Bench-scale electrochemical system for generation of CO and syn-gas

A flow cell based, bench-scale electrochemical system for generation of synthesis-gas (syn-gas) is reported. Sensitivity to operating conditions such as CO₂ flow, current density, and elevated temperature are described. By increasing the temperature of the cell the kinetic overpotential for the reduction of CO₂ was lowered with the cathode voltage at 70 mA cm⁻² decreased by 0.32 V and the overall cell voltage dropping by 1.57 V. This equates to an 18% increase in cell efficiency. By closely monitoring the products it was found that at room temperature and 70 °C the primary products are CO and H₂. By controlling the current density and the flow of CO₂ it was possible to control the H₂:CO product ratio between 1:4 and 9:1. The reproducibility of performing experiments at elevated temperature and the ability to generate syn-gas for extended periods of time is also discussed.     

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).     

Supercritical CO2-assisted extrusion foaming: A suitable process to produce very lightweight acrylic polymer micro foams

A strategy of CO₂-assisted extrusion foaming of PMMA-based materials was established to minimize both foam density and porosities dimension. First a highly CO₂-philic block copolymer (MAM: PMMA-PBA-PMMA) was added in PMMA in order to improve CO₂ saturation before foaming. Then the extruding conditions were optimized to maximize CO₂ uptake and prevent coalescence. The extruding temperature reduction led to an increase of pressure in the barrel, favorable to cell size reduction. With the combination of material formulation and extruding strategy, very lightweight homogeneous foams with small porosities have been produced. Lightest PMMA micro foams (ρ = 0.06 g cm⁻³) are demonstrated with 7 wt% CO₂ at 130°C and lightest blend micro foams (ρ = 0.04 g cm⁻³) are obtained at lower temperature (110°C, 7.7 wt% CO₂). If MAM allows a reduction of T^foaming, it also allows a much better cell homogeneity, an increase in cell density (e.g., from 3.6 10⁷ cells cm⁻³ to 2 to 6 10⁸ cells cm⁻³) and an overall decrease in cell size (from 100 to 40 μm). These acrylic foams produced through scCO₂-assisted extrusion has a much lower density than those ever produced in batch (ρ ≥ 0.2 g cm⁻³).     

Effect of ZnO:Cs2CO3 on the performance of organic photovoltaics

We demonstrate a new solution-processed electron transport layer (ETL), zinc oxide doped with cesium carbonate (ZnO:Cs₂CO₃), for achieving organic photovoltaics (OPVs) with good operational stability at ambient air. An OPV employing the ZnO:Cs₂CO₃ ETL exhibits a fill factor of 62%, an open circuit voltage of 0.90 V, and a short circuit current density of −6.14 mA/cm² along with 3.43% power conversion efficiency. The device demonstrated air stability for a period over 4 weeks. In addition, we also studied the device structure dependence on the performance of organic photovoltaics. Thus, we conclude that ZnO:Cs₂CO₃ ETL could be employed in a suitable architecture to achieve high-performance OPV.     

Highly CO2RR activity and electrochemical performance of A-site deficient symmetrical electrode materials (La0.6Sr0.4)1−xFe0.8Ni0.2O3-δ for CO2 electrolysis

A-site deficient (La_0.6Sr_0.4)_1−xFe_0.8Ni_0.2O_3-δ (x = 0, 0.05, 0.1) perovskite oxide materials (LSFN100, LSFN95, and LSFN90) are evaluated as symmetrical electrode materials for CO₂ electrolysis. All three perovskite oxides display pure cubic perovskite structure. The introduction of A-site deficiency results in greater tendency of in-situ exsolution and stronger CO₂ adsorption capacity, which are verified by temperature-programmed reduction of H₂ and temperature-programmed desorption of CO₂. Furthermore, the current densities with LSNF90 symmetrical cell are 1.72, 1.18 and 0.72 A·cm⁻² under the applied voltage of 1.8 V at 850, 800 and 750 °C to electrolysis CO₂, respectively. Low polarization resistance of 0.186, 0.267 and 0.454 Ω·cm² is also observed under open circuit conditions at 850, 800 and 750 °C, respectively. A-site deficiency of perovskite materials reduces the activation energy of oxygen evolution reaction (OER) and carbon dioxide reduction reaction (CO₂RR). Symmetrical cell with LSFN90 electrode shows good electrochemical performance and long-term stability for CO₂ electrolysis.     

