“Deactivation of copper electrode” in electrochemical reduction of CO2

Metallic Cu electrode can electrochemically reduce CO₂ to CH₄, C₂H₄ and alcohols with high yields as revealed by the present authors. Many workers reported that formation of CH₄ and C₂H₄ rapidly diminishes during electrolysis of CO₂ reduction. This paper shows that such deactivation of Cu electrode is reproduced with electrolyte solutions prepared from reagents used by these workers. Deactivated Cu electrodes recovered the electrocatalytic activity for CO₂ reduction by anodic polarization at −0.05 V versus she in agreement with the previous reports. Features of the deactivation depend greatly on the individual chemical reagents. Purification of the electrolyte solution by preelectrolysis with a Pt black electrode effectively prevents the deactivation of Cu electrode. Anode stripping voltammetry of Cu electrodes, which were deactivated during electrolysis of CO₂ reduction, showed anodic oxidation peaks at ca. −0.1 or −0.56 V versus she. The severer the deactivation of the Cu electrode was, the higher electric charge of the anodic peak was observed. It is presumed that some impurity heavy metal, originally contained in the electrolyte, is deposited on the Cu electrode during the CO₂ reduction, poisoning the electrocatalytic activity. On the basis of the potential of the anodic peaks, Fe²⁺ and Zn²⁺ are assumed to be the major contaminants, which cause the deactivation of the Cu electrode. Deliberate addition of Fe²⁺ or Zn²⁺ to the electrolyte solutions purified by preelectrolysis exactly reproduced the deactivation of a Cu electrode in CO₂ reduction. The amount of the deposited Fe or Zn on the electrode was below the monolayer coverage. Electrothermal atomic absorption spectrometry (etaas) showed that Fe originally contained in the electrolyte solution is effectively removed by the preelectrolysis of the solution. Mechanistic difference is discussed between Fe and Zn in the deterioration of the electrocatalytic property of Cu electrode in the CO₂ reduction. The concentration of the impurity substances originally contained in the chemical reagents as Fe or Zn is estimated to be far below the standard of the impurity levels guaranteed by the manufacturers. Presence of trimethylamine in the electrolyte solution also severely poisons a Cu electrode in the CO₂ reduction. It was concluded that the deactivation of Cu electrode in CO₂ reduction is not caused by adsorption of the products or the intermediates produced in CO₂ reduction.     

Improved gas diffusion electrodes for hybrid polymer electrolyte fuel cells

In this study, the performance of the anionic electrodes for hybrid polymer electrolyte fuel cells was improved. The anion exchange membrane (AEM) electrodes were initially characterized as the cathode on a proton exchange membrane (PEM) anode/membrane half-assembly (i.e. hybrid polymer electrolyte fuel cell). The electrode performance was improved by tailoring the ionomer distribution within the electrode structure so as to better balance the electronic, ionic, and reactant transport within the catalyst layer. An ionomer impregnation method was used to achieve a non-uniform ionomer distribution and higher performance. Traditional electrode fabrication methods (i.e. thin-film method) lead to a uniform ionomer distribution. The peak power density at 70 °C for a H₂/O₂ hybrid fuel cell was 44 mW cm⁻² using the thin-film electrode, and 120 mW cm⁻² using the ionomer impregnated electrode. A hydrophobic additive used in the catalyst layer further improved the electrode performance, giving a peak power density of 315 mW cm⁻² for H₂/O₂ at 70 °C. Electrochemical impedance spectroscopy was used as an in situ diagnostic tool to help understand the origin of the electrode improvements. The increase in performance was attributed to improved catalyst utilization due to the creation of facile gas transport domains in the AEM electrode structure. Similarly, the AEM anode prepared by ionomer impregnation with polytetrafluoroethylene resulted in a three-fold increase in the peak power density compared to ones made by the thin-film method, which has no polytetrafluoroethylene.     

