The electrochemical oxidation of aqueous sulfur dioxide: A critical review of work with respect to the hybrid sulfur cycle

Literature regarding the mechanism of the electrochemical oxidation of aqueous sulfur dioxide to sulfuric acid has been critically evaluated to provide a detailed understanding of the reaction under various applied conditions. This reaction is of high relevance to the hybrid sulfur cycle for large scale hydrogen production, as well as other industrial applications such as flue gas desulfurisation. Widespread disagreement in the literature and non-reproducible behaviour of the electrochemical oxidation reaction has been found in this review to often be a result of poorly defined electrode preconditioning procedures. It has also been found that the mechanistic pathway of the oxidation reaction is heavily influenced by the electrode material, solution pH and the applied anodic potential. These factors are thought to influence adsorption and the reductive formation of sulfur species at low potentials.     

Activation of monolithic catalysts based on diatomaceous earth for sulfur dioxide oxidation

The formation of the active phases during the activation process of monolithic catalysts based on V₂O₅–K₂SO₄ supported on diatomaceous earth for SO₂ to SO₃ oxidation in flue gases, has been shown to be a crucial factor to achieve satisfactory catalytic performance. As the temperature is increased from room temperature to 470°C, SO₂ and SO₃ are taken up by the green catalyst and the precursors are transformed into the active species. The role of each component of the catalyst during the activation was analyzed by studying the behavior towards SO₂ adsorption of four materials, which contained: diatomaceous earth, diatomaceous earth + V, diatomaceous earth + K, and diatomaceous earth + V + K. The influence of the potassium sulfate accessibility in the green catalyst was studied by using two different preparation methods, which gave rise to differences in the catalysts SO₂ adsorption properties and catalytic performance. Furthermore, the influence of the activation atmosphere was studied using nitrogen, oxygen or a flue gas composition. It was shown that pyrosulfate species should be formed at temperatures below 400°C, to keep the vanadium in the active 5+ oxidation state.     

The influence of sulfur dioxide on propane oxidation activity over supported platinum and palladium

Earlier studies have shown that sulfur dioxide and metal-support interaction can strongly influence propane oxidation over platinum. In particular, oxidation activity is enhanced when platinum is supported on sulfated -alumina or zirconia compared to -alumina. Therefore, it is of interest to compare the performance of palladium under the same experimental conditions. Four model catalysts were examined: Pt/-alumina, Pt/zirconia, Pd/-alumina and Pd/zirconia. The metal loading was kept at or below 0.05 wt% to emphasize changes in activity attributable to metal-support interaction. Reaction rates were measured with and without sulfur dioxide. Surface sulfation was analyzed by measuring acid strength and evaluating spectra obtained by Fourier-transform infrared spectroscopy. In contrast to platinum, sulfation does not promote propane oxidation on Pd/-alumina, and Pd/zirconia is less active than Pd/-alumina.     

The electrochemical oxidation of aqueous phenol at a glassy carbon electrode

The electrooxidation of phenol is of interest as a model compound for the treatment of aqueous organic wastes. The effect of voltage, concentration and temperature on the electrochemical oxidation of acidic dilute aqueous solutions of phenol was studied. Electrolysis was carried out by recirculating phenol solutions through a flow-by electrochemical reactor employing a reticulated glassy carbon anode. Concentrations of phenol and some breakdown products were monitored using HPLC analysis. Increased voltage was found to shift the product distribution to favour more oxidized products but also to increase electrode corrosion and decrease current efficiency. Higher phenol concentrations (over the range of 5-20 mmol/L) showed a shift in product distribution to favour less oxidized, mostly insoluble products. Elevated temperatures (about 50°C and higher) showed a marked ability to reduce electrode passivation and increase the phenol oxidation rate.     