Computer simulation of high-discharge-rate battery systems

Simulations were carried out for a proposed two-dimensional high-discharge-rate cell under load with an interelectrode gap of the order of 100 m. A finite difference program was written to solve the set of coupled, partial differential equations governing the behaviour of this system. Cell dimensions, cell loads, and kinetic parameters were varied to study the effects on voltage, current and specific energy. Trends in cell performance are noted, and suggestions are made for development of cells to meet specific design criteria. Modelling difficulties are discussed and suggestions are made for improvement.Nomenclature A surface area of unit cell (cm²) - A _k conductivity parameter (cm^{2 –1} mol^–1) - b Tafel slope (V) - c concentration (mol cm^–3) - c ₀ concentration of bulk electrolyte (mol cm^–3) - D diffusivity (cm² s^–1) - D _h lumped diffusion parameter (J s cm^–2 mol^–1) - D _s lumped diffusion coefficient (A cm² mol^–1) - E rest potential of electrode (V) - F Faraday constant (96 500 C mol^–1) - i current density (A cm^–2) - I total current for unit cell (A) - i ₀ exchange current density (A cm^–2) - N flux of charged species (mol cm² s^–1) - R gas constant (8.314 J mol^–1 K^–1) - R _ext resistance external to cell () - t time (s) - T temperature (K) - t ₀ transference number - u mobility (cm² mol J^–1 s^–1) - V volume of an element in the cell (cm³) - V _ext voltage external to cell (V) - z charge on an ion - _c concentration overpotential (V) - _s surface overpotential (V) - conductivity (^–1 cm^–1) - stoichiometric coefficient - electric potential in solution (V)     

Boosting catalytic and CO2 adsorption ability by in situ Cu nanoparticle exsolution for solid oxide electrolysis cell cathode

Solid oxide electrolysis cell (SOEC) is recognized as an effective means to accomplish sustainable development since it is an efficient electrochemical technology for CO₂ emission reduction. However, the electrocatalytic reduction activity of the cathode for CO₂ restricts the development of SOEC. Herein, an A-site deficient perovskite Sr_1·9Fe_1·3Cu_0·2Mo_0·4Ti_0·1O_6-δ (SFCMT) was proposed as cathode material that can in situ exsolve uniform Cu nanoparticles. The exsolution of Cu increases the concentration of oxygen vacancies and provides abundant adsorption sites for CO₂, resulting in excellent electrochemical catalytic capacity. Cu@SFCMT-based single cells exhibit excellent electrolytic performance under pure CO₂, with current densities up to 3.21 A cm⁻² at 1.8 V and 800 °C and interface polarization resistance (Rp) as low as 0.20 Ω cm² at 800 °C. Furthermore, the current density changes slightly after the 140 h stability test at 1.2 V. Cu@SFCMT exhibits outstanding electrochemical activity and durability, making it a viable SOEC cathode material.     

Electrochemically Activated CNT Sheet as a Cathode for Zn-CO2 Batteries

High demand for electrochemical storage devices is increasing the need for high-performance batteries. A Zn-CO₂ battery offers a promising solution for CO₂ reduction as well as energy storage applications. For this study, a Zn-CO₂ battery was fabricated using a Carbon Nanotube (CNT) sheet as a cathode and a Zn plate as an anode. The electrochemical activation technique was used to increase the surface area of the CNT electrode by roughly 4.5 times. Copper (Cu) as a catalyst was then deposited onto the activated CNT electrode using electrodeposition method and different Cu loadings were investigated to optimize CO₂ reduction. The final assembled Zn-CO₂ battery has a 1.6 V output voltage at a current density of 0.063 mA/cm², which is higher than most devices reported in the literature. This study demonstrates the importance of activation process which enabled more catalyst loading on the cathode resulted in additional active sites for electroreduction process. This paper presents the activated CNT sheet as a promising cathode material for Zn-CO₂ batteries.     

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.     

