysis of factors affecting capacitances

Supplementary files

Article information

Article type
Paper
Submitted
05 Dec 2023
Accepted
16 Jan 2024
First published
17 Jan 2024

Dalton Trans., 2024,53, 3499-3510

Six polyoxotungstate-based transition metal compounds for electrochemical capacitor application and a comparative analysis of factors affecting capacitances

C. Peng, G. Li, K. Li and X. Cui, Dalton Trans., 2024, 53, 3499 DOI: 10.1039/D3DT04052F

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