DESIGN OF AN ELECTROLYTIC CELL FOR A MONOLITHIC PHOTOVOLTAIC-ELECTROLYTIC HYDROGEN GENERATION SYSTEM: THE ELECTRODE ASPECTS

The combination of a photovoltaic (PV) and an electrolytic cell into one single system, a monolithic PV-electrolytic cell, has been suggested as an efficient solar hydrogen generation system. In this study, we demonstrate an efficient prototype electrolysis system applied to a monolithic PV-electrolytic cell. Specifically, the relatively large unit cell (active area of 36 cm²) used in the study made it possible to directly measure in volume the amount of hydrogen and oxygen generated. To enhance the activity of the electrodes we introduced channels, Co₃O₄ film, and Pt particles on stainless steel (SUS) substrates. The highest hydrogen production rate was obtained in the system in which Co₃O₄ electrocatalytic film on a SUS foil and Pt particles on a SUS plate with channels were used as an anode and a cathode, respectively.     

Electrochemically assisted photocatalytic degradation of oxalic acid on particulate TiO2 film in a batch mode plate photoreactor

Electrochemically assisted photocatalytic degradation of oxalic acid was studied in a batch mode plate photoreactor composed of particulate TiO₂ film immobilized on Ti metal plate (Ti/TiO₂ electrode) and Pt wires immersed in a flowing film of aqueous solution (Pt counter electrode). The degradation rate of oxalic acid was followed as a function of the potential of the Ti/TiO₂ electrode, the oxygen concentration and the light intensity. The presence of oxalic acid caused an increase in the measured photocurrent by one order of magnitude which is due to its reaction with photogenerated holes. The degradation rate increased with increasing potential up to 0.5 V vs SCE, then the increase was more gradual. Electrochemically assisted photocatalytic degradation of oxalic acid also proceeded in the absence of oxygen. The photogenerated electrons caused hydrogen evolution (low oxygen concentration) or predominantely oxygen reduction (high oxygen concentration) on the Pt counter electrode.     

Deactivation and regeneration of Pt anodes for the electro-oxidation of phenol

Electro-oxidation tests with different electrolytes (Na₂SO₄, NaCl, H₂SO₄) and anode types (Pt, Ti lined with Ir and Ta oxides, PbO₂, activated carbon) were performed on aqueous solutions containing phenol to assess the mechanism and nature of electrode deactivation phenomena. For the Pt electrode, the nature of the electro-deposited organic species was investigated by ATR-FTIR and FESEM-EDS analyses, which showed adsorption of intermediate oxidation products (e.g. benzoquinone, hydroquinone) is likely responsible for the early deactivation stages. Conversely, in the longer term, formation of polymeric films is promoted. Potentiostatic tests showed that anode regeneration can be achieved by anodic polarisation above 1.1 V (vs Hg/Hg₂SO₄). This reactivation was found to be easier in the presence of significant amounts of chloride ions. Conversely, the deactivated state is maintained for the Ti/IrO₂/Ta₂O₅ electrode even though anodic polarisation at high positive potentials is applied. Cyclic voltammetric curves on PbO₂ electrodes did not provide satisfactory results as the intensity of the lead-dioxide reduction peak was so high that peaks for phenol oxidation were hardly detectable. Finally, the activated carbon based electrode was found to be promising as it enables simultaneous adsorption of the organic pollutant and oxidation of the pollutant itself to constitute a sort of self-regenerating adsorber unit.     

Components for PEM fuel cell systems using hydrogen and CO containing fuels

Proton exchange membrane fuel cells (PEMFC) show a significant performance drop in CO containing hydrogen as fuel gas in comparison to pure hydrogen. The lower performance is due to CO adsorption at the anode thus poisoning the hydrogen oxidation reaction. Two approaches to improve the cell performance are discussed. First, the use of improved electrocatalysts for the anode, such as PtRu alloys, can significantly enhance the CO tolerance. On the other hand, CO poisoning of the anode could be avoided by the use of non-electrochemical methods. For example, the addition of liquid hydrogen peroxide to the humidification water of the cell leads to the formation of active oxygen by decomposition of H₂O₂ and the oxidation of CO. In such a way a complete recovery of the CO free cell performance is achieved for H₂/100 ppm CO.     