Carbon-free dry reforming of methane to syngas over NdCoO3 perovskite-type mixed metal oxide catalyst

CoNdO_x (Co/Nd = 1) is a highly promising catalyst for the carbon-free CO₂ reforming of methane. Influence of the Co/Nd ratio on the catalyst performance in the CO₂ reforming and also on the crystalline phases and reduction by temperature programmed reduction (TPR) of the CoNdO_x catalyst has also been investigated. The CoNdO_x (CoNd = 1.0) catalyst consisted of mainly NdCoO₃ perovskite-type mixed metal oxide and it showed not only a high resistance to carbon formation at different process conditions (viz. temperature = 750–900 °C and gas hourly space velocity (GHSV) = 10000–50000 cm³ g^–1 h^–1) but also high activity and selectivity in the CO₂ reforming process. The high resistance to carbon formation for this catalyst is attributed mostly to strong metal (Co°)–support (Nd₂O₃) interactions.     

CO tolerance and catalytic activity of Pt/Sn/SnO2 nanowires loaded on a carbon paper

Electrochemical activities and structural features of Pt/Sn catalysts supported by hydrogen-reduced SnO₂ nanowires (SnO₂NW) are studied, using cyclic voltammetry, CO stripping voltammetry, scanning electron microscopy, and X-ray diffraction analysis. The SnO₂NW supports have been grown on a carbon paper which is commercially available for gas diffusion purposes. Partial reduction of SnO₂NW raises the CO tolerance of the Pt/Sn catalyst considerably. The zero-valence tin plays a significant role in lowering the oxidation potential of CO_ads. For a carbon paper electrode loaded with 0.1 mg cm⁻² Pt and 0.4 mg cm⁻² SnO₂NW, a conversion of 54% SnO₂NW into Sn metal (0.17 mg cm⁻²) initiates the CO_ads oxidation reaction at 0.08 V (vs. Ag/AgCl), shifts the peak position by 0.21 V, and maximizes the CO tolerance. Further reduction damages the support structure, reduces the surface area, and deteriorates the catalytic activity. The presence of Sn metal enhances the activities of both methanol and ethanol oxidation, with a more pronounced effect on the oxidation current of ethanol whose optimal value is analogous to those of PtSn/C catalysts reported in literature. In comparison with a commercial PtRu/C catalyst, the optimal Pt/Sn/SnO₂NW/CP exhibits a somewhat inferior activity toward methanol, and a superior activity toward ethanol oxidation.     

Infrared and carbon dioxide chemisorption study of Mo/ZrO2 catalysts

The interaction of Mo with zirconia has been investigated by infrared spectroscopy (IR) and carbon dioxide chemisorption. Quantitative analysis of the IR results indicated that Mo interacts preferentially with the most basic hydroxyl group (high frequency band at 3775 cm^–1). An approximately 79% decrease in the 3775 cm^–1 band is observed vs. 21% for the low frequency band at 3673 cm^–1, with increasing the Mo loading up to 1 wt%. The relative decrease of the IR band at 3775 cm^–1 was identical to that measured for the CO₂ uptake. The Mo cross-sections estimated from CO₂ chemisorption results were much higher than those typically reported for the Mo system. It was concluded that, as previously reported for the Mo/Al₂o₃ system, CO₂ chemisorption overestimates the surface coverage of Mo/ZrO₂ catalysts.     

Porosity engineering of biochar-based single-atom Ni catalysts to promote CO2 electroreduction over a broad potential window

Developing electrocatalysts for CO₂ electroreduction with high activity and superior selectivity is extremely important and desirable from both academic and industrial perspectives. However, owing to competition with hydrogen evolution, highly efficient CO₂ reduction is mostly achieved with high CO selectivity in a narrow potential range, which is incompatible with a large cell voltage required for industrial-level CO₂ reduction. Herein, we report an effective strategy to regulate CO₂ reduction performances of single-atom Ni electrocatalysts over a broad potential window by engineering their pore structures (micropores, mesopores, or hierarchical pores with both micropores and mesopores). It is revealed that hierarchically pores can significantly promote CO₂ reduction efficiency of single-atom Ni electrocatalysts. The hierarchically porous electrocatalyst achieves a maximum CO Faradaic efficiency (FE_CO) of 97.4% at −1.2 V (vs. RHE) and shows high FE_CO of >85% over a broad potential window from −0.7 to −1.7 V, much superior to electrocatalysts with other pore structures. More impressively, turnover frequency of the hierarchically porous electrocatalyst increases rapidly with increasing the applied potential and reaches 50,067 h⁻¹ at −1.7 V. Such CO₂ electroreduction promotion could be attributed to a synergistic effect of micropores for enhancing CO₂ adsorption and mesopores for facilitating rapid release of product bubbles, which significantly improves CO₂ reduction and suppresses hydrogen evolution.     