The electrochemical oxidation of sulfite on gold: UV-Vis reflectance spectroscopy at a rotating disk electrode

Certain aspects of the electrochemical oxidation of sulfite in buffered, mildly acidic aqueous solutions (pH 5.23) have been examined using in situ near normal incidence UV-Vis reflectance spectroscopy (NNI-UVRS) at a Au rotating disk electrode (RDE). The dependence of the limiting current, i_lim, on the rotation rate of the RDE was found to display classical Levich behavior up to potentials well within the range in which Au forms a surface oxide in the neat (sulfite-free) supporting electrolyte. However, simultaneous in situ NNI-UVRS measurements performed at λ=500 nm during sulfite oxidation failed to show any evidence for the presence of oxide on the Au surface within that entire potential range. Polarization of the Au RDE at more positive potentials led to a sudden drop in i_lim, ca. an order of magnitude, which correlated with an abrupt decrease in the intensity of the reflected light, consistent with formation of (one or more forms of) Au oxide on the surface. On the basis of these and other observations a model has been proposed in which sulfite reacts chemically with adsorbed oxygen on the surface (oxygen atom transfer) in the region that precedes partial inhibition. As the potential is increased, adsorbed oxygen undergoes Au-O place exchange forming two-dimensional nuclei on the surface, which undergo rapid (autocatalytic) growth, covering an area large enough to block significantly sulfite oxidation.     

Nonlinear phenomena during electrochemical oxidation of hydrogen on platinum electrodes

H₂ oxidation on Pt electrodes, a comparatively simple electrocatalytic reaction, has been known for a long time to exhibit a variety of complex temporal oscillations, depending on the composition of the supporting electrolyte. We report, on the one hand, recent observations of spatial instabilities in the bistable and oscillatory region in this system. The studies indicate that the spatio-temporal dynamic is by far richer than has been assumed so far. On the other hand, aperiodic responses of the system in cyclic voltammetric experiments are described. This behavior is similar to the one observed in potentiodynamic measurements during the electro-oxidation of small organic molecules. A possible common origin of all these complex, current–voltage responses is discussed.     

电沉积Ni-P-ZrO2复合电极析氢电催化性能的研究

用电沉积方法制备了镍－磷－二氧化锆复合电极。通过阴极极化曲线,交流阻抗等电化学技术研究其析氢催化性能,并用扫描电镜观察电极的表面形貌。实验结果表明,在80℃,25％氢氧化钠碱性溶液中镍－磷－二氧化锆的表观交换电流密度及表面粗糙度皆大于镍,镍－磷电极,而反应电阻较小。说明镍－磷中引入二氧化锆所形成的复合镀层具有较高的析氢催化活性和良好的电化学稳定性。     

Studies on the deactivation of NOx storage-reduction catalysts by sulfur dioxide

The interaction of sulfur dioxide with a commercial NO_x storage-reduction catalyst (NSR) has been investigated using in situ IR and X-ray absorption spectroscopy. Two pathways of catalyst deactivation by SO₂ were identified. Under lean conditions (exposure to SO₂ and O₂) at 350 °C the storage component forms barium sulfates, which transform from surface to hardly reducible bulk sulfate species. The irreversible blocking of the Ba sites led to a decrease in NO_x storage capacity. Under fuel rich conditions (SO₂/C₃H₆) at 350–500 °C evidence for the formation of sulfides on the oxidation/reduction component (Pt) of the catalyst was found, which blocks the metal surface and thus hinders the further reduction of the sulfides.     

Effects of porosity on the electrochemical oxidation performance of Ti4O7 electrode materials

Ti₄O₇ is a kind of conductive ceramic material with a high electrical conductivity and excellent electrochemical performance, rendering it a potential candidate for electrode applications. Here, for the first time, we report the successful preparation of Ti₄O₇ electrodes with different porosities by adding a pore-forming agent. The results showed that the as-prepared Ti₄O₇ electrodes contained both mesoporous and macroporous structures. In addition, with an increase in the porosity of the electrodes, the electrochemical oxidation degradation of high-concentration methyl orange (MO) solution first increased, until reaching a critical point, and then decreased. The Ti₄O₇ electrode with a porosity of 34.9% and an electrical conductivity of 336.1 S cm^-1 exhibited the highest electrochemical oxidation ability. The electrochemical oxidation rate constants for MO and chemical oxygen demand (COD) of the porous Ti₄O₇ electrode were 1.7 times those of the dense Ti₄O₇ electrode. Compared to commercial stainless steel, graphite, and Ti/RuO₂ electrodes, the Ti₄O₇ porous electrode showed superior electrochemical oxidation performance under the same experimental conditions. The result of this study provide new directions for the application of Ti₄O₇ electrode materials.     