Simulations and study of electrochemical hydrogen energy conversion in EasyTest Cell

An EasyTest Cell concept is applied to study the performance characteristics of the electrochemical processor for polymer electrolyte membrane electrochemical hydrogen energy converters (PEM EHEC), broadly known as a membrane electrode assembly (MEA). A series of MEAs consisting of Nafion 117 polymer electrolyte and magnetron sputtered Pt, IrO_x, and composite IrO_x/Pt/IrO_x catalysts with varying catalytic loadings were investigated. The partial electrode reactions proceeding in the real PEM EHEC, namely hydrogen oxidation (HOR), hydrogen evolution (HER), oxygen reduction (ORR), and oxygen evolution (OER), are simulated and studied in a recently developed test cell with a unitized gas compartment. The EasyTest Cell design gives possibilities for strict control of the experimental conditions by avoiding the usage of any auxilliary gas conditioning equipment. By varying the thickness of the sputtered Pt film, the catalyst loading is remarkably reduced (from 0.5 to 0.06 mg cm⁻² or about 8 times) for both HOR and HER without any sacrifice of the electrode performance. The electrode with 0.2 mg cm⁻² sputtered IrO_x shows the best OER performance. The composite IrO_x/Pt/IrO_x electrode demonstrated a bi-functional catalytic activity toward both OER and ORR, as well as improved gas diffusion properties toward ORR compared to the single Pt layer with the same catalytic loading.A phenomenological criterion for evaluating the gas diffusion properties of the electrodes is proposed. The applied testing approach is validated via comparison of the results obtained in the EasyTestCell and the common laboratory PEM electrolytic cell.     

Electrochemical oxidation of simple indoles at a PbO2 anode

Simple indoles undergo electrolytic degradation at potentials near +1 V vs the normal hydrogen electrode at a Pb/PbO₂ anode. Oxidation is first order in both current and indole concentration. The reaction is characterized by low CO₂ yields and high TOC values, that is, most of the carbon of the starting material remained in the solution after electrolysis. Monomeric, isolable oxidation products were not found even at high conversion. These results are consistent with the intermediacy of hydroxyl radicals, which are produced at the surface of the Pb/PbO₂ anode by electrolysis of water, initiating the polymerization of the starting materials to water soluble products with high net current efficiency.     

MnO2/MCMB electrocatalyst for all solid-state alkaline zinc-air cells

Nanostructured MnO₂/mesocarbon microbeads (MCMB) composite has been prepared successfully for use in zinc-air cell as electrocatalyst for oxygen reaction. The scanning electron microscope (SEM) images showed that the MnO₂ nanorods were formed and covered on the surface of MCMB in bird’s nest morphology. X-ray diffraction (XRD) pattern indicated that the MnO₂ has the hollandite structure with a composition approximating KMn₈O₁₆. By the cathodic polarization curve tests, the nanostructured material demonstrated excellent electrocatalytic activity as a kind of oxygen electrode electrocatalyst compared with electrolytic MnO₂. An all solid-state zinc-air cell has been fabricated with this material as electrocatalyst for oxygen electrode and potassium salt of cross-linked poly(acrylic acid) as an alkaline polymer gel electrolyte. The cell has good discharge characteristics at room temperature.     

Size Dependent Study of MeOH Decomposition Over Size-selected Pt Nanoparticles Synthesized via Micelle Encapsulation

We communicate experimental results for the oxidation of methane by oxygen over alumina supported Pd and Pt monolith catalysts under transient conditions. Temperature programmed reaction (TPReaction) and reactant pulse-response (PR) experiments have been performed, using a continuous gas-flow reactor equipped with a downstream mass spectrometer for gas phase analysis. Special attention was paid to the influence of gas composition changes, i.e., O₂ and H₂ pulsing, respectively, on the methane conversion. For Pt/Al₂O₃ oxygen pulsing can significantly increase the methane conversion which can be even further improved by pulsing hydrogen instead. Such transient effects are not observed for the Pd/Al₂O₃ catalyst for which instead constantly lean conditions is beneficial. Our results suggest that under lean conditions Pd and Pt crystallites may undergo bulk- and partial (surface oxide formation) oxidation, respectively, which for Pd results in more active surfaces, while for Pt the activity is reduced. The latter seems to connect to a lowering of the ability to dissociate methane.     

