Lanthanide derivatives of Ta/W mixed-addendum POMs as proton-conducting materials

Peng, Qingpo; Li, Shujun; Wang, Ruoya; Liu, Shuxia; Xie, Lin‐Hua; Zhai, Jianxin; Zhang, Jie; Zhao, Qianyi; Chen, Xuenian

doi:10.1039/c7dt00091j

Cited by 31 publications

(20 citation statements)

References 29 publications

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“…As shown in Table , the self-assembly of {P 2 W 15 Ta 3 } with RE (Y III and the entire series of lanthanide ions La III –Lu III except for the radioactive Pm ), can produce 15 compounds, which include two structural types: monomers (Figure a) and one-dimensional chain compounds (Figure b). Four of the five chain compounds ( La-POM , Ce-POM , Pr-POM , and Nd-POM ) have been reported in our previous work . Eleven compounds, including the 10 monomers ( Y-POM , Eu-POM , Gd-POM , Tb-POM , Dy-POM , Ho-POM , Er-POM , Tm-POM , Yb-POM , and Lu-POM ) and one chain compound ( Sm-POM ) are reported here for the first time.…”

Section: Resultsmentioning

confidence: 59%

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Controllable Synthesis and Catalytic Performance of Nanocrystals of Rare-Earth-Polyoxometalates

Zhou

Peng

et al. 2018

Inorg. Chem.

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Large-scale isolation of nanocrystals of rare-earth-polyoxometalates (RE-POMs) catalysts is important in fundamental research and applications. Here, we synthesized a family of monomeric RE-POMs by the self-assembly of Ta/W mixed-addendum POM {PWTaO} and rare-earth (RE) ions. These RE-POMs with molecular formulas of [RE(HO)]PWTaO· nHO (RE = Y, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) are all electroneutral molecular clusters, insoluble in water and common organic solvents. The electronic structures, electrochemical properties, and catalytic activities of them have been investigated by experimental and computational methods. In particular, based on a mild and controllable synthetic process, a convenient and controllable approach to prepare nanocrystals and self-organized aggregates of these monomers has been developed. They exhibit remarkable heterogeneous catalytic activity for cyanosilylation. Both the increased Lewis acid strength of RE in the title compounds, as indicated by theoretical calculations, and the decreased particle size contribute to their high catalytic performances.

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Section: Resultsmentioning

confidence: 59%

“…[Sm 3 (H 2 O) 19 ][P 2 W 15 Ta 3 O 62 ]·18H 2 O ( Sm-POM ) was prepared following the procedure descried for La-POM , but using Sm(NO 3 ) 3 as rare-earth reagent. The final yield for Sm-POM (tufted crystals) was 56%.…”

Section: Methodsmentioning

confidence: 99%

Controllable Synthesis and Catalytic Performance of Nanocrystals of Rare-Earth-Polyoxometalates

Zhou

Peng

et al. 2018

Inorg. Chem.

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“…Finally, the activation energy is calculated according to the Arrhenius equation (σ T = σ 0 exp(− E a / k B T )). The E a at 98% RH for 1-Ce was calculated to be 0.34 eV (Figure e), suggesting that the conduction proceeds by the Grotthuss mechanism, given that the activation energy is in the range of 0.1–0.4 eV. − This may be ascribed to the presence of discrete protonated [H 2 en] 2+ cations interacting with some lattice water molecules and polyoxyanions to form a hydrogen bond network. With the temperature rising, the water movement and the vibration frequency of the N–H bond are accelerated, which promote the hopping of protons in the hydrogen-bond network and thus improve the proton conductivity .…”

Section: Resultsmentioning

confidence: 99%

Organoamine-Directed Assembly of 5p–4f Heterometallic Cluster Substituted Polyoxometalates: Luminescence and Proton Conduction Properties

Xiao

Zhang

et al. 2021

Inorg. Chem.

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The assembly of heterometallic cluster substituted polyoxometalates (POMs) remains a great challenge for inorganic synthetic chemistry up to now. Herein, a series of 5p–4f heterometallic cluster substituted POMs were successfully isolated by a facile one-step hydrothermal reaction method, namely H17(H2en)3[SbIII 9SbVLn3O14(H2O)3][(SbW9O33)3(PW9O34)]·28H2O(1-Ln, Ln = Ce, Sm, Eu, Gd, Tb, Dy) (en = ethylenediamine). Interestingly, by replacing en with imidazole, another series of 5p–4f heterometallic cluster substituted POMs H13(HIm)4K2Na4(H2O)9[SbIII 9SbVLn3O14(H2O)3][(SbW9O33)3(PW9O34)]·26H2O (2-Ln, Ln = Sm, Eu, Gd, Tb, Dy, Im = imidazole) were obtained. Structural analyses indicate that both 1-Ln and 2-Ln are made up of an unprecedented 5p–4f heterometallic {Sb10Ln3O14(H2O)3} cluster stabilized simultaneously by mixed trilacunary heteropolyanions including {A-α-PW9O34} and {B-α-SbW9O33}. Impedance measurements indicate that both compounds exhibit different proton conduction properties, and the conductivity of 2 can reach up to 1.64 × 10–2 S cm–1 at 85 °C under 98% relative humidity. Moreover, the fluorescence emission behaviors of both compounds have been studied.

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“…Due to the abundant oxygen and the pleasant mobility of the dissociated hydrated protons (e. g., H + , H 3 O + and NH 4 + ) [17] conjoined with the POMs anions, which can assemble the unhampered hydrogen‐bond chains by affordable proton‐jumping sites, making POMs get more focuses in the field of proton conductivity [18] . In 2013, Wei [19] and co‐workers synthesized a novel MOF, [Cu(bpdc)(H 2 O) 2 ] n and two poly‐POM‐MOFs, {H[Cu(Hbpdc)(H 2 O) 2 ] 2 [PM 12 O 40 ] ⋅ nH 2 O} n (M=Mo for 2 ,W for 3 ).…”

Section: Guest Molecule Doping In Mofsmentioning

confidence: 99%

Designable Guest‐Molecule Encapsulation in Metal–Organic Frameworks for Proton Conductivity

Wang

Hao

et al. 2022

Chemistry A European J

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Metal-organic frameworks (MOFs), as a porous frame material, exhibit considerable electrical conductivity. In recent decades, research on the proton conductivity of MOFs has made gratifying progress. In this review, the designable guest molecules encapsulated into MOFs are summarized and generalized into four types in terms of promoting proton conductive performance, and then recent progress in the promotion of proton conductivity by MOFs encapsulating guest molecules is discussed. The existing challenges and prospects for the development of this strategy for promoting MOFs' proton conductivity are also listed.

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Lanthanide derivatives of Ta/W mixed-addendum POMs as proton-conducting materials

Cited by 31 publications

References 29 publications

Controllable Synthesis and Catalytic Performance of Nanocrystals of Rare-Earth-Polyoxometalates

Controllable Synthesis and Catalytic Performance of Nanocrystals of Rare-Earth-Polyoxometalates

Organoamine-Directed Assembly of 5p–4f Heterometallic Cluster Substituted Polyoxometalates: Luminescence and Proton Conduction Properties

Designable Guest‐Molecule Encapsulation in Metal–Organic Frameworks for Proton Conductivity

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