Electrochemical oxidation of sulfide ion at a boron-doped diamond anode

Waterston, Katie; Bejan, Dorin; Bunce, Nigel J.

doi:10.1007/s10800-006-9267-z

Cited by 49 publications

(42 citation statements)

References 23 publications

(31 reference statements)

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“…Zero-order kinetics (kinetic control) was observed in the presence and in the absence of NaCl during the oxidation of S 2-at BDD. 8 These results are significantly different from those obtained in the oxidation of S 2-using a Ti/IrO 2 -Ta 2 O 5 anode, with kinetic orders ranging from 0.5 and 0.9. 4 The feasibility of S 2-electro-oxidation was also observed in the electrolysis of a tannery wastewater with Ti/MO (MO = metal oxide) anodes, without, however, being identified the formed intermediates.…”

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confidence: 56%

“…7 Thus, it can be removed from the aqueous solution without the production of sludge, by oxidation to elemental sulfur or oxyanions, like SO 4 2-, which are ecologically benign. 8 According to the potential diagrams , using NaCl as supporting electrolyte, and observed sulfur deposition on the surface of the graphite anode, a fact that was also observed later. 11 According to these authors, the continuous oxidation to sulfur oxyanions should be much slower than the oxidation of S 2-to sulfur.…”

mentioning

confidence: 57%

“…7 In the past, the removal of S 2-from effluents was performed by precipitation, as ZnS, and by oxidation with chromate in alkaline media. 8 However, these treatments are expensive, due to the added chemicals, and environmentally incompatible, because of the disposal of the resulting toxic sludge. The biological oxidation to remove S 2-can also be performed, but it is slow and applies only to low S 2-concentrations.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, the formation and deposition of sulfur seems to be influenced by the S 2-concentration. The electrochemical oxidation of S 2-was also performed by Waterston et al, 8 using a boron-doped diamond (BDD) anode, and it was found that its conversion to SO 4 2-occurred almost quantitatively with a current efficiency of 90%. This situation seems to show the best performance of this electrode material, BDD, when compared to others.…”

mentioning

confidence: 98%

“…25 Despite the studies found in the literature describing the S 2-anodic electro-oxidation, only a few are focused on the electro-oxidation of sulfide to sulfate. 8 Also, in these few studies low sulfide concentration was used, with low assay duration and small range of applied current density. This situation limits the understanding of the kinetics of the conversion sulfide/sulfate.…”

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confidence: 99%

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Anodic Oxidation of Sulfide to Sulfate: Effect of the Current Density on the Process Kinetics

Caliari¹,

Ciríaco²,

Lopes³

2016

Journal of the Brazilian Chemical Society

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The kinetics of the conversion of sulfide to sulfate by electro-oxidation, using a boron-doped diamond (BDD) electrode was studied. Different applied current densities were tested, from 10 to 60 mA cm -2 . The results showed that the electrochemical conversion of sulfide to sulfate occurs in steps, via intermediate production of other sulfur species. The oxidation rate of the sulfide ion is dependent on its concentration and current density. The reaction order varies with the current intensity, being 2 for the lower applied current intensity and high S 2-concentration, which is compatible with a mechanism involving two S 2-ions to give S 2 2-. For higher current densities, where current control is less important, reaction order varies from 0.15 to 0.44 for the current densities of 20 and 60 mA cm -2 , respectively. For the formation of SO 4 2-from S 2-electro-oxidation, the reaction orders with respect to sulfide concentration and current intensity are 0 and 1, respectively.

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confidence: 57%

Section: Introductionmentioning

confidence: 99%

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confidence: 98%

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confidence: 99%

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Anodic Oxidation of Sulfide to Sulfate: Effect of the Current Density on the Process Kinetics

Caliari¹,

Ciríaco²,

Lopes³

2016

Journal of the Brazilian Chemical Society

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Sulfophobic and Vacancy Design Enables Self‐Cleaning Electrodes for Efficient Desulfurization and Concurrent Hydrogen Evolution with Low Energy Consumption