Comparative Study of Electrocoagulation and Electrooxidation Processes for the Degradation of Ellagic Acid From Aqueous Solution

A comparative study of electrocoagulation and electrooxidation processes for the degradation of ellagic acid from aqueous solution was carried out. For the electrocoagulation process, metallic iron was used as electrodes whereas graphite and RuO₂/IrO₂/TaO₂ coated titanium electrodes were used for the electrooxidation processes. The effect of the process variables such as initial pH, concentration of the supporting electrolyte, applied current density, electrolysis time, and anode materials on COD removal were systematically examined and discussed. Maximum COD removal of 93% was obtained at optimum conditions by electrocoagultion using an iron electrode. The ellagic acid was degraded completely by electrooxidation using graphite electrodes under the optimum conditions. During electrooxidation, the chloride ion concentration was estimated and the effect of the Cl^? ion was discussed. The finding of this study shows that an increase in the applied current density, NaCl concentration, and electrolysis time enhanced the COD removal efficiency. The UV–Vis spectra analysis confirms the degradation of ellagic acid from aqueous solution.     

Electrochemical study of benzene on Pt of various surface structures in alkaline and acidic solutions

The electrochemical behaviour of benzene on platinum electrodes (polycrystalline and single-crystal electrodes) has been studied in acidic and alkaline solutions. In acid solutions the reduction of benzene to cyclohexane takes place in all the platinum surface structure employed, however it does not occur in alkaline media (0.1 M NaOH). In this case, the hydrogen adsorption-desorption processes displace the adsorbed benzene from the electrode surface. The oxidation of benzene is also affected by the pH of the electrolyte and also by the surface structure of the platinum electrode used. In acid solutions, this oxidation at higher potentials (1.4 V vs. RHE) yields CO₂, benzoquinone and α,β-unsaturated esters or lactones, however in alkaline media carbonate anions coming from CO₂ and salts of carboxylic acids have been detected by in situ FTIR spectroscopy using a platinum polycrystalline electrode. Bulk electrolysis of benzene solutions using a platinum electrode in acid and alkaline media was performed in order to confirm the results obtained by spectroscopic measurements.     

Electroreduction-Oxidation and Quantitative Determination of CO2 on A New SPE-Based System

Electroreduction—oxidation of CO₂ was studied by anodic stripping voltammetry on different SPE electrodes. The catalytic capacity of these electrodes for CO₂ electroreduction was examined by comparing the oxidation charges of both the products (R(CO₂)) produced by electroreduction of CO₂(Q_ox) and the adsorbed hydrogen (Q_H). SEM analysis was used to understand the catalytic capacity of different electrodes. A new electrochemical system based on a PtAu-SPE electrode, which had the best comprehensive catalytic capacity among the investigated electrodes, showed a satisfactory linear response (Q_ox) to CO₂ concentration in the range 0–40% when adsorption time t _ad≤ 1 min. In addition, this system possessed advantages such as no leakage, high efficiency, excellent reproducibility and good stability. Furthermore, the composition of R(CO₂) on the Pt-SPE and the Pt alloy-SPE electrodes was investigated by XPS analysis.     

Electro-reduction of carbon dioxide to formate on lead electrode in aqueous medium

The electrochemical reduction of carbon dioxide on a lead electrode was studied in aqueous medium. Preliminary investigations carried out by cyclic voltammetry were used to determine the optimized conditions of electrolysis. They revealed that the CO₂ reduction process was enhanced at a pH value of 8.6 for the cathodic solution i.e. when the predominant form of CO₂ was hydrogenocarbonate ion. Long-term electrolysis was carried out using both potentiometry and amperometry methods in a filter-press cell in which the two compartments were separated by a cation-exchange membrane (Nafion^® 423). Formate was detected and quantified by chromatography as the exclusive organic compound produced with a high Faradaic yield (from 65% to 90%). This study also revealed that the operating temperature played a key role in the hydrogenation reaction of carbon dioxide into formate in aqueous medium.     