Structural and electrical characteristics of high-κ Er2O3 and Er2TiO5 gate dielectrics for a-IGZO thin-film transistors

In this letter, we investigated the structural and electrical characteristics of high-κ Er₂O₃ and Er₂TiO₅ gate dielectrics on the amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film transistor (TFT) devices. Compared with the Er₂O₃ dielectric, the a-IGZO TFT device incorporating an Er₂TiO₅ gate dielectric exhibited a low threshold voltage of 0.39 V, a high field-effect mobility of 8.8 cm²/Vs, a small subthreshold swing of 143 mV/decade, and a high I_on/I_off current ratio of 4.23 × 10⁷, presumably because of the reduction in the oxygen vacancies and the formation of the smooth surface roughness as a result of the incorporation of Ti into the Er₂TiO₅ film. Furthermore, the reliability of voltage stress can be improved using an Er₂TiO₅ gate dielectric.     

Application of a polymer heterojunction in dye-sensitized solar cells

Using a blend heterojunction consisting of a C₆₀ derivative, [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM), and poly(3-hexylthiophene) (P3HT) as a charge carrier transfer medium to replace the I₃⁻/I⁻ redox electrolyte, a novel TiO₂/dye/PCBM/P3HT dye-sensitized solar cell was fabricated and characterized. It was found that the P3HT/PCBM heterojunction widened the incident light harvest range from ultraviolet to visible light, and improved the photoelectrical response of the dye-sensitized solar cell. We investigated the influence of the PCBM/P3HT ratio and barrier layer on the photoelectric performance of the solar cell and proposed optimized preparation conditions. The optimized solar cell with a barrier layer and PCBM/P3HT ratio of 1:2 had a short circuit current density of 5.52 mA cm⁻², an open circuit voltage of 0.87 V, a fill factor of 0.640 and a light-to-electric energy conversion efficiency of 3.09% under a simulated solar light irradiation of 100 mW cm⁻².     

H2/Cl2 fuel cell for co-generation of electricity and HCl

A H₂/Cl₂ fuel cell system with an aqueous electrolyte and gas diffusion electrodes has been investigated and the effects of electrolyte concentration and temperature on the open circuit voltage (OCV) and cell performance have been evaluated. Furthermore, the kinetics and long-term stability of Pt as electrocatalyst have been studied under various conditions. In addition, the long-term stability of Rh electrocatalyst has been evaluated. The OCV obtained showed that the Cl₂ reduction is more reversible than O₂ reduction. The ohmic drop was determining the cell performance at high current densities. An output power of about 0.5 W cm^–2 was achieved with this system.     

Comparative study on the electrochemical performance of Sr(Ti0.3Fe0.7)O3-δ fuel electrode in different fuel gases for solid oxide electrochemical cells

Sr(Ti_1-xFe_x)O_3?δ (STF) perovskite has been developed as one of the alternatives to Nickel-base fuel electrodes for solid oxide electrochemical cells (SOCs) that can provide good tolerance to redox cycling and fuel impurities. Recent results on STF fuel electrodes present excellent electrochemical performance and outstand stability both under H₂ fuel cell mode and H₂O electrolysis mode, however, the electrochemical characteristics in other fuel gases, such as CO, CO–H₂ mixture, CH₄, and CO–CO₂ mixture have not been investigated. Herein, we report the electrochemical performance of Sr(Ti_0.3Fe_0.7)O_3?δ fuel electrode on La_0.8Sr_0.2MnO_3?δ-Zr_0.92Y_0.16O_2?δ (LSM-YSZ) oxygen electrode supported SOCs with thin YSZ electrolyte using different fuel gases. At 800 °C, the peak power density slightly decreased from 0.9 W/cm² in wet H₂ to 0.68 W/cm² in wet CO under fuel cell mode. However, the cell only showed a peak power density of 0.27 W/cm² at 800 °C in wet CH₄, reaching 0.75 W/cm² at 850 °C, when the open-circuit voltage increased from 0.9 V to 1.02 V. STF fuel electrode exhibited much worse CO₂ electrolysis performance than steam electrolysis, especially in high CO₂ concentration due to the increased ohmic resistance and electrode polarization resistance.     