Electrochemical degradation of 2,4-dichlorophenol on a palladium modified gas-diffusion electrode

Pd/C catalyst was prepared by hydrogen reduction method and used for the Pd/C gas-diffusion electrode. It was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) techniques. The electrochemical degradation of 2,4-dichlorophenol was investigated in a diaphragm electrolysis system, feeding firstly with hydrogen gas then with air, using the Pd/C gas-diffusion electrode and the carbon/polytetrafluoroethylene (C/PTFE) gas-diffusion electrode as a cathode, respectively. The results indicated that the self-made Pd/C gas-diffusion cathode can not only reductively dechlorinate 2,4-dichlorophenols by feeding hydrogen gas, but also accelerate the two-electron reduction of O₂ to hydrogen peroxide (H₂O₂) by feeding air. Therefore, both the removal efficiency and the dechlorination degree of 2,4-dichlorophenol reached about 100% after 80 min, and the average removal efficiency of 2,4-dichlorophenol in terms of total organic carbon (TOC) exceeded 76% after 160 min by using Pd/C gas-diffusion cathode, which were better than that of the C/PTFE gas-diffusion cathode. The analysis of high-performance liquid chromatography (HPLC) identified that 4-chlorophenol, 2-chlorophenol, and phenol were the dechlorination products, and hydroquinone, benzoquinone, maleic, fumaric, crylic, malonic, oxalic, acetic and formic acids were the main oxidation intermediates. A reaction scheme involving all these intermediates was proposed.     

Micromolar determination of sulfur oxoanions and sulfide at a renewable sol-gel carbon ceramic electrode modified with nickel powder

The sol-gel technique was used to fabricate nickel powder carbon composite electrode (CCE). The nickel powder successfully used to deposit NiO_x thin film on conductive carbon ceramic electrode for large surface area catalytic application. Repetitive cycling in potential range −0.2 to 1.0 V was used to form of a thin nickel oxide film on the surface carbon composite electrode. The thin film exhibits an excellent electro-catalytic activity for oxidation of SO₃²⁻, S₂O₄²⁻, S₂O₃²⁻, S₄O₆²⁻ and S²⁻ in alkaline pH range 10-14. Optimum pH values for detection of all sulfur derivatives is 13 and catalytic rate constants are in range 2.4 × 10³-8.9 × 10³ M⁻¹ s⁻¹. The hydrodynamic amperometry at rotating modified CCE at constant potential versus reference electrode was used for detection of sulfur derivatives. Under optimized conditions the calibration plots are linear in the concentration range 10 μM-15 mM and detection limit 1.2-34 μM and 0.53-7.58 nA/μM (sensitivity) for electrode surface area 0.0314 cm². The nickel powder doped modified carbon ceramic electrode shows good reproducibility, a short response time (2.0 s), remarkable long term stability, less expense, simplicity of preparation, good chemical and mechanical stability, and especially good surface renewability by simple mechanical polishing and repetitive potential cycling. This sensor can be used into the design of a simple and cheap chromatographic amperometry detector for analysis of sulfur derivatives.     

Studies on electrochemical oxidation of azithromycin and Hemomycin at gold electrode in neutral electrolyte

The aim of the present study was to examine the oxidative properties and an assay of azithromycin and Hemomycin^® at a gold electrode in neutral electrolyte using cyclic linear sweep voltammetry. The maximum value of the current of the oxidation peak of pure azithromycin and azithromycin from Hemomycin^® at 0.6 V versus SCE in 0.05 M NaHCO₃ and in a mixture methanol −0.05 M NaHCO₃ (1:1) at a scan rate of 50 mV s⁻¹ is a linear function of the concentration in the range of 0.235-0.588 mg/cm³. HPLC analysis of the bulk of electrolyte confirmed the data obtained by analysis of the values of the current peak concerning the concentration of antibiotic in the investigated concentration range. The role of methanol, when present, is discussed. In the case of azithromycin, the presence of methanol leads to higher current peak values. However, in the case of Hemomycin^®, methanol should be avoided because of its inhibiting influence on the qualitative and quantitative determination of azithromycin and on the azithromycin/lactose separation.     

