Evaluation of novel ZnO–Ag cathode for CO2 electroreduction in solid oxide electrolyser

CO₂ and steam/CO₂ electroreduction to CO and methane in solid oxide electrolytic cells (SOEC) has gained major attention in the past few years. This work evaluates, for the very first time, the performance of two different ZnO–Ag cathodes: one where ZnO nanopowder was mixed with Ag powder for preparing the cathode ink (ZnO_mix–Ag cathode) and the other one where Ag cathode was infiltrated with a zinc nitrate solution (ZnO_inf –Ag cathode). ZnO_mix–Ag cathode had a better distribution of ZnO particles throughout the cathode, resulting in almost double CO generation while electrolysing both dry CO₂ and H₂/CO₂ (4:1 v/v). A maximum overall CO₂ conversion of 48% (in H₂/CO₂) at 1.7 V and 700 °C clearly indicated that as low as 5 wt% zinc loading is capable of CO₂ electroreduction. It was further revealed that for ZnO_inf –Ag cathode, most of CO generation took place through RWGS reaction, but for ZnO_mix–Ag cathode, it was the synergistic effect of both RWGS reaction and CO₂ electrolysis. Although ZnO_inf –Ag cathode produced trace amount of methane at higher voltages, with ZnO_mix–Ag cathode, there was absolutely no methane. This seems to be due to strong electronic interaction between Zn and Ag that might have suppressed the catalytic activity of the cathode towards methanation.

     

Polymer electrolyte membrane fuel cell as a hydrogen flow rate monitoring device

There is a substantial demand for hydrogen flow rate monitoring devices in applications where hydrogen is utilised or produced and which include oil refineries, ammonia production, food and chemical industries, coal gasification, methane steam reforming and water electrolysis. In this paper, a polymer electrolyte membrane (PEM) fuel cell has been demonstrated for measuring accurate flow rates of hydrogen or hydrogen-containing gases. The concept involves applying a constant voltage to a PEM fuel cell to oxidise the entire hydrogen supplied to the anode compartment of the fuel cell and observing limiting current values attained and relating these to the hydrogen flow rates. PEM fuel cells with an active area of 50 cm² were constructed and used to accurately measure the flow rates of hydrogen up to 170 mL/min. A device with a capability to monitor significantly higher hydrogen flow rates can be constructed by using several cells in a stacking arrangement or by using electrically isolated cells in a single device. The paper discusses advantages and limitations of the technique and the flow rate-measuring response for gases containing 5–100 % hydrogen. The response time for hydrogen gas was of the order of 1–2 min. However, the fuel cell flow field design can be optimised for faster response times.     

Recherches dans la série des cyclitols XLVI. Actions de diazoalcanes sur la pentahydroxy-2,4,6/3,5-cyclohexanone et sur son dérivé penta-O-acétylé II. Etude de pentahydroxy-alkyl-C-cycloheptanones

On treatment with higher diazoalkanes, 2,4,6/3,5-penta-acetoxy-cyclohexanone (penta-O-acetyl-myo-inosose-2 or -scyllo-inosose) afforded by ring expansion all-trans-penta-acetoxy-C-alkyl-cycloheptanones, which by deacylation were converted to hemiacetals. The reactions with diazoalkanes of the penta-acetoxy-inosose in the presence of aluminium chloride and of the free inosose in water solution have also been studied. The structure, the configuration, and, in some cases, the conformation of the new compounds have been established and some of their reactions have been investigated. The mechanisms of formation of the ring expansion products and of the concomitant spiro-epoxides have been discussed.     

Hydrogen and oxygen generation with polymer electrolyte membrane (PEM)-based electrolytic technology

With dwindling liquid fuel resources, hydrogen offers a credible alternative. The use of hydrogen in a fuel cell offers the highest fuel conversion efficiency compared with all other technologies and it also has the potential to substantially reduce greenhouse gas and particulate emissions at least at the end-user sites. One of the major barriers to the introduction of the hydrogen economy and its wider acceptance is the lack of the rather costly hydrogen generation, transportation and distribution infrastructure to meet the local transport fuel demands. On-site or distributed hydrogen generation would remove the need for this up-front infrastructure requirements and assist with the early large-scale trials of the fuel cell technology for both transport and stationary applications and also introduction of the hydrogen economy. In this paper, the development of polymer electrolyte membrane electrolysis technology for on-site, on-demand hydrogen generation has been discussed. The major emphasis is given on reducing catalyst cost; interface design and modifications; interconnect materials, design and fabrication; and investigation of the sources of degradation. Stacks to 2 kW_{H 2} capacity have been constructed and tested and show initial efficiencies of >87% at 1 A cm⁻².     

