Elsevier

Polyhedron

Volume 204, 1 August 2021, 115245
Polyhedron

Two Anderson-type POM-based metal-organic complexes as multifunctional materials for electrocatalytic sensing and zinc-ion batteries

https://doi.org/10.1016/j.poly.2021.115245Get rights and content

Abstract

Two Anderson-type polyoxometalate (POM)-based metal-organic complexes (MOCs), {Cd(3-Hbpah)2(H2O)2[CrMo6(OH)5O19]}(1), {Zn(3-Hbpah)2(H2O)2[CrMo6(OH)5O19]} (2), (3-bpah = N,N′-bis(3-pyridinecarboxamide)-1,2-cyclohexane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra and powder X-ray diffraction. Complexes 12 reveal similar 1D structure and can be taken as a kind of aqueous multifunctional materials. Their electrochemical sensing performance and energy storage performance as zinc-ion battery cathode were studied, respectively. Complexes 12 also exhibit high adsorption performance towards methylene blue and gentian violet, respectively.

Graphical abstract

In this work, two isomorphic POM-based complexes were obtained. The electrochemical behaviour and dye adsorption properties of the title complexes have been investigated. In addition, aqueous ZIBs were constructed using complex 1 as the cathode, which shows good storage performance and cycle stability.

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Introduction

With the exhaustion of non-renewable energy resources, developing advanced technology for energy storage and conversion has aroused urgent need [1], [2]. Polyoxometalates (POMs), constructed from inorganic metal-oxygen clusters, show promises to a wide range of applications in electrochemistry and catalysis [3], [4], [5]. As is well known, POMs exhibit various shapes and sizes with high negative charges. Their negatively charged structures can accelerate the electron transport during electrochemical processes, which play a vital role for electrochemical applications [6], [7], [8]. Currently, many reports have focused on introducing POMs into metal-organic complexes (MOCs), which enable the polyoxoanions to show excellent stability in aqueous environment, while retaining their electrochemical property [9].

As a kind of emerging electrochemical applications, aqueous zinc-ion batteries (ZIBs) exhibit great promise due to their high energy density and acceptable cycling stability. Therefore, it is very important to develop new materials for ZIBs [10], [11], [12], [13]. The reversible redox reaction in the active electrode material can lead to charge storage in rechargeable batteries. POMs-based MOCs, with the ability to reversibly transfer multi-electrons, show advantage in controlling redox reactions in energy storage [14].

On the other side, nitrite is equally dominant in people’s lives. It is the most common preservative in our lives, so accurate and efficient detection of nitrite is very important [15]. It can cause side effect on and even harmful to human health [16], [17], [18], [19]. Among all kinds of nitrite detection methods, the electrochemical sensor has gained much interest attributed to its high sensitivity, simple operation, low cost and easy miniaturization. [20]. It has been reported that the POMs-based MOCs show good electrocatalytic activity to nitrite, attributed to the fast electron transfer and abundant redox-active sites of POMs, which indicate the potential for electrochemical sensors towards nitrite [21].

Based on the above, POMs-based MOCs obtained by hydrothermal method show promise for rechargeable aqueous ZIBs and electrochemical sensors for detecting diverse ions. Herein, N,N′-bis(3-pyridinecarboxamide)-1,2-cyclohexane (3-bpah) was designed and used as the organic ligand (Scheme 1). By systematically adjusting the metal salts and pH values, two isomorphic Anderson-type POM-based metal-organic complexes were isolated: {Cd(3-Hbpah)2(H2O)2[CrMo6(OH)5O19]} (1), {Zn(3-Hbpah)2(H2O)2[CrMo6(OH)5O19]} (2). Furthermore, an aqueous ZIB was constructed using complex 1 as cathode material. Energy storage behaviour was discussed in detail, and their electrochemical sensing behaviour and the dye adsorption properties have been investigated.

Section snippets

Characterization of the title complexes

Complexes 12 were obtained under hydrothermal conditions and the detailed synthetic method was placed in the Supporting information. The characterization methods (including X-Ray Crystallography and measurements) were provided in ESI. X-ray crystal structure analysis reveals that the title complexes were isomorphic and present one-dimensional chains composed of Anderson-type polyoxoanions. Except for the central metal, both complexes 1 and 2 possess similar structures, so only the structure of

Conclusions

In summary, two CrMo6-based MOCs were assembled and adopted as multifunctional materials. Their obvious electrochemical sensing performance towards the presence of KNO2 can be observed. Furthermore, the aqueous ZIBs constructed by complex 1 exhibited acceptable energy storage activity and cycling stability. MB and GV in aqueous solution can be effectively adsorbed by the title complexes. This work shows an example for achieving multifunctional materials constructed from Anderson-type POM-based

CRediT authorship contribution statement

Yuan Tian: Writing - original draft. Zhi-Han Chang: Writing - original draft. Yu-Chen Zhang: Writing - original draft. Xiu-Li Wang: Writing - original draft. Yong-zhen Chen: Writing - original draft. Qian-qian Liu: Writing - original draft. Le Yu: Writing - original draft.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 21971024, 21671025) and Liao Ning Revitalization Talents Program (XLYC1902011), which are gratefully acknowledged.

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