Analysis of sulfur poisoning on a PEM fuel cell electrode

The extent of irreversible deactivation of Pt towards hydrogen oxidation reaction (HOR) due to sulfur adsorption and subsequent electrochemical oxidation is quantified in a functional polymer electrolyte membrane (PEM) fuel cell. At 70 °C, sequential hydrogen sulfide (H₂S) exposure and electrochemical oxidation experiments indicate that as much as 6% of total Pt sites are deactivated per monolayer sulfur adsorption at open-circuit potential of a PEM fuel cell followed by its removal. The extent of such deactivation is much higher when the electrode is exposed to H₂S while the fuel cell is operating at a finite load, and is dependent on the local overpotential as well as the duration of exposure. Regardless of this deactivation, the H₂/O₂ polarization curves obtained on post-recovery electrodes do not show performance losses suggesting that such performance curves alone cannot be used to assess the extent of recovery due to sulfur poisoning. A concise mechanism for the adsorption and electro-oxidation of H₂S on Pt anode is presented. H₂S dissociatively adsorbs onto Pt as two different sulfur species and at intermediate oxidation potentials, undergoes electro-oxidation to sulfur and then to sulfur dioxide. This mechanism is validated by charge balances between hydrogen desorption and sulfur electro-oxidation on Pt. The ignition potential for sulfur oxidation decreases with increase in temperature, which coupled with faster electro-oxidation kinetics result in the easier removal of adsorbed sulfur at higher temperatures. Furthermore, the adsorption potential is found to influence sulfur coverage of an electrode exposed to H₂S. As an implication, the local potential of a PEM fuel cell anode exposed to H₂S contaminated fuel should be kept below the equilibrium potential for sulfur oxidation to prevent irreversible loss of Pt sites.     

Potential and current oscillations during formaldehyde oxidation on platinum particles dispersed in three-dimensional pore networks of TiOx/Ti

Electrochemical oscillations during the anodic oxidation of formaldehyde (HCHO) were studied on a modified electrode of platinum particles highly dispersed in the three-dimensional pore networks of TiO_x/Ti (Pt-TiO_x/Ti). Under conditions of room temperature and stationary electrode, not only current oscillations under both cyclic voltammetric and potentiostatic conditions but also potential oscillations under galvanostatic conditions were obtained. The intensity of current oscillations strongly depends on the concentration of HCHO or H₂SO₄, upper potential limit (upl) of cyclic voltammetry, applied constant potential and duration of time (t_d) at constant potential. Potential oscillations exhibit various patterns such as periodic, quasi-periodic, mixed-mode oscillations and other different bifurcations, which are greatly effected by the applied constant current and the concentration of HCHO or H₂SO₄. Meanwhile, the oscillatory system has a bistable characteristic with stable states at both low and high potentials. The observed potential and current oscillations are caused by the cyclic formation/removal of intermediate poison CO from the electrode surface during HCHO oxidation. The highly dispersed Pt particles on the surface of Pt-TiO_x/Ti electrode improve the electrocatalytic activity of the electrode, which greatly facilitates the formation of CO by the oxidation of HCHO and the removal of CO by its reaction with hydroxyl radicals (OH). Furthermore, the three-dimensional pore networks of the electrode's TiO_x/Ti support are favorable to the adsorption/desorption of reactants or intermediate product and thus increase the rate of reactions giving rise to electrochemical oscillations.     

Multiple steady-states for the oxidation of aqueous ethanol with oxygen on a carbon supported platinum catalyst

The selective oxidation of aqueous ethanol by dioxygen over a platinum on carbon catalyst was investigated in a three-phase continuously stirred tank reactor at a total pressure of 600 kPa, a temperature of 323 K, a pH of 8.4, and a catalyst concentration of 2.3 kg m^–3. Multiple steady-states were obtained by systematic changes in the start-up procedure and variation of the feed concentration of ethanol and partial oxygen pressure in the reactor. The ethanol feed concentration was varied from 100 to 2500 mol m^–3 and the partial oxygen pressure from 8 to 120 kPa. On the time scale of the experiments, i.e. 21 ks, two steady-states of the net disappearance rate of ethanol are observed in the ethanol feed concentration range from 500 to 2500 mol m^–3 at a partial oxygen pressure of 58 kPa and in the range of partial pressure of oxygen from 8 to 120 kPa at an ethanol feed concentration of 500 mol m^–3. Three steady-states are observed in the feed ethanol concentration range from 200 to 400 mol m^–3 and a partial oxygen pressure of 58 kPa.     