Direct methanol alkaline fuel cells with catalysed anion exchange membrane electrodes

Membrane electrodes prepared by chemical deposition of platinum directly onto the anion exchange membrane electrolyte were tested in direct methanol alkaline fuel cells. Data on the cell voltage against current density performance and anode potentials are reported. The relatively low fuel cell performance was probably due to the low active surface area of Pt deposits on the membrane comparing to other membrane electrode assembly (MEA) fabrication methods. However, the catalysed membrane electrode showed good performance for oxygen reduction. A reduction in cell internal resistance was also obtained for the catalysed membrane electrode. By combining the catalysed membrane electrodes with a catalysed mesh, maximum current density of 98 mA cm^–2 and peak power density of 18 mW cm^–2 were achieved.     

Electrochemical reduction of high pressure CO2 at a Cu electrode in cold methanol

The electrochemical reduction of high pressure CO₂ with a Cu electrode in cold methanol was investigated. A high pressure stainless steel vessel, with a divided H-type glass cell, was employed. The main products from CO₂ by the electrochemical reduction were methane, ethylene, carbon monoxide and formic acid. In the electrolysis of high pressure CO₂ at low temperature, the reduction products were formed in the order of carbon monoxide, methane, formic acid and ethylene. The best current efficiency of methane was of 20% at −3.0 V. The maximum partial current density for CO₂ reduction was approximately 15 mA cm⁻². The partial current density ratio of CO₂ reduction and hydrogen evolution, i(CO₂)/i(H₂), was more than 2.6 at potentials more positive than −3.0 V. This work can contribute to the large-scale manufacturing of fuel gases from readily available and inexpensive raw materials, CO₂-saturated methanol from industrial absorbers (the Rectisol process).     

The electrochemical reduction of CO2 to CH4 and C2H4 at Cu/Nafion electrodes (solid polymer electrolyte structures)

The construction of copper/Nafion electrodes (solid polymer electrolyte structures) by an electroless plating method is described. These electrodes were used for the gas phase electrochemical reduction of CO₂ to hydrocarbon products, including CH₄ and C₂H₄. The faradaic efficiencies of the electrodes under ambient conditions with a counter solution of 1 mM H₂SO₄ at a potential of –2.00 V vs. SCE reached a steady-state value of about 20% after 30 min of electrolysis. This corresponded to a rate of total hydrocarbon production of approximately 9.8×10^–7 mole h^–1 cm^–2. Increasing the potential of the electrode to more negative potentials, or increasing the proton concentration of the counter solution, caused a decrease in the faradaic efficiencies due to a relative increase in the rate of proton reduction vs. that of CO₂ reduction. If the proton concentration of the counter solution was decreased to an alkaline pH, hydrocarbon production quickly ceased because of proton starvation.     

CO2 attraction by specifically adsorbed anions and subsequent accelerated electrochemical reduction

The electrochemical reduction of CO₂ was studied on a copper mesh electrode in aqueous solutions containing 3 M solutions of KCl, KBr and KI as the electrolytes in a two and three phase configurations. Electrochemical experiments were carried out in a laboratory-made, divided H-type cell. The working electrode was a copper mesh, while the counter and reference electrodes were Pt wire and Ag/AgCl electrode, respectively. Results of our work suggest a reaction mechanism for the electrochemical reduction of CO₂ in the two phase configuration where the presence of Cu-X as the catalytic layer facilitates the electron transfer from the electrode to CO₂. Electron-transfer to CO₂ may occur via the X_ad⁻(Br⁻, Cl⁻, I⁻)-C bond, which is formed by the electron flow from the specifically adsorbed halide anion to the vacant orbital of CO₂. The stronger the adsorption of the halide anion to the electrode, the more strongly CO₂ is restrained, resulting in higher CO₂ reduction current. Furthermore, it is suggested that specifically adsorbed halide anions could suppress the adsorption of protons, leading to a higher hydrogen overvoltage. These effects may synergistically mitigate the overpotential necessary for CO₂ reduction, and thus increase the rate of electrochemical CO₂ reduction.     

