Effective Storage of Electrons in Water by the Formation of Highly Reduced Polyoxometalate Clusters

Chen, Jiajia; Vilà‐Nadal, Laia; Solé‐Daura, Albert; Chisholm, Greig; Minato, Takuo; Busche, Christoph; Zhao, Tingting; Kandasamy, Balamurugan; Ganin, Alexey Y.; Smith, Rachelle M.; Colliard, Ian; Carbó, Jorge J.; Poblet, Josep M.; Nyman, May; Cronin, Leroy

doi:10.1021/jacs.1c10584

Cited by 57 publications

(48 citation statements)

References 33 publications

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“…These features broaden the application of POMs and make them good candidates for energy storage and conversion. [136][137][138][139][140][141] Recently, a new kind of RAILs has been prepared by replacing the anions of ILs with polyoxometalates, which are described as POM-ILs. [142][143][144] This kind of RAILs combines the properties of both POMs and ILs, which gives them the characteristics of tunable properties and ease of processing.…”

Section: Railsmentioning

confidence: 99%

The Novel Ionic Liquid and Its Related Self‐Assembly in the Areas of Energy Storage and Conversion

et al. 2022

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ILs unique properties such as ionic conductivity, low volatility, noninflammability, high chemical and electrochemical stability, and so on. [3] These properties coupled with adjustable structure and functionality allow ILs to evolve from unique liquid mediums to the solvents/electrolytes widely used across multiple disciplines in science and engineering. [4][5][6][7][8][9] The incorporation of ILs and advanced energy storage and conversion technology seems to be a nice strategy to meet the increasing demand for clean and sustainable energy. [10] However, traditional ILs based on ammonium, alkylpyridinium, dialkylimidazolium, and phosphonium cations, are generally expensive, nonbiodegradable, and toxicities, which are unfavorable to achieving the aforementioned goals. [11] Thus, numerous efforts have been devoted to exploring the advanced ILsderived materials, which retain most of the characteristics of ILs and are endowed with new features. Novel ILs, including deep eutectic solvents (DESs), [12,13] poly(ionic liquid)s (PILs), [14][15][16] ionic liquid crystals (ILCs), [17,18] and redox-active ionic liquids (RAILs), [19,20] have been synthesized and have been proved to be promising materials to compensate for the inadequacies of the traditional ILs.In general, those four types of novel ILs exhibit unique features and advantages in the fields of energy storage and conversion, respectively. For example, DESs are inexpensive, biodegradable, and nontoxic, they have great advantages in building environmental-friendliness energy storage devices. [21,22] The PILs have a polymeric structure while maintaining ionic conductivity. This means they are excellent potential materials for preparing binder, membranes, and solid-state electrolyte. [23] They are also a kind of building blocks for self-assembly. ILCs with enhanced ordered structure and unique phase behavior are able to achieve the efficient and directional conduction of species, which are excellent properties to construct high-performance energy storage devices. [24] Besides, RAILs are a liquid material with ionic conductivity and redox centers and have exhibited promising potentiality for use as redox additives and electroactive electrolytes. [25] In this review, we focus on the intrinsic properties of novel ILs and their related self-assembly behavior for constructing highperformance energy storage and conversion devices. In the following four chapters, we discuss the unique properties,

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Section: Railsmentioning

confidence: 99%

The Novel Ionic Liquid and Its Related Self‐Assembly in the Areas of Energy Storage and Conversion

et al. 2022

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“…To further explore the difference between oxidized and reduced Dawson POM cluster, Chen et al investigated oxidized and highly reduced POMs by small-angle X-ray scattering (SAXS). [87] By comparing the SAXS of oxidized state of POM {P 2 W 18 } and reduced state of POM {P 2 W 18 }-18e with different cations (K + , Na + and Li + ), it was found that the coulomb peak of K-{P 2 W 18 }-18e and Na-{P 2 W 18 }-18e were almost shielded while the coulomb peak of Li-{P 2 W 18 }-18e was partially shielded (Figure 4b) between q = 0.1 ~0.3 Å À 1 . The appearance of the coulomb peak is related to the orderly arrangement of the POM species in the solution, and when it disappears, it represents the aggregation behaviour of the POM.…”