Fuel quality and operational issues for polymer electrolyte membrane (PEM) fuel cells

Polymer electrolyte membrane (PEM) fuel cells are susceptible to degradation due to the catalyst poisoning caused by CO present in the fuel above certain limits. Although the amount of CO in the fuel may be within the permissible limit, the fuel composition (% CO₂, CH₄, CO and H₂O) and the operating conditions of the cell (level of gas humidification, cell temperature and pressure) can be such that the equilibrium CO content inside the cell may exceed the permissible limit leading to a degradation of the fuel cell performance. In this study, 50 cm² active area PEM fuel cells were operated at 55–60 °C for periods up to 250 hours to study the effect of methane, carbon dioxide and water in the hydrogen fuel mix on the cell performance (stability of voltage and power output). Furthermore, the stability of fuel cells was also studied during operation of cells in a cyclic dead end / flow through configuration, both with and without the presence of carbon dioxide in the hydrogen stream. The presence of methane up to 10% in the hydrogen stream showed a negligible degradation in the cell performance. The presence of carbon dioxide in the hydrogen stream even at 1–2% level was found to degrade the cell performance. However, this degradation was found to disappear by bleeding only about 0.2% oxygen into the fuel stream.     

Evaluation of solid electrolyte cells with a versatile electrochemical technique

Voltage losses in fuel cells and other solid electrolyte systems are due to several mass transport and kinetics processes at the electrode/electrolyte interface as well as to ohmic contributions from the electrolyte, electrodes, current collectors and contact resistances. Electrochemical impedance spectroscopy (EIS) has been in use for several decades in fuel cell research and is quite effective in determining the contribution of individual electrode and electrolyte processes. However, data acquisition and analysis can be time-consuming and the technique has many limitations whilst cell performance and operating conditions are varying rapidly with time especially when the cells are under current load. The galvanostatic current interruption (GCI) technique is fast and can be used under a wide range of operating as well as for rapidly varying loads and cell performance conditions. In this paper a totally new and very simple way of adapting commercially available equipment has been described to perform high quality, reliable and fast GCI measurements over a range of different currents in one sequence without having to use an electronic switch or a solid state relay or a separate fast data logging system. Its versatility has been demonstrated with a number of standard RC circuits simulating slow electrode and fast electrolyte processes and by evaluating a number of solid oxide fuel cell materials. The GCI technique has been shown to be able to determine the composition of all standard test circuits within ±1 % of those determined from the EIS technique and actual values of circuit components. The technique has been applied to investigating solid electrolyte cells and produced excellent results.     

Materials issues and recent developments in molten carbonate fuel cells

Molten carbonate fuel cell is one of the most promising high efficiency and sustainable power generation technologies, as demonstrated by the availability of several commercial units nowadays. Despite the significant progress made over the past few decades, the issues like component stability in carbonate melts and lower power density as compared to other high-temperature fuel cell systems need to be overcome to meet cost and lifetime targets. An improvement in the catalysts and system design for in situ reforming of fuel is critical to make molten carbonate fuel cells (MCFCs) compatible with real world fuels with minimal preprocessing requirements. Thus a significant opportunity exists for materials R&D in the MCFC area. In the present review, the key issues with MCFC component materials: cathode, anode, matrix, current collectors and bipolar plates, are discussed. The alternative materials and strategies adapted by the MCFC R&D community to mitigate these issues are discussed with emphasis on research trends and developments over the past decade.     

Recherches dans la série des cyclitols XLV. Action des diazoalcanes sur la pentahydroxy-2,4,6/3,5-cyclohexanone et sur son dérivé penta-O-acétylé. I. Etude des spiro-époxydes

On treatment with diazomethane, 2,4,6/3,5-penta-acetoxy-cyclohexanone(penta-O-acetyl-myo-inosose-2 or -scyllo-inosose) gave only a spiroepoxide. In contrast, replacement of diazomethane by higher diazoalkanes furnished a mixture of alkylspiroepoxides and of ring expansion products (cycloheptanone derivatives). The configuration and the reactions of the spiro-epoxides have been studied.     

Methanol-water co-electrolysis for sustainable hydrogen production with PtRu/C-SnO<Subscript>2</Subscript> electro-catalyst

Hydrogen at present is mainly produced from fossil fuels for use in ammonia synthesis, the petrochemical industry, and chemical production. In the future, hydrogen will be increasingly used as an energy vector. Although water electrolysis to produce hydrogen with renewable electricity offers a clean process, the approach is energy intensive, requiring a large renewable resource footprint. Methanol-water co-electrolysis can reduce the energy input by >?50%; its electrochemical oxidation poses complex issues such as poisoning of the catalyst, sluggish oxidation kinetics, and degradation over time. The addition of nano-sized SnO₂ to PtRu/C catalyst, to reduce noble metal loading, has been shown here to reduce catalyst leaching and increase the chemical, micro-structural, and performance stability of the methanol-water co-electrolysis process during extended periods of testing. The electrochemical characterization, analysis of the methanol solution, and exit gases, post-cell testing, revealed complete oxidation of methanol with little performance degradation. This is further supported by the stability of the catalyst composition and structure as revealed by the post-mortem XRD and XPS analysis of the cell. The energy balance calculations show that methanol-water co-electrolysis can significantly reduce the renewable energy footprint, and the process can become carbon neutral if bio-methanol is used with renewable electricity.