Electrochemical impedance spectroscopic investigation of CO2 reduction on polyaniline in methanol

The ac response of polyaniline thin films on platinum electrodes was measured at different dc potentials during the CO₂ reduction in methanol/LiClO₄ electrolyte with a small amount of 0.5 M H₂SO₄. The complex capacitance curves were simulated and the data obtained were used to calculate kinetic parameters, based on the assumption that the thermodynamic potential E₀ is in the region of −0.2-−0.1 V versus saturated calomel electrode (SCE). With E₀=−0.2 V versus SCE and β=0.6, a j₀ value of ca. 10⁻⁴ A cm⁻² was found for the electroreduction of CO₂ on the polyaniline electrode.     

Hydrogen evolution on RuxTi1−xO2 in 0.5 M H2SO4

Hydrogen evolution from 0.5 M H₂SO₄ on Ti electrodes coated with a Ru_xTi_1−xO₂ (x=0.04-0.5) layer has been studied by potentiostatic polarisation, cyclic voltammetry and ac-impedance spectroscopy. The results indicate that after a certain activation period the performance of such an electrode coating is comparable to platinum. The addition of small amounts of sodium molybdate increased the capacitance of the electrode and a reduction of the performance was observed. Increasing the temperature of the pure electrolyte from 20 to 75 °C caused an increase in the rate of the hydrogen evolution and in addition an increase of the electrode capacitance. The electrodes have been found to be rather tolerant to chloride and Fe²⁺ ions, and could hence be promising candidates as catalyst materials for solid polymer water electrolysis systems. From steady state measurements the Tafel slopes were found to change from −105 mV/decade for pure titanium to about −40 mV/decade for the (RuTi)O₂ coated electrodes. The exchange current densities were calculated from the steady state curves, as well as from impedance data, to be about 10⁻⁴ A cm⁻² after activation.     

Stable spinel type cobalt and copper oxide electrodes for O2 and H2 evolutions in alkaline solution

The stability of one material, Ti/Cu_xCo_3−xO₄, as anode and also cathode was investigated for electrolysis of alkaline aqueous solution. The electrodes were prepared by thermal decomposition method with x varied from 0 to 1.5. The accelerated life test illustrated that the electrodes with x = 0.3 nominally showed the best performance, with a total service life of 1080 h recorded in 1 M NaOH solution under alternating current direction at 1 A cm⁻² and 35 °C. The effects of copper content in electrode coating were examined in terms of electrode stability, surface morphology, coating resistivity and coating compositions. The presence of Cu in the spinel structure of Co₃O₄ could significantly enhance the electrochemical and physicochemical properties. The trends of crystallographic properties and surface morphology have been analyzed systemically before, during and after the electrodes were employed in alkaline electrolysis. The oxygen evolution would lead to the consumption of the coating material and the progressive cracking of the coating. Along with hydrogen evolution, cobalt oxide could be reduced to metal Co and Co(OH)₂ with particle sizes changed to smaller values in crystal and/or amorphous form at the cathode. The formation of Co is the key process for this electrode to serve as both anode and cathode. It is also the main reason leading to the eventual failure of the electrodes.     

Determination of open-circuit potentials at gas/electrode/YSZ boundary versus molten carbonate reference electrode at medium temperatures: I. Potentials of Au and Pt in O2 and H2 + H2O atmospheres

