Keplerate polyoxometalate compounds: a multifunctional nano-platform for advanced materials

Wang, Ken; Iwano, Tsukasa; Uchida, Sayaka

doi:10.1039/d4dt02114b

Dalton Trans.

2024

DOI: 10.1039/d4dt02114b

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Keplerate polyoxometalate compounds: a multifunctional nano-platform for advanced materials

Ken Wang,

Tsukasa Iwano,

Sayaka Uchida

Abstract: Keplerates, as giant porous polyoxometalates (POMs), serve as multifunctional nanoplatforms with unique properties. This review highlights their use in nanocontainers, catalysis, and batteries, discussing challenges and future directions.

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Cited by 2 publications

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Enhanced Proton Conduction via Proton-Coupled Electron Transfer Reaction by a Keplerate-Type Polyoxometalate Capsule

Iwano,

Uchida

2024

Inorg. Chem.

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Polyoxometalates (POMs), anionic metal-oxide clusters, are actively studied for their versatile structural designs and element selectivity. A series of Keplerate-type POMs with core−shell structures, known as POM capsules, that feature a Keggin-type POM core, has been reported. These POM capsules, with their neutral to negative charge and large molecular surface area, can serve as platforms for proton (H + ) conduction. In this study, we aimed to introduce proton carriers into the POM capsule through a proton-coupled electron transfer (PCET) reaction. It is crucial to avoid excessive reduction, as it increases electrostatic interaction between the proton and the POM capsule, hindering proton conduction. The number of incorporated electrons was varied from 0 to 11, and the POM capsule containing 3 electrons exhibited proton conductivity an order of magnitude higher than that of pristine or highly reduced POM capsules. This study serves as a proof of concept, demonstrating that PCET, combined with the core−shell structure, can effectively enhance the proton conductivity without being limited by the choice of constituent elements.

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Enhanced Proton Conduction via Proton-Coupled Electron Transfer Reaction by a Keplerate-Type Polyoxometalate Capsule

Iwano,

Uchida

2024

Inorg. Chem.

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Synthesis of Hollowed Polyoxometalate with a Flipped VO₅ Unit by the Elimination of a Centered Organic Molecule

Kikukawa,

Taga,

Horikawa

et al. 2024

Inorg. Chem.

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Mechanistic understanding of the formation of clusters plays a role in designing the structure-dependent properties. Based on the fact that anions act as templates to form spherical polyoxovanadates, various structures were reported by changing anions in the synthetic solution. In this work, another factor in the formation of spherical polyoxometalates was demonstrated. By the reaction of [V 10 O 26 ] 4− in acetonitrile with a reductant to increase the number of tetravalent V 4+ and p-toluene sulfonic acid to convert tetrahedral VO 4 units to square-pyramidal VO 5 , acetonitrile-containing polyoxovanadate [V 24 O 60 (CH 3 CN)] 6− (I CH3CN ) was synthesized. The bulky and hydrophobic aromatic rings prevented the formed anions from acting as a template. By changing the synthetic solvent, encapsulated moieties were controlled. Nitromethane was also encapsulated to afford [V 24 O 60 (CH 3 NO 2 )] 6− (I CH3NO2 ). When acetone was used as the solvent, the contaminated water was encapsulated to form [V 24 O 60 (H 2 O)] 6− (I H2O ). The encapsulated acetonitrile molecule was eliminated by heating I CH3CN up to 230 °C under N 2 flow conditions to give hollowed polyoxovanadate [V 24 O 60 ] 6− (II), even though I CH3CN possesses no pores for acetonitrile to pass. From the X-ray crystallographic analysis of II, one of the 24 VO 5 units was flipped. The electrochemical properties and catalytic performances between I CH3CN and II were also investigated.

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Keplerate polyoxometalate compounds: a multifunctional nano-platform for advanced materials

Abstract: Keplerates, as giant porous polyoxometalates (POMs), serve as multifunctional nanoplatforms with unique properties. This review highlights their use in nanocontainers, catalysis, and batteries, discussing challenges and future directions.

Cited by 2 publications

References 75 publications

Enhanced Proton Conduction via Proton-Coupled Electron Transfer Reaction by a Keplerate-Type Polyoxometalate Capsule

Enhanced Proton Conduction via Proton-Coupled Electron Transfer Reaction by a Keplerate-Type Polyoxometalate Capsule

Synthesis of Hollowed Polyoxometalate with a Flipped VO₅ Unit by the Elimination of a Centered Organic Molecule

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Keplerate polyoxometalate compounds: a multifunctional nano-platform for advanced materials

Abstract: Keplerates, as giant porous polyoxometalates (POMs), serve as multifunctional nanoplatforms with unique properties. This review highlights their use in nanocontainers, catalysis, and batteries, discussing challenges and future directions.

Cited by 2 publications

References 75 publications

Enhanced Proton Conduction via Proton-Coupled Electron Transfer Reaction by a Keplerate-Type Polyoxometalate Capsule

Enhanced Proton Conduction via Proton-Coupled Electron Transfer Reaction by a Keplerate-Type Polyoxometalate Capsule

Synthesis of Hollowed Polyoxometalate with a Flipped VO5 Unit by the Elimination of a Centered Organic Molecule

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Product

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Synthesis of Hollowed Polyoxometalate with a Flipped VO₅ Unit by the Elimination of a Centered Organic Molecule