Porous Co/Co–Ni–Pt nanostructures prepared by galvanic replacement towards methanol electro-oxidation

The nanostructured Co/Co–Ni–Pt catalyst were synthesized by electrodeposition process and galvanic replacement reaction. The alloy prepared on a copper electrode (Cu/Co/Co–Ni–Zn) was dipped in platinum containing alkaline solution to produce a porous Cu/Co/Co–Ni–Pt catalyst. The catalyst was characterized by energy dispersive X-ray and scanning electron microscopy techniques and its electrocatalytic properties were evaluated using cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry techniques. The results showed that the Co/Co–Ni–Pt coatings are porous, and composed of discrete Pt nanoparticles with the crystallite size of about 66 nm. It was shown from cyclic voltammograms in alkaline solutions that the oxidation current of methanol on the nanostructured Cu/Co/Co–Ni–Pt electrode was much higher than that on flat platinum. Electrochemical impedance spectra on the Co/Co–Ni–Pt electrode reveal that the charge transfer resistance decreases with the increase of anodic potentials. All results show that the Co/Co–Ni–Pt catalysts can be potential anode catalysts for the direct methanol fuel cell.     

Electrocatalysis of the hydrogen oxidation in the presence of CO on RhO2/C-supported Pt nanoparticles

This work presents a study on the kinetics of the hydrogen oxidation reaction (HOR) in the absence and in the presence of CO in ultra thin porous layer and in PEM fuel cell electrodes formed with Pt supported on RhO₂/C substrates. Together with the electrochemical measurements, the structural and electronic properties of these catalysts were characterized, enabling to correlate their structural and electronic properties with the HOR kinetics. The results show that the presence of Rh oxides leads to an emptying of the Pt 5d band and a consequent reduction of the back-donation of electrons from Pt to CO, weakening the Pt-CO bond and diminishing the CO degree of coverage on Pt, leaving more sites available to HOR. These changes in the electronic spectra do not lead to any perceptible change in the kinetics or the reaction of pure hydrogen. Also, the formation of CO₂ monitored by the MS experiments in the fuel cell anode outlet indicates that the bifunctional mechanism is also operative, but the major CO tolerance is achieved by the electronic effect induced by the RhO₂ support.     

Roles of adsorbed OH and adsorbed H in the oxidation of hydrogen and the reduction of UO<Stack><Subscript>2</Subscript><Superscript>2+</Superscript></Stack> ions at Pt electrodes under non-conventional conditions

The roles of adsorbed hydroxyl radicals, OH, at a high temperature and adsorbed hydrogen atoms, H, in an acidic solution were investigated in the electrochemical reactions on Pt electrode by using potentiodynamic polarisation experiment, cyclic voltammetry and constant-potential electrolysis combined with UV/VIS analysis. From the analysis of the polarisation curves obtained from Pt electrode in a 0.185 M H₃BO₃ solution at 473 K, it was found that the reducing capability of dissolved hydrogen is significantly enhanced due to the increases of the mass transfer and the electron transfer rates. Especially, it is suggested that the stable Pt-OH_ad plays a significant role in the passivation reaction in the potential range from 0.60 to 0.75 V_SHE. From the analyses of the experimental results for the electrochemical reduction of UO₂²⁺ ions on Pt surface in a 1.0 M HClO₄ solution, it is recognised that the reduction reaction of UO₂²⁺ to U⁴⁺ ions is strongly dependent on the hydrogen atoms adsorbed on Pt electrode (indirect reduction of UO₂²⁺) as well as on the electrons transferred from Pt electrode (direct reduction of UO₂²⁺). In addition, the reduction mechanism of UO₂²⁺ ions involved in Pt-H_ad is also proposed.     

Effects of poly-1,5-diaminoanthraquinone morphology on oxygen reduction in acidic solution

The poly-1,5-diaminoanthraquinone (P15DAAQ) modified Pt electrodes show electrocatalytic activity for oxygen reduction reaction (ORR) with oxygen reduction peak at about 0.39 V in 0.1 M H₂SO₄. The P15DAAQ with different thickness has different morphology. The effects of morphologies on the electrocatalytic behaviors of P15DAAQ for oxygen reduction reaction are investigated using cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements. We propose two different O₂-transport processes on electrodes modified with thin P15DAAQ and thick P15DAAQ. Together with the quantitative analysis with O₂-transport dynamics, electron-transfer resistance, and catalytic reaction rate during ORR, thin P15DAAQ electrode performs better electrocatalysis for ORR, although thick P15DAAQ provides higher real surface area and more reactive sites which is beneficial for ORR within a short time.     