A double gas concentration cell as combination of the cell with the yttria stabilized zirconia (YSZ) electrolyte and the cell with molten Li₂CO₃ + Na₂CO₃ eutectics is proposed as an alternative cell system with a standard reference electrode for measurements of the open-circuit potential (OCP) values of electrodes in oxygen concentration cell with the yttria stabilized zirconia (YSZ) electrolyte. In this double-cell one electrode is common for the two cells and the reference electrode is the standard molten carbonate half-cell with 0.33O₂ + 0.67CO₂ atmosphere. This reference electrode should enable the monitoring of OCP and overpotential values in polarization studies in the three-electrodes configuration. If the possible reaction between the solid YSZ and liquid molten carbonates electrolyte is very slow, the measured values of the open-circuit-voltage (OCV) of this cell may be considered equal to the respective reversible electromotive forces (EMF). Very good resistance of the smooth YSZ products to the corrosion in highly dehydrated Li/Na molten carbonates has been shown in experiments lasting few 1000 h. Hence, the consistency of OCV values with the respective EMF values have been tested at various partial pressures of CO₂ and O₂ in the gas mixtures above the molten carbonate electrolyte and at various partial pressures of O₂ + Ar or H₂ + H₂O gas mixtures at the Au or Pt electrodes/YSZ interface. The results have shown the reliability of the double-cell in determination of the open-circuit potentials (OCP) of gas electrodes at the YSZ surface as measured versus the reference electrode with molten carbonate electrolyte. The consistency of OCP and EMF values has been shown satisfying and enhances to use the proposed double-cell in further investigations of OCP and overpotential values at TPB of electrode/YSZ/mixture of reacting gases. At high differences of O₂ partial pressures on both sides of the YSZ membrane some permeation of this gas through the YSZ membrane has been observed. Probably, this effect has an electrochemical character.     

<Emphasis Type="Italic">In situ</Emphasis> microobservation of the cathode in molten carbonate fuel cells

In molten carbonate fuel cells (MCFC), the wettability of the electrode and the electrolyte distribution are very important factors influencing the active reaction area. We have observed the molten carbonate behaviour directly on the cathode (porous NiO) and the electrolyte plate (LiAlO₂) under various gas conditions and at controlled potentials using an environmental scanning electron microscope (ESEM) equipped with a hot stage. We estimated the liquid electrolyte distribution in the cathode and measured the contact angles on NiO and LiAlO₂ in the electrolyte. Moreover, the electrolyte movement in the reaction CO₂ + O₂ + 2e^– = CO₃ ^2– was observed on the surface of the porous NiO in a CO₂/O₂ atmosphere. The reaction CO₃ ^2– + 2e^– = CO + 2 O^2– of the gas generation was observed in a H₂O atmosphere. The active reaction points on the electrode are the areas where the electrolyte film is thin.     

Electro-oxidation of coal on NiO and/or Co3O4 modified TiO2/Pt electrodes

A TiO₂/Pt based electrode exhibited better activity for the oxidation of coal in a basic system compared to Ti/Pt, TiO₂–Cu/Pt and pure metal electrodes. The surface morphologies and composition of the electrodes were studied by SEM and XRD, respectively. Linear sweep voltammetry was employed to investigate the catalytic effects of electrodes, and the product of coal oxidization was determined by a gas collection test. The TiO₂/Pt electrodes that were modified with NiO and/or Co₃O₄ exhibited higher average currents and a lower decrease in mass during electrolysis compared to the other electrodes; this finding indicated that NiO and Co₃O₄ play important roles as catalysts.     

Electrochemical detoxification of waste water without additives using solid polymer electrolyte (SPE) technology

Ion exchange membranes as solid polymer electrolytes (SPE) facilitate the electrochemical detoxification of waste water without addition of supporting electrolyte. Cation exchange membranes as H⁺ ion conductors or anion exchange membranes as OH^? ion conductors were used in combination with different electrode materials. A variety of cell configurations were investigated which differ in the direction of the electro-osmotic stream (EOS). This is a characteristical property of SPE technology, caused by the solvation shells of the ions during their migration through the membrane. Dependent on cell configuration mass transfer at the electrodes can be hindered or enhanced by EOS. In the latter case it is appropriate to increase EOS by preparation of Nafion^® membranes in order to decrease energy consumption per m³ waste water. Using a perforated membrane, which operates in this case only as ion conducting solid polymer electrolyte but not as cell separator, flow rates through the cell can be adjusted independent of the EOS and a further decrease of energy consumption is possible. The best results were obtained using anodic oxidation followed by cathodic reduction: 2-chlorophenol as example compound was destroyed almost completely and more than 80% of the chlorine was mineralized to chloride ions. By-products were detected in very low amounts, less than the remaining traces of 2-chlorophenol.     

