Cyclic Voltammetric Studies on [SMo12O40]2- and [SMo12O40]3- at Macrodisk Electrodes in Acetonitrile With and Without Added Supporting Electrolyte

Bond, Alan M.; Coomber, Darren C.; Harika, Rita; Hultgren, Victoria M; Rooney, Melissa Bunin; Vu, Truc; Wedd, Anthony G.

doi:10.1002/1521-4109(200112)13:18<1475::aid-elan1475>3.0.co;2-f

Cited by 5 publications

(3 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…According to previous studies of the voltammetry of [XV V Mo 11 O 40 ] 4‑ (X = P, As) in MeCN and [SV V Mo 11 O 40 ] 3‑ in mixed MeCN/H 2 O solvent, the initial process is assigned to a V V/IV reduction (eq ), and the second, at more negative potential, is ascribed to the reduction of molybdenum in the POM framework (eq ). TTF ⇌ TTF + + normale ‐ goodbreak0em1em⁣ italicE normalm 1 = 0.03 .25em normalV TTF + ⇌ TTF 2 + + normale ‐ goodbreak0em1em⁣ italicE normalm 2 = 0.41 .25em normalV false[ SV normalV Mo 11 normalO 40 false] 3 ‐ + normale ‐ ⇌ false[ SV IV Mo 11 normalO 40 false] 4 ‐ goodbreak0em1em⁣ italicE normalm 3 = 0.148 .25em normalV A minor redox process detected at about −0.34 V is attributed to protonation from adventitious water. Proton sources are known to modify the voltammetry of related systems. , In summary, the fact that E m3 = 0.148...…”

Section: Resultsmentioning

confidence: 99%

Spontaneous Redox Synthesis of the Charge Transfer Material TTF₄[SVMo₁₁O₄₀]

Boas

et al. 2012

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

The charge-transfer material TTF-SV(IV)Mo(11)O(40) (TTF = tetrathiafulvalene) was prepared by a spontaneous redox reaction between TTF and the vanadium-substituted polyoxometalate (n-Bu(4)N)(3)[SV(V)Mo(11)O(40)] in both solution and solid state phases. Single crystal X-ray diffraction gave the stoichiometry TTF(4)[SVMo(11)O(40)]·2H(2)O·2CH(2)Cl(2), with the single V atom positionally disordered with eight Mo atoms over the whole α-Keggin polyanion [SVMo(11)O(40)](4-). Raman spectra support the 1+ charge assigned to the oxidized TTF deduced from bond lengths, and elemental and voltammetric analysis also are consistent with this formulation. Scanning electron microscopy images showed a rod-type morphology for the new charge-transfer material. The conductivity of the solid at room temperature is in the semiconducting range. The TTF and (n-Bu(4)N)(3)[SV(V)Mo(11)O(40)] solids also undergo a rapid interfacial reaction, as is the case with TTF and TCNQ (TCNQ = tetracyanoquinodimethane) solids. EPR spectra at temperatures down to 2.6 K confirm the presence of two paramagnetic species, V(IV) and the oxidized TTF radical. Spectral evidence shows that the TTF-SV(IV)Mo(11)O(40) materials prepared from either solution or solid state reactions are equivalent. The newly isolated TTF-SV(IV)Mo(11)O(40) material represents a new class of TTF-polyoxometalate compound having dual electrical and magnetic functionality derived from both the cationic and anionic components.

show abstract

Section: Resultsmentioning

confidence: 99%

Spontaneous Redox Synthesis of the Charge Transfer Material TTF₄[SVMo₁₁O₄₀]

Boas

et al. 2012

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…29,30 Electrochemical studies of POMs are extensive and the effects of acid, small cations and solvent have been reported. 20,[31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] Generally, a series of one-electron reduction steps takes place in neutral solution, while multiple electron transfers take place in acidic and some cation-rich electrolytes. In a thermodynamic context, a linear relationship between the first reversible potential for reduction and the total charge on Keggin-type POMs is well established.…”

Section: Introductionmentioning

confidence: 99%

Structurally characterised vanadium(v)-substituted Keggin-type heteropolysulfates [SVM11O40]3− (M = Mo, W): voltammetric and spectroscopic studies related to the V(v)/V(iv) redox couple

Ueda

Nambu

et al. 2014

Dalton Trans.