Investigation of hydrogen transport through Mm(Ni3.6Co0.7Mn0.4Al0.3)1.12 and Zr0.65Ti0.35Ni1.2V0.4Mn0.4 hydride electrodes by analysis of anodic current transient

Hydrogen transport through such metal-hydride electrodes as Mm(Ni_3.6Co_0.7Mn_0.4Al_0.3)_1.12 and Zr_0.65Ti_0.35Ni_1.2V_0.4Mn_0.4 was investigated in 6 M KOH solution by using potentiostatic current transient technique. From the shape of the anodic current transient and the dependence of the initial current density on the discharging potential, the boundary conditions at the electrode surface were established during hydrogen extraction from the as-annealed and as-surface-treated electrodes. Especially, it was experimentally confirmed that the diffusion-limited boundary condition is no longer valid at the electrode surface during hydrogen transport in case hydrogen diffusion is coupled with either the interfacial charge transfer reaction or the hydrogen transfer reaction between adsorbed state on the electrode surface and absorbed state at the electrode sub-surface. From the transition behaviour of the boundary condition, it was further recognised that the boundary condition at the electrode surface during hydrogen transport is not fixed at the specific electrode/electrolyte system by itself, but it is rather simultaneously determined even at any electrode/electrolyte system by the potential step and the nature of the electrode surface, depending upon e.g. the presence or absence of the surface oxide scales.     

High performance electrode for electrochemical oxygen generator cell based on solid electrolyte ion transport membrane

A double-layer composite electrode based on Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ + Sm_0.2Ce_0.8O_1.9 (BSCF + SDC) and BSCF + SDC + Ag was investigated to be a promising cathode and also anode for the electrochemical oxygen generator based on samaria doped ceria electrolyte. The Ag particles in the second layer were not only the current collector but also the improver for the oxygen adsorption at the electrode. a.c. impedance results indicated that the electrode polarization resistance, as low as 0.0058 Ω cm² was reached at 800 °C under air. In oxygen generator cell performance test, the electrode resistance dropped to half of the value at zero current density under an applied current density of 2.34 A cm⁻² at 700 °C, and on the same conditions the oxygen generator cell was continual working for more than 900 min with a Faradic efficiency of ∼100%.     

EIS study of the influence of BrCl on the behavior of electrodes in Li/SOCl<Subscript>2</Subscript> cells

The influence of BrCl on the impedance response of both the lithium anode and the carbon cathode in Li/SOCl₂ cells was studied. The impedance of the lithium anode increases with storage time while the addition of BrCl to Li/SOCl₂ cells decreases the impedance. However, the porous carbon cathode shows a small film resistance before discharge. The addition of BrCl to Li/SOCl₂ cells also decreases the impedance, especially for that part of the interface reaction resistance R₂. As a rule, the film resistance of the lithium anode decreases sharply during the early period of discharge, while that of the porous carbon cathode rises rapidly. It follows that the porous carbon cathode is the rate controlling electrode during discharge.     

High specific surface area Ce0.8Zr0.2O2 promoted Pt/C electro-catalysts for hydrogen oxidation and CO oxidation reaction in PEMFCs

A series of Pt–Ce_0.8Zr_0.2O₂/C electrocatalysts with various content of Ce_0.8Zr_0.2O₂ were synthesized by one-pot synthesis process by ethylene glycol (EG) method. High specific surface area nanosized Ce_0.8Zr_0.2O₂ was prepared by a surfactant-templated method. Effect of the addition of Ce_0.8Zr_0.2O₂ for the electro-catalytic activities of Pt/C catalysts were detected by cyclic voltammetry (CV), liner cyclic voltammetry (LSV) and CO-stripping techniques. It was found that 40 wt%Pt–10 wt%Ce_0.8Zr_0.2O₂ exhibited a better activity among those catalysts for hydrogen and CO oxidation reaction. The membrane-electrode assembly (MEA) fabricated with 40 wt%Pt–10 wt%Ce_0.8Zr_0.2O₂ as the anode exhibited the excellent catalytic activity toward hydrogen oxidation reaction (HOR) and reached 490 mW cm⁻² at 0.49 V in a single cell test. The electrocatalytic effect related to the change in the electrocatalyst structure was discussed based on the XRD and TEM data. Also, the electrochemical impedance spectra (EIS) were used to assess the effect of the addition of Ce_0.8Zr_0.2O₂ for the performance of fuel cells.     

