Electrocatalytic reduction of nitrite and nitric oxide to ammonia with iron-substituted polyoxotungstates

Toth, James E.; Anson, Fred C.

doi:10.1021/ja00189a012

Cited by 311 publications

(216 citation statements)

References 3 publications

(6 reference statements)

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“…Nitrite ion reduction has been used previously [6,[36][37][38] to assess the electrocatalytic activity of LBL films. Figure 5 shows the nitrite concentration dependence of the cathodic current increase of the POM's W-O II redox process observed at an electrode modified with the Ni7POM-RuD LBL film of 16 assembly steps.…”

Section: Preliminary Electrocatalytic Properties Of Lbl Filmsmentioning

confidence: 99%

“…Being catalytic analogues to porphyrins, monosubstituted polyoxometalates (POMs) have the additional advantage of thermal stability, robustness and inertness towards oxidizing environments. Since the late 1980s [5,6] the electrocatalytic reduction of nitrite has been employed as a classical test for the investigation into the electrocatalytic properties of POMs. The last decade has marked increasing interest in higher nuclearity POM-based transition metal clusters.…”

Section: Introductionmentioning

confidence: 99%

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Electrocatalysis by crown-type polyoxometalates multi-substituted by transition metal ions; Comparative study

Naseer

Mal

Kortz

et al. 2015

Electrochimica Acta

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The difference in electrochemical properties of three crown-type polyoxometalates multisubstituted by Fe 3+ , Ni 2+ or Co 2+ ions and their precursor has been rationalized with respect to their electrocatalytic performances studied in solution and in the immobilized state within the layer-by-layer film formed with a positively charged pentaerythritol-based Ru(II)-metallodendrimer. The film assembly was monitored with electrochemical methods and characterized by surface analysis techniques. An influence of the terminal layer on the electrode reaction and on film porosity has been observed. The electrocatalytic performance of the compounds on nitrite reduction was assessed in solution and in the immobilized state.

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Section: Preliminary Electrocatalytic Properties Of Lbl Filmsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electrocatalysis by crown-type polyoxometalates multi-substituted by transition metal ions; Comparative study

Naseer

Mal

Kortz

et al. 2015

Electrochimica Acta

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“…HPAs have been previously shown to be effective electrocatalysts for the reduction of nitrite [34,[44][45][46][47] as a standard reaction for the assessment of HPA electrocatalytic performance [48]. Rare examples of transitional metal ion-substituted HPAs demonstrated the electrocatalytic activity towards NRR in mild acidic media (approx.…”

Section: Introductionmentioning

confidence: 99%

“…The favorable effect on NRR catalysis of accumulation of substituent ion within the same molecule has been shown for sandwich-type Cu 2+ - [52] and Ni 2+ -multisubstituted HPA [52,57] in comparison with monosubstituted derivatives. Starting with the reduction to nitrite by the HPA, the whole reaction goes through nitric oxide (NO) [55] down to ammonia [48]. The significant cathodic overpotential up to 750 mV is observed for NRR electrocatalysis with HPA in comparison with nitrite reduction illustrating the low reactivity of the nitrate ion [49].…”

Section: Introductionmentioning

confidence: 99%

Nitrate and Nitrite Electrocatalytic Reduction at Layer-by-Layer Films Composed of Dawson-type Heteropolyanions Mono-substituted with Transitional Metal Ions and Silver Nanoparticles

Imar

Yaqub

Maccato

et al. 2015

Electrochimica Acta

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“…Our group is primarily concerned with the application of this family of HPAs in the development of electrochemical sensors with the HPA acting as a possible electrocatalyst. HPAs in the past have been employed as electrocatalysts for a variety of substrates, such as, NO [16][17][18][19][20][21][22][23][24], H 2 O 2 [25][26][27][28], NADH [29][30][31][32] and the hydrogen evolution reaction [33][34][35][36]. A crucial step in the development of any electrochemical based sensor is the immobilisation of the electrocatalyst onto the electrode surface.…”

Section: Introductionmentioning

confidence: 99%

Solution and solid phase electrochemical behaviour of [Os(bpy)3]3[P2W18O62]

Fay¹,

Dempsey²,

McCormac³

2005

Electrochimica Acta

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Abstract[Os (bpy) indicating surface based processes were present. Electroactive films of the complex were formed on carbon macroelectrodes by the redox switching of the transition metal within the complex. Voltammetric investigations into the film's behaviour in a range of buffer solutions (pH 2.0, 4.5 and 7.0) were performed. The films were found to possess better stability in acidic pH and the same pH dependence for the tungsten-oxo framework of the heteropolyanions as in solution. Solid state electrochemical measurements on mechanically attached microparticles of the complex were performed, with the effect of both the nature and concentration of the aqueous electrolyte on this behaviour being investigated. Upon redox switching between the Os 2+/3+ redox states there is an associated insertion/expulsion of anions from/to the solution phase. Scanning electron micrographs of these solid state films were attained before and after redox cycling. Apparatus and ProceduresThe reference electrode that was employed in organic solvents was a silver wire in contact IR SpectroscopyThe Differential pulse anodic stripping voltammetric (DPASV) experiments were performed so as to confirm the adsorption phenomenon observed in 0.01M electrolyte concentration. Figure 3 illustrates the DPASV of a modified carbon electrode in 0.1M Et 4 NPF 6 after an accumulation step at - As discussed in the previous section the oxidative processes of the Os 2+ centre exhibits characteristics pointing to an interaction between the complex and the electrode surface. As a result a film of the complex could be deposited onto the electrode surface by continuous redox switching through the osmium metal redox couple. Films were formed by cycling the potential of the glassy carbon electrode through the Os 3+/2+ redox process for 250 cycles from 9 a 0.1M TBAPF 6 DMSO solution of the starting complex. Figure 4 [79,80]. Despite the FWHM pointing to the first redox process being monoelectronic we believe it is bielectronic for two reasons. At slower scan rates a slight shoulder has been observed on the first redox process and it is well known that the first two monoelectronic processes are very close in potential. Secondly it is well know that the parent HPA can accept 6 electrons reversibly.The P 2 W 18 O 62 6-Dawson species is stable in pH's from 2.00 to 8.00 and its electrochemical behaviour depends upon the pH of the contacting electrolyte with some of the tungsten-oxo based redox processes involving protonation [75]. As a result we were interested in investigating the effect of solution pH on the redox activity of the film. With increasing pH, the losses. The lower stability of the film towards redox cycling in pH 4.50 is linked to the pH dependent nature of the tungsten-oxo reductions, when at more alkaline pH's the availability of protons which accompany the reductions is less, relative to that in pH 2.00. Scan rate studies were also performed at both pH 2.00 and 4.50, it was found that the peak potentials were independent of scan rate and th...

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Electrocatalytic reduction of nitrite and nitric oxide to ammonia with iron-substituted polyoxotungstates

Cited by 311 publications

References 3 publications

Electrocatalysis by crown-type polyoxometalates multi-substituted by transition metal ions; Comparative study

Electrocatalysis by crown-type polyoxometalates multi-substituted by transition metal ions; Comparative study

Nitrate and Nitrite Electrocatalytic Reduction at Layer-by-Layer Films Composed of Dawson-type Heteropolyanions Mono-substituted with Transitional Metal Ions and Silver Nanoparticles

Solution and solid phase electrochemical behaviour of [Os(bpy)3]3[P2W18O62]

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