Section: Spectroscopy Characterization Of Polyoxometalate Redox Behav...mentioning

confidence: 99%

The Cluster Design and Redox Behavior Characterization of Polyoxometalates for Redox Flow Batteries

Han

Lan

et al. 2022

Chemistry An Asian Journal

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Polyoxometalates (POMs) are a class of metaloxygen cluster molecular materials formed by covalently linking transition metal atoms and oxygen atoms. Those molecular cluster materials also shows multiple electron reversible redox capabilities and high solubility in solution. Thus, POMs also recently present interesting applications as redox active electrolyte in redox flow batteries (RFBs). In this review, we mainly focus on the structural design of POMs and analysis factors affecting the electrochemical properties of POMs. Spectroscopic characterizations are introduced to deeply explore the structural changes of POMs during the redox process. Furthermore, we summarize the cases of POMs used as liquid-phase redox couple in aqueous or nonaqueous redox flow batteries and discuss the advantages and deficiency of POMs with various configurations.

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“…3,15,16 In context, a comprehensive study of the physical−chemical events occurring along their electrochemical reduction appears as crucial from a fundamental aspect but also for (i) their rational integration as active components in batteries (Li-ion, Na-ion, or redox flow) and (ii) their use as redox mediators in electro(photo)catalytic processes. 3,5,15 The Keggin-type silicotungstate α-[Si(W VI 3 O 10 ) 4 ] 4− (abbreviated as SiW 12 -0), containing a central SiO 4 tetrahedron surrounded by four triads {W 3 O 13 } mutually connected through corner-shared junctions, represents a popular charge carrier used in ground-breaking electrochemical devices. 16−19 Nevertheless, pioneered works have revealed that its electrolysis at controlled potential in an acidic solution can lead to well-defined six-electron-reduced POMs [Si-(W IV 3 O 7 (H 2 O) 3 )(W VI 3 O 10 ) 3 ] 4− (notated SiW 12 -VI′) in which 5d electrons are localized in three metal−metal bonds, forming a W IV -based trinuclear cluster.…”

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confidence: 99%

Making Heterometallic Metal–Metal Bonds in Keggin-Type Polyoxometalates by a Six-Electron Reduction Process

et al. 2023

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Polyoxometalates (POMs) represent a promising class of molecular electron reservoirs. However, their multielectron reduction gives rise to intricate physical–chemical phenomena that must be fully understood for their future use in energy-storage devices. Herein, we show that bulk electrolysis of the archetypal Keggin-type POM [Si(WVI 2MoVIO10)(WVI 3O10)3]4– in aqueous solution leads to the six-electron-reduced derivative [Si(WIV 2MoIVO7(H2O)3)(WVI 3O10)3]4– (notated SiW 11 Mo-VI′) in which the mixed-metal triad acts as a storage unit for six electrons and six protons. X-ray diffraction analysis and multinuclear NMR (183W and 95Mo) studies reveal that this electron-rich species represents the first example of POMs containing heterometallic metal–metal bonds between addenda centers. This electron-rich POM can be further reduced through multielectronic events, while its full oxidation restores the structure of the oxidized parent ion. Remarkably, the formation of SiW 11 Mo-VI′ results from a fast clustering process compared to that observed for the entirely W-based analogue, revealing that the formation of metal–metal bonds in the mixed-metal Mo/W POM is facilitated because the reaction rate is not limited by a slow disproportionation step. Last, we evaluate the supramolecular properties of SiW 11 Mo-VI′ using a method based on the cloud-point measurement of a nonionic surfactant. This investigation demonstrates that the clustering process has dramatic consequences on the solution behavior of the POM, canceling its superchaotropic character due to a local structuring effect of the hydration shell. These fundamental results pave the way for applications using the massive electron-storage properties of mixed-metal POMs.

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Effective Storage of Electrons in Water by the Formation of Highly Reduced Polyoxometalate Clusters

Cited by 57 publications

References 33 publications

The Novel Ionic Liquid and Its Related Self‐Assembly in the Areas of Energy Storage and Conversion

The Novel Ionic Liquid and Its Related Self‐Assembly in the Areas of Energy Storage and Conversion

The Cluster Design and Redox Behavior Characterization of Polyoxometalates for Redox Flow Batteries

Making Heterometallic Metal–Metal Bonds in Keggin-Type Polyoxometalates by a Six-Electron Reduction Process

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