Zhang

Zhou

Shen

et al. 2021

Adv Funct Materials

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Sulfide oxidation reaction (SOR) is one central step of electrochemical desulfurization and sulfur‐based batteries. However, the electrochemical performance of desulfurization and sulfur batteries has been severely hindered by sulfur passivation. Here, a discovery of sulfophobic phenomenon of electrocatalysts having weak interaction to sulfur species is reported. A self‐cleaning NiS2 electrode is developed to avoid the long‐perplexing passivation issue of solid sulfur during the SOR. Furthermore, sulfur‐vacancies are engineered into NiS2 lattice to synthesize v‐NiS2 for the hydrogen evolution reaction (HER). The resultant lattice expansion and electron redistribution can adjust the adsorbed hydrogen to reach a nearly thermos‐neutral state, enabling high catalytic activity for the HER. By coupling the HER and SOR, efficient desulfurization and simultaneous hydrogen production is demonstrated. Bifunctional NiS2 enables such a one‐stone‐kills‐two‐birds strategy to realize continuous electrochemical desulfurization with superior energy efficiency (1.05 gsulfur Wh−1). As a general design principle, sulfophobic electrocatalysts can improve the properties of lithium–sulfur batteries by minimizing the passivation of S8 during charge. In brief, interfacial interaction between electrocatalysts and sulfur species are systematically investigated and a sulfophobic strategy to significantly enhance the electrochemical performance of the SOR is offered.

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Oxidation of sulfide ion in synthetic geothermal brines at carbon‐based anodes

2011

Self Cite

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Geothermal brines associated with natural gas extraction present an environmental problem because of the need to avoid the escape of toxic and odorous hydrogen sulfide. In this work, carbon-based anodes (including graphite, granulated activated carbon (GAC), and industrial coke) were used in the electrochemical oxidation of sulfide ion in synthetic geothermal brines in both batch and flow cells, with a view to remediating this troublesome contaminant. Experiments were carried out in alkaline solution (to prevent volatilisation of H 2 S), in the absence or presence of added chloride ion and naphthenic acids (NAs). The product spread was variable due to the large number of competing reactions, including formation of polysulfide, oxidation to sulfate (either directly or via hypochlorination), sacrificial anode oxidation combined with sulfide trapping, and Kolbe oxidation of NAs combined with sulfide trapping. From the technological perspective, the product distribution is immaterial, because sour brines contain such high concentrations of inorganic and naphthenate salts that reinjection of the treated brine will always be required. The most efficient systems, on the basis of charge per mol sulfide remediated, employed packed bed reactors with ground coke or GAC anodes. In these reactors, the disappearance of sulfide ion was promoted, as expected, at low flow rate and high current. However, the packed beds were limited to low applied current, in order to avoid compromising the electrical conductivity of the anode bed by the production of gas (O 2 ).Les saumures géothermiques associéesà l'extraction du gaz naturel présentent un problème environnementalà cause du besoin d'éviter l'échappement de sulfures d'hydrogène toxiques et malodorants. Dans cetteétude, des anodes au carbone (y compris graphite, charbon actif en granulés et coke industriel) ontété utilisées pour l'oxydationélectrochimique de l'ion sulfure dans des saumures géothermiques synthétiques, a la fois en lots et en cuvesà flux continu, avec l'objectif d'éliminer ce contaminant ennuyeux. Des expérimentations ontété effectuées dans une solution alcaline (pour prévenir la volatilisation de H2S), en l'absence ou présence d'ions chlorures ajoutés et d'acides naphthéniques. La répartition du produitétait variable en raison du grand nombre de réactions concurrentes, y compris la formation of polysulfide, l'oxydation en sulfates (soit directement, soit par hypochloration), l'oxydation de l'anode sacrificielle combinéeà un piégeage du sulfure et une oxydation Kolbe d'acides naphthéniques combinéeà un piégeage du sulfure. Dans cette perspective technologique, la distribution du produit est immatérielle car les saumures acides contiennent de telles fortes concentrations de sels inorganiques et naphthénates qu'une réinjection de la saumure traitée sera toujours requise. Les systèmes les plus efficients, sur la base d'une charge par mole de sulfureéliminée, employaient des réacteursà lit fixe avec anodesà coke ouà carbon actif en granulés. Dans ces réacteurs, la dispar...

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Electrochemical oxidation of sulfide ion at a boron-doped diamond anode

Cited by 49 publications

References 23 publications

Anodic Oxidation of Sulfide to Sulfate: Effect of the Current Density on the Process Kinetics

Anodic Oxidation of Sulfide to Sulfate: Effect of the Current Density on the Process Kinetics

Sulfophobic and Vacancy Design Enables Self‐Cleaning Electrodes for Efficient Desulfurization and Concurrent Hydrogen Evolution with Low Energy Consumption

Oxidation of sulfide ion in synthetic geothermal brines at carbon‐based anodes

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