Iron(II) and copper(II) paratungstates B: a single-crystal X-ray diffraction study

Gumerova, Nadiia I.; Dobrov, Anatolie; Roller, Alexander; Rompel, Annette

doi:10.1107/s2053229618010021

Cited by 6 publications

(4 citation statements)

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“…2). The centrosymmetric paratungstate B anion [W 12 O 40 (OH) 2 ] 10is structurally very similar to previously described ones (Radio et al, 2010(Radio et al, , 2011Gumerova et al, 2015Gumerova et al, , 2018 and consists of four groups, viz. two {W 3 O 13 } and two {W 3 O 14 } units, with common vertices (Fig.…”

Section: Structural Commentarysupporting

confidence: 75%

“…The [W 12 O 40 (OH) 2 ] 10paratungstate B anion is stable in aqueous acidic solution and has a cluster-like structure of twelve W-centered distorted octahedra {WO 6 } (Evans & Rollins, 1976;Pope, 1983). Due to its high surface charge density q/m = 0.83 (q = net charge, m = number of metal ions), the paratungstate B anion can act as a multidentate ligand for alkaline (Peresypkina et al, 2014) or transition-metal cations (Radio et al, 2010(Radio et al, , 2011Gumerova et al, 2015Gumerova et al, , 2018 and as a precursor for the synthesis of catalytically active sandwich-type polyoxotungstates (POTs) (Sokolov et al, 2012).…”

Section: Chemical Contextmentioning

confidence: 99%

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Crystal structure of hexasodium tetraserinolium paratungstate B decahydrate, [Na₆{(CH₂OH)₂CHNH₃}₄][W₁₂O₄₀(OH)₂]·10H₂O

et al. 2022

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The title polyoxometalate-based organic–inorganic hybrid compound, [Na6(C3H10NO2)4][W12O40(OH)2]·10H2O, consists of a di-μ 3-hydroxido-tetra-μ 3-oxido-octadeca-μ-oxido-octadecaoxidododecatungstate (paradodecatungstate B) anion, [W12O40(OH)2]10–, and six sodium cations coordinated by the oxygen ions of the polyanions, serinol ligands protonated at the N atom, and water molecules. The centrosymmetric paratungstate B anion shows characteristic features in terms of bond lengths and angles. The three-dimensional framework structure is established by bonding of the sodium cations with oxygen ions of the paratungstate B anions and a network consisting of N—H...O and O—H...O hydrogen bonds of medium strength between the protonated serinol cations, water molecules and the paratungstate B anions. The title compound was also characterized by means of elemental analysis, IR spectroscopy and thermogravimetric analysis.

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Section: Structural Commentarysupporting

confidence: 75%

Section: Chemical Contextmentioning

confidence: 99%

Crystal structure of hexasodium tetraserinolium paratungstate B decahydrate, [Na₆{(CH₂OH)₂CHNH₃}₄][W₁₂O₄₀(OH)₂]·10H₂O

et al. 2022

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“…The hexa-hydroxylation on a paratungstate type POM cluster anion makes this system a new member (we have named this as paratungstate-D) of the paratungstate family of paratungstate-A, paratungstate-B, and paratungstate-D. The structurally characterized paratungstate B (i.e., having two W–OH groups) is known in many reported compounds. − The presence of these hydroxyl groups in compound 1 is validated by bond valence sum (BVS) calculations using its crystal data (for details, see Supporting Information, Section S2) and XPS analysis of compound 1 (vide infra). The void spaces of the 3D network in the crystal structure of compound 1 have trapped H 2 S, N 2 , distorted tetrahedral lithium–aqua–complex cations, and lattice water molecules, as shown in Figure d.…”

Section: Resultsmentioning

confidence: 94%

“…Notably, the title paratungstate is characterized with six hydroxyl groups, which is, to our knowledge, the first example of this kind. The dihydroxy paratungstate, [W VI 12 O 40 (OH) 2 ] 10– , known as “paratungstate B”, is well known and known to be formed in the pH range of 5–6.5. − In this context, it can be noted that the “paratungstate A” ion has the formula, [W VI 12 O 42 ] 12– . According to this naming convention, [W VI 12 O 38 (OH) 4 ] 8– (hypothetical one) should be named as “paratungstate C”, and therefore, the title paratungstate anion (in the present work) [W VI 12 O 36 (OH) 6 ] 6– can be named “paratungstate D”.…”

Section: Resultsmentioning

confidence: 99%

Hydroxylated Polyoxometalate with Cu(II)- and Cu(I)-Aqua Complexes: A Bifunctional Catalyst for Electrocatalytic Water Splitting at Neutral pH