Comparative study of CO and CO2 hydrogenation over supported Rh–Fe catalysts

The hydrogenation of CO, CO + CO₂, and CO₂ over titania-supported Rh, Rh–Fe, and Fe catalysts was carried out in a fixed-bed micro-reactor system nominally operating at 543 K, 20 atm, 20 cm³ min^− 1 gas flow (corresponding to a weight hourly space velocity (WHSV) of 8000 cm³ g_cat^− 1 h^− 1), with a H₂:(CO + CO₂) ratio of 1:1. A comparative study of CO and CO₂ hydrogenation shows that while Rh and Rh–Fe/TiO₂ catalysts exhibited appreciable selectivity to ethanol during CO hydrogenation, they functioned primarily as methanation catalysts during CO₂ hydrogenation. The Fe/TiO₂ sample was primarily a reverse water gas shift catalyst. Higher reaction temperatures favored methane formation over alcohol synthesis and reverse water gas shift. The effect of pressure was not significant over the range of 10 to 20 atm.     

Batch foaming of SAN/clay nanocomposites with scCO2: A very tunable way of controlling the cellular morphology

This paper aims at elucidating some important parameters affecting the cellular morphology of poly(styrene-co-acrylonitrile) (SAN)/clay nanocomposite foams prepared with the supercritical CO₂ technology. Prior to foaming experiments, the SAN/CO₂ system has first been studied. The effect of nanoclay on CO₂ sorption/desorption rate into/from SAN is assessed with a gravimetric method. Ideal saturation conditions are then deduced in view of the foaming process. Nanocomposites foaming has first been performed with the one-step foaming process, also called depressurization foaming. Foams with different cellular morphology have been obtained depending on nanoclay dispersion level and foaming conditions. While foaming at low temperature (40 °C) leads to foams with the highest cell density (∼10¹²-10¹⁴ cells/cm³), the foam expansion is restricted (d∼0.7-0.8 g/cm³). This drawback has been overcome with the use of the two-step foaming process, also called solid-state foaming, where foam expansion occurs during sample dipping in a hot oil bath (d∼0.1-0.5 g/cm³). Different foaming parameters have been varied, and some schemes have been drawn to summarize the characteristics of the foams prepared - cell size, cell density, foam density - depending on both the foaming conditions and nanoclay addition. This result thus illustrates the huge flexibility of the supercritical CO₂ batch foaming process for tuning the foam cellular morphology.     

Investigation on electrochemical reduction process of Nb2O5 powder in molten CaCl2 with metallic cavity electrode

The direct electrochemical reduction process of Nb₂O₅ powder was investigated by cyclic voltammetry and constant potential electrolysis with a novel metallic cavity electrode in molten calcium chloride at 850 °C. The products of both constant potential and constant voltage electrolysis were characterized by XRD, SEM and EDX. CaNb₂O₆ was formed upon addition of solid Nb₂O₅ into molten CaCl₂ when CaO was present. During the electrolysis solid Nb₂O₅ was reduced to various niobium oxides of lower oxidation states, including some composite oxides, and then was converted completely to metallic niobium near −0.35 V (vs. Ag/AgCl), which was more positive than the reduction potential of Ca²⁺. Constant potential electrolysis was applied at the potentials near the reduction current peaks derived from the cyclic voltammetry curves, and cell voltages were monitored. The voltage was near 2.4 V when the oxide was metallized at −0.35 V (vs. Ag/AgCl). Nb₂O₅ pellet could be used to prepared metallic niobium at cell voltage 2.4 V in a larger electrolysis bath filled with calcium chloride at 850 °C. The experiment results further demonstrated the direct electrochemical reduction mechanism of Nb₂O₅ powder in a molten system.