Self Cite

View full text Add to dashboard Cite

Structures of the n-tetrabutylammonium salts of [SVM11O40](3-) (M = Mo, W) have been determined by X-ray crystallography and exhibit 3D networks with the V atom disordered over several sites. The cyclic voltammetric behavior of SVM11 in neutral and acidified acetonitrile solutions also has been investigated with respect to the V(V)/V(IV) couple. Results have been interpreted in conjunction with data provided by (51)V NMR spectroscopy on the oxidized V(V) form and by EPR spectroscopy on the reduced V(IV) form. Based on mechanistic details inferred from these studies, simulations of the cyclic voltammograms have been undertaken and results compared with experimental data in acidic media (two protonated forms) in order to provide estimates of equilibrium and kinetic parameters. For the V(V)/V(IV) couple in the series [XVM11O40](n-) (X = Si,Ge,P,As,S; M = Mo,W), the reversible potentials in neutral acetonitrile linearly depend on the total charge of the vanadium-substituted polyoxometalates, similar to the dependence previously reported for the non-substituted parent Keggin polyoxometalates [XM12O40](m-).

show abstract

“…Although the electrochemistry of POMs is well-documented, , voltammetric studies of POMs in the absence of added supporting electrolyte are rare. Bond and co-workers have reported the cyclic voltammetric studies on [SMo 12 O 40 ] 2– and [SMo 12 O 40 ] 3– and the reversible reduction of [S 2 Mo 18 O 62 ] 4– to [S 2 Mo 18 O 62 ] 5– and [S 2 Mo 18 O 62 ] 6– , at a macrodisk electrode in acetonitrile, in the absence of added supporting electrolyte.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Metallic Nanoparticles Using Electrogenerated Reduced Forms of [α-SiW₁₂O₄₀]^4– as Both Reductants and Stabilizing Agents

et al. 2011

View full text Add to dashboard Cite

In this paper, controlled potential bulk electrolysis at a glassy carbon working electrode was conveniently employed to produce the reduced forms of H4[α-SiW12O40] with little or no supporting electrolyte. Consequently, without the need for separation and purification, these reduced forms of [α-SiW12O40]4– were directly used as both the reductants and the stabilizing agents for the size-controlled synthesis of various types of metallic and alloy nanoparticles, including Au, Ag, Pt, Pd and Ag–Au. Ni nanoparticles were also successfully synthesized using highly reduced [α-SiW12O40]4– under neutral pH condition. The Pt nanoparticles thus obtained displayed attractive electrocatalytic properties in methanol oxidation.

show abstract

Cyclic Voltammetric Studies on [SMo12O40]2- and [SMo12O40]3- at Macrodisk Electrodes in Acetonitrile With and Without Added Supporting Electrolyte

Cited by 5 publications

References 10 publications

Spontaneous Redox Synthesis of the Charge Transfer Material TTF₄[SVMo₁₁O₄₀]

Spontaneous Redox Synthesis of the Charge Transfer Material TTF₄[SVMo₁₁O₄₀]

Structurally characterised vanadium(v)-substituted Keggin-type heteropolysulfates [SVM11O40]3− (M = Mo, W): voltammetric and spectroscopic studies related to the V(v)/V(iv) redox couple

Synthesis of Metallic Nanoparticles Using Electrogenerated Reduced Forms of [α-SiW₁₂O₄₀]^4– as Both Reductants and Stabilizing Agents

Contact Info

Product

Resources

About

Cyclic Voltammetric Studies on [SMo12O40]2- and [SMo12O40]3- at Macrodisk Electrodes in Acetonitrile With and Without Added Supporting Electrolyte

Cited by 5 publications

References 10 publications

Spontaneous Redox Synthesis of the Charge Transfer Material TTF4[SVMo11O40]

Spontaneous Redox Synthesis of the Charge Transfer Material TTF4[SVMo11O40]

Structurally characterised vanadium(v)-substituted Keggin-type heteropolysulfates [SVM11O40]3− (M = Mo, W): voltammetric and spectroscopic studies related to the V(v)/V(iv) redox couple

Synthesis of Metallic Nanoparticles Using Electrogenerated Reduced Forms of [α-SiW12O40]4– as Both Reductants and Stabilizing Agents

Contact Info

Product

Resources

About

Spontaneous Redox Synthesis of the Charge Transfer Material TTF₄[SVMo₁₁O₄₀]

Spontaneous Redox Synthesis of the Charge Transfer Material TTF₄[SVMo₁₁O₄₀]

Synthesis of Metallic Nanoparticles Using Electrogenerated Reduced Forms of [α-SiW₁₂O₄₀]^4– as Both Reductants and Stabilizing Agents