Effect of concentration and temperature on electrochemical oscillations during sulfide oxidation on Ti/Ta2O5-IrO2 electrodes

The impact of current density, concentration, and temperature on the potential oscillations observed during the anodic oxidation of sulfide on Ti/Ta₂O₅-IrO₂ oxide electrodes is investigated. Electrochemical methods including: cyclic voltammetry, linear voltammetry, linear galvanic voltammetry, galvanostatic technique and electrochemical impedance spectroscopy are used in this study. The observed potential oscillations are caused by the periodic formation/removal of sulfur from the electrode surface. Increasing current density has the effect of increasing the frequency of oscillations as well as increasing the onset potential. Both increasing concentration and temperature gave rise to significant increases in current density prior to the onset of potential oscillations. The activation energy for electrochemical oxidation of sulfide was estimated from the temperature studies. Lifetime experiments were also conducted and demonstrated that potential oscillations have a detrimental impact on the electrode lifetime.     

Effect of carbon dioxide on the selectivities obtained during the partial oxidation of methane and ethane over Li+/MgO catalysts

AtT 650 °C carbon dioxide either formed during reaction or added to the system increases the selectivity for the desired hydrocarbon products during the oxidative coupling of methane and the oxidative dehydrogenation of ethane reaction over Li⁺/MgO catalysts. Similarly, CO₂ inhibits secondary reactions of CH₃-radicals with the surface of the Li⁺/MgO. The improved selectivities are attributed to the poisoning effect that CO₂ has on the secondary reactions of alkyl radicals with the surface.     

In situ electrochemical oxidation of ethylenediamine on Co–B alloy electrode during cycling for improving its electrochemical properties at elevated temperature

A Co–B alloy/ethylenediamine (EDA) hybrid electrode system has been developed by adding EDA into electrolyte. Charge–discharge measurements show that the inorganic–organic hybrid electrode system exhibits high discharge capacity and long cycle life at elevated temperature (55 °C). Specifically, in the electrolyte containing 0.09 M EDA additive, the discharge capacity of Co–B alloy electrode after 100 cycles is still up to 601.7 m Ah g⁻¹ at 55 °C. However, for the electrode in EDA-free electrolyte, its discharge capacity is sharply decreased to only 138.5 m Ah g⁻¹ after 100 cycles. ICP-OES and IR measurements are used to clarify the reason of the improvement in the electrochemical properties. These results show that beneficial effect of EDA on electrochemical properties of Co–B alloy electrode can be attributed to in situ electrochemical oxidation of EDA during discharge cycles. First the oxidation of EDA contributes to part of the discharge capacity and secondly the oxidation products absorbed on the electrode may help to suppress the dissolution of Co at elevated temperature. Evidence is presented suggesting that the oxidation of Co can induce co-oxidation of EDA.     

Oxidation of aqueous sulfur dioxide catalyzed by poly-4-vinylpyridine–Cu(II) complex. Part 1: Homogeneous phase oxidation

The oxidation of aqueous sulfur dioxide in the presence of polymer-supported copper(II) catalyst is also accompanied by homogeneous oxidation of aqueous sulfur dioxide catalyzed by leached copper(II) ions. Aqueous phase oxidation of sulfur dioxide of low concentrations by oxygen in the presence of dissolved copper(II) has therefore been studied. The solubility of SO₂ in aqueous solutions is not affected by the concentration of copper(II) in the solution. In the oxidation reaction, only HSO is the reactive S(IV) species. Based on this observation a rate model which also incorporates the effect of sulfuric acid on the solubility of SO₂ is developed. The rate model includes a power-law type term for the rate of homogeneous phase reaction obtained from a proposed free-radical chain mechanism for the oxidation. Experiments are conducted at various levels of concentrations of SO₂ and O₂ in the gas phase and Cu(II) in the liquid phase. The observed orders are one in each of O₂, Cu(II) and HSO. This suggests a first-order termination of the free radicals of bisulfite ions.     

Studies on the electrochemical degradation of Acid Orange II wastewater with cathodes modified by quinones

The electrochemical oxidation of dye wastewater with the cathode modified by quinones has been investigated. Under the optimal conditions, the decolorization efficiency can reach 96.0% after 120 min. The addition of tert-butanol significantly decreased the decolorization efficiency, suggesting the involvement of •OH radicals in the decomposition of H₂O₂. A potential difference may result in a quinone radical on the cathode which can catalyze the reduction of O₂ to H₂O₂. UV–vis spectrum and GC/MS analysis revealed that the dye molecule was firstly initiated by the cleavage of NN, and decomposed to aromatic intermediates, further degraded to ring opening products and finally mineralized.