2023

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A sole inorganic framework material [Li(H2O)4][{CuI(H2O)1.5} {CuII(H2O)3}2{WVI 12O36(OH)6}]·N2·H2S·3H2O (1) consisting of a hydroxylated polyoxometalate (POM) anion, {WVI 12O36(OH)6}6–, a mixed-valent Cu(II)– and Cu(I)–aqua cationic complex species, [{CuI(H2O)1.5}{CuII(H2O)3}2]5+, a Li(I)-aqua complex cation, and three solvent molecules, has been synthesized and structurally characterized. During its synthesis, the POM cluster anion gets functionalized with six hydroxyl groups, i.e., six WVI–OH groups per cluster unit. Moreover, structural and spectral analyses have shown the presence of H2S and N2 molecules in the concerned crystal lattice, formed from “sulfate-reducing ammonium oxidation (SRAO)”. Compound 1 functions as a bifunctional electrocatalyst exhibiting oxygen evolution reaction (OER) by water oxidation and hydrogen evolution reaction (HER) by water reduction at the neutral pH. We could identify that the hydroxylated POM anion and copper-aqua complex cations are the functional sites for HER and OER, respectively. The overpotential, required to achieve a current density of 1 mA/cm2 in the case of HER (water reduction), is found to be 443 mV with a Faradaic efficiency of 92% and a turnover frequency of 4.66 s–1. In the case of OER (water oxidation), the overpotential needed to achieve a current density of 1 mA/cm2 is obtained to be 418 mV with a Faradaic efficiency of 88% and turnover frequency of 2.81 s–1. Diverse electrochemical controlled experiments have been performed to conclude that the title POM-based material functions as a true bifunctional catalyst for electrocatalytic HER as well as OER at the neutral pH without catalyst reconstruction.

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A Proton-Conductive Co(II)-Polyoxometalate Acts as a Precatalyst for Efficient Electrocatalytic Water Oxidation

Jana,

Premanand,

Chandran

et al. 2024

Inorg. Chem.

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A cobalt(II)-containing polyoxometalate, [H 3 O] 5 [{Co(H 2 O) 4 } 3 {Na(H 2 O) 4 }W 12 O 42 ]•3H 2 O (Co-POM), has been isolated in a one-step facile aqueous synthesis and characterized unambiguously using single-crystal X-ray crystallography along with routine spectral analysis. The paratungstate cluster anion [W 12 O 42 ] 12− coordinates with {Co II (H 2 O) 4 } 2+ and {Na(H 2 O) 4 } + complex cations resulting in the formation of the water-insoluble Co-POM compound having three-dimensional (3-D) extended structure.Motivated by the protonated water molecules existing as the counter cations in Co-POM, herein, we demonstrate the detailed proton conductivity studies of the Co-POM, reaching a value of 1.04 × 10 −2 S cm −1 at 80 °C and 98% relative humidity (RH). The temperature-and humidity-dependent proton conductivity in Co-POM is governed by Grotthus mechanism with E a = 0.25 eV. In addition, we examined the electrochemical behavior of Co-POM, in an alkaline borate buffer where it is found to be electrochemically unstable and acts as a precatalyst (and not a true catalyst) for oxygen evolution reaction (OER). We also discuss the "post-mortem" analysis of the postelectrolysis sample to identify the active species which turns out to be a cobalt oxide material (Co 3 O 4 ) incorporating small amounts of tungsten. Thus, in the present electrocatalysis work, the Co-POM molecule transforms into an efficient water oxidation catalyst (WOC).

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Iron(II) and copper(II) paratungstates B: a single-crystal X-ray diffraction study

Abstract: Two new isopolytungstates, Na5Fe2.5[W12O40(OH)2]·36H2O and Na4Cu3[W12O40(OH)2]·28H2O, have been prepared and structurally characterized. The compounds exhibit a three-dimensional structure, in which the paratungstate anions coordinate to FeII or CuII ions in a polydentate mode.

Cited by 6 publications

References 39 publications

Crystal structure of hexasodium tetraserinolium paratungstate B decahydrate, [Na₆{(CH₂OH)₂CHNH₃}₄][W₁₂O₄₀(OH)₂]·10H₂O

Crystal structure of hexasodium tetraserinolium paratungstate B decahydrate, [Na₆{(CH₂OH)₂CHNH₃}₄][W₁₂O₄₀(OH)₂]·10H₂O

Hydroxylated Polyoxometalate with Cu(II)- and Cu(I)-Aqua Complexes: A Bifunctional Catalyst for Electrocatalytic Water Splitting at Neutral pH

A Proton-Conductive Co(II)-Polyoxometalate Acts as a Precatalyst for Efficient Electrocatalytic Water Oxidation

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Iron(II) and copper(II) paratungstates B: a single-crystal X-ray diffraction study

Abstract: Two new isopolytungstates, Na5Fe2.5[W12O40(OH)2]·36H2O and Na4Cu3[W12O40(OH)2]·28H2O, have been prepared and structurally characterized. The compounds exhibit a three-dimensional structure, in which the paratungstate anions coordinate to FeII or CuII ions in a polydentate mode.

Cited by 6 publications

References 39 publications

Crystal structure of hexasodium tetraserinolium paratungstate B decahydrate, [Na6{(CH2OH)2CHNH3}4][W12O40(OH)2]·10H2O

Crystal structure of hexasodium tetraserinolium paratungstate B decahydrate, [Na6{(CH2OH)2CHNH3}4][W12O40(OH)2]·10H2O

Hydroxylated Polyoxometalate with Cu(II)- and Cu(I)-Aqua Complexes: A Bifunctional Catalyst for Electrocatalytic Water Splitting at Neutral pH

A Proton-Conductive Co(II)-Polyoxometalate Acts as a Precatalyst for Efficient Electrocatalytic Water Oxidation

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Crystal structure of hexasodium tetraserinolium paratungstate B decahydrate, [Na₆{(CH₂OH)₂CHNH₃}₄][W₁₂O₄₀(OH)₂]·10H₂O

Crystal structure of hexasodium tetraserinolium paratungstate B decahydrate, [Na₆{(CH₂OH)₂CHNH₃}₄][W₁₂O₄₀(OH)₂]·10H₂O