Electrochemical characterization of zirconium-doped LiNi0.8Co0.2O2 cathode materials and investigations on deterioration mechanism

The electrochemical performance and the degradation mode of the zirconium doped cathode material, LiNi_0.8Co_0.18Zr_0.02O₂ were investigated and compared with the pristine cathode, LiNi_0.8Co_0.2O₂. The cyclic performance of the doped cathode was superior to the pristine cathode, especially under the high voltage cutoff, although its rate capability remained unimproved. The trend in the graphs of the differential capacity showed that the impedance growth of the cell made of the pristine cathode was much faster than the doped. From the results of the XRD pattern changes between before and after the galvanostatic cycling, less cation mixing and more ordered hexagonal structure were observed for the doped cathode. The impedance spectra showed that the charge transfer resistance for the pristine cathode grew significantly with cycling, while that for the doped cathode increased just moderately. Considerable decrease in the impedance was observed when the new lithium was substituted with the cycled anode, which implied that the interfacial impedance growth on the anode accounted for about 20% of the total impedance measured. It is concluded that the fading mode for LiNi_0.8Co_0.2O₂ is mainly due to the cation mixing, partially contributed by the impedance growth on the anode and by doping the pristine cathode with Zr, cation mixing can be efficiently suppressed.     

A “proton pump” concept for the investigation of proton transport and anode kinetics in proton exchange membrane fuel cells

A novel concept for the measurement of proton transport properties and electrode kinetics in proton exchange membrane fuel cells (PEMFC) is presented. The “proton pump” is essentially a fuel cell operated with pure nitrogen or very low hydrogen partial pressure instead of oxygen-containing gas on the cathode side, avoiding the complicated electrode kinetics of oxygen reduction. In this first study using this concept, we investigated the proton transport in high temperature PEMFC based on polybenzimidazole (PBI)/phosphoric acid membranes. The impedance spectra of the proton pump allow the clear distinction between anode and cathode kinetics and proton transport in the membrane. Identifying and analyzing the contribution of the anodic processes in the impedance spectra enabled the quantitative investigation of anode kinetics based on the Butler-Volmer equation. The proton transport was investigated in more detail in the current saturation region, where proton transport turned out to be the limiting process in case of sufficient H₂ supply at the anode. The maximum proton transport capacity of the PBI/phosphoric acid membrane was found to be comparable to those of Nafion^® membranes.     

Structure sensitivity of dimethylamine deep oxidation over Pt/Al2O3 catalysts

The deep oxidation of dimethylamine (DMA) was studied over Pt/Al₂O₃ catalysts with small (1 nm) and large (7.8–15.5 nm) Pt crystallite sizes. The turnover frequency (TOF) was higher for the large than for the small Pt crystallites, indicating that the reaction is structure sensitive. Two kinetic models were used to interpret the obtained results, i.e., the Mars van Krevelen and a mechanism based on the adsorption of oxygen and adsorption of dimethylamine on different active sites were employed. Both models showed that the activation energy for the oxygen chemisorption rate constant (k_o) decreased with increasing of Pt crystallite size and that the activation energy for the surface reaction rate constant (k_i) was independent of the Pt crystallite size. The structure sensitivity may be explained by differences in the reactivity of the oxygen adsorbed on these Pt crystallites.The Mars van Krevelen model fits the TOF values very well at concentrations of DMA higher than 1500 ppm, while in the lower concentrations region, the model under predicts the experimental data. The model based on the adsorption of oxygen and DMA on different active sites fits the experimental data quite well over the whole temperature and concentration range. The fitted values of the Henry adsorption constant are independent of the Pt crystallite size.     

Catalytic roughening of surface layers of BDD for various applications

The surface layers of BDD electrodes have been roughened through excavation by small Ni, Co and Pt particles in a flowing gas mixture of H₂(10%) and N₂(90%) between 800 °C and 1000 °C. The specific surface area of the BDD evaluated with the double layer capacitance was enhanced by the excavation of up to nearly 15 times as much pristine BDD electrode. The following potential applications for the surface-roughened BDD were proposed: (1) interlayer of the porous oxide catalyst layer and metal substrate of IrO₂-Ta₂O₅/(Ti or Nb) electrode, for instance, and (2) supporting material with large surface area for catalyst metal particles.