Electro-organic synthesis without supporting electrolyte: Possibilities of solid polymer electrolyte technology

The application of ion exchange membranes as solid polymer electrolytes (SPE) in fuel cells is state-of-the-art. This technology needs no supporting electrolyte; consequently it can be applied for electro-organic syntheses in order to save process steps. In this case the process is not predetermined to a maximized energy efficiency so that the selection of the cell design, of the electrode materials and of the operating conditions can be focused on a high selectivity of the electrode reactions. The electro-osmotic stream, which is caused by the solvation shells of the ions during their migration through the membrane, and hence is a typical property of SPE technology, has a significant effect on the electrode reactions. It generates enhanced mass transfer at the electrodes, which is beneficial for reaction selectivity. It can be influenced by the choice of, and possibly by the preparation of, the membrane. An additional remarkable advantage of SPE technology is the exceptional long durability of oxide coated electrodes. By combination of several process engineering methods stable operation of SPE cells has been realized, even for examples of non-aqueous reaction systems. Experiments up to 6000 h duration and in cells of up to 250 cm² membrane area show the potential for industrial application.     

A direct electrochemical route from oxide precursors to the terbium-nickel intermetallic compound TbNi5

Successful direct electrochemical reduction of mixed powders of terbium oxide (Tb₄O₇) and nickel oxide (NiO) to the intermetallic compound, TbNi₅, is demonstrated in molten CaCl₂ at 850 °C by constant voltage (2.4-3.2 V) electrolysis. The reduction mechanism was investigated by cyclic voltammetry using a molybdenum cavity electrode in conjunction with characterisations of the products from both constant voltage and potentiostatic electrolysis under different conditions by XRD, SEM and EDX. It was found that the reduction started from NiO to Ni, followed by that of Tb₂O₃ (resulting from Tb₄O₇ decomposition) on the pre-formed Ni to form the intermetallic compound. The reduction speed increased with increasing the cell voltage, but the speed gain was counterbalanced by decreased current efficiency and increased electric energy consumption. At 2.4 V, the current efficiency reached 63.2%, and the energy consumption by electrolysis was as low as 3.2 kWh/kg TbNi₅ when the oxide phase was converted fully to the metal phase (XRD) in 4 h. The oxygen level in the produced TbNi₅ could readily reach 1800 ppm by electrolysis at 3.2 V for 12 h with the energy consumption being 18.9 kWh/kg TbNi₅.     

Bifunctional electrodes for an integrated water-electrolysis and hydrogen-oxygen fuel cell with a solid polymer electrolyte

An alternative concept of an integrated water electrolysis/hydrogen-hydrogen fuel cell using metal electrocatalysts and a solid polymer electrolyte is described. Instead of operating both electrodes as hydrogen and oxygen electrodes respectively the electrodes are used as oxidation and reduction electrodes in both modes of operation. A more suitable selection of electrocatalysts and an improved cell design are possible; both can increase the efficiency of the cell considerably. New results on the electrocatalytic activity of various noble-metal containing catalysts with respect to both oxygen evolution and hydrogen oxidation in a proton exchange membrane-cell at 80°C are reported. Kinetic data derived from Tafel plots of the oxygen evolution polarization curves agree closely with those of experiments with aqueous sulphuric acid electrodes. This agreement allows the determination of kinetic parameters for electrocatalysts difficult to prepare in solid smooth electrodes but easy to be made into porous deposits. Polarization curves of the hydrogen oxidation reaction clearly indicate a relative activity rating of the studied catalysts. In cycling tests the lifetime stability of the new bifunctional oxidation electrode was determined. Polarization data obtained under these conditions agree with those obtained in earlier experiments where electrodes were exposed to only one type of oxidation reaction. During a test of 10 cycles (30 min of electrolyser and 30 min of fuel cell mode each) no changes in the electrode potential were observed. With the conventional cell design employing a hydrogen and an oxygen electrode both catalyzed with platinum and a current density of 100 mA cm^–2 a storage efficiency of 50% was calculated; with the alternative concept of oxidation and reduction electrodes and selected oxidation catalysts this was improved to 57%. With further improvements these efficiencies seem possible even at current densities of 500 mA cm^–2.