High temperature H2/CO2 separation using cobalt oxide silica membranes

In this work high quality cobalt oxide silica membranes were synthesized on alumina supports using a sol–gel, dip coating method. The membranes were subsequently connected into a steel module using a graphite based proprietary sealing method. The sealed membranes were tested for single gas permeance of He, H₂, N₂ and CO₂ at temperatures up to 600 °C and feed pressures up to 600 kPa. Pressure tests confirmed that the sealing system was effective as no gas leaks were observed during testing. A H₂ permeance of 1.9 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ was measured in conjunction with a H₂/CO₂ permselectivity of more than 1500, suggesting that the membranes had a very narrow pore size distribution and an average pore diameter of approximately 3 Å. The high temperature testing demonstrated that the incorporation of cobalt oxide into the silica matrix produced a structure with a higher thermal stability, able to resist thermally induced densification up to at least 600 °C. Furthermore, the membranes were tested for H₂/CO₂ binary feed mixtures between 400 and 600 °C. At these conditions, the reverse of the water gas shift reaction occurred, inadvertently generating CO and water which increased as a function of CO₂ feed concentration. The purity of H₂ in the permeate stream significantly decreased for CO₂ feed concentrations in excess of 50 vol%. However, the gas mixtures (H₂, CO₂, CO and water) had a more profound effect on the H₂ permeate flow rates which significantly decreased, almost exponentially as the CO₂ feed concentration increased.     

BaCe0.85Tb0.05Co0.1O3−δ perovskite hollow fibre membranes for hydrogen/oxygen permeation

Co-doped BaCe_0.85Tb_0.05Co_0.1O_3−δ (BCTCo) nanopowder was synthesized via a sol–gel method using ethylenediaminetetraacetic acid (EDTA) and citric acid as the chelating agents. Using the resultant powder, BCTCo perovskite hollow fibre membranes were then fabricated by the combined phase inversion and sintering technique. Properties of the BCTCo powder and the hollow fibre membranes in terms of crystalline phase, morphology, electrical conductivity, porosity, mechanical strength and hydrogen/oxygen permeation were investigated by a variety of characterization methods. The results indicated that doping of cobalt in the BCTb oxide led to a higher electrical conductivity and lower calcination temperature for the powder precursor to a perovskite structure as well as sintering temperature for the hollow fibre precursors to gastight membranes. In order to obtain gastight and robust hollow fibre membranes, the sintering temperature should be controlled between 1300 and 1450 °C. The maximum hydrogen flux through the BCTCo hollow fibre membranes reached up to 0.385 mL cm⁻² min⁻¹ at 1000 °C under 50% H₂–He/N₂ gradient, which is higher than that of the un-doped BCTb hollow fibre membranes with the same effective thickness, and especially much higher than that obtained from other proton conductors due to the asymmetric structure of the membrane designed. Moreover, the BCTCo hollow fibre membrane also exhibited noticeable oxygen permeation fluxes, i.e. 0.122 mL cm⁻² min⁻¹ at 1000 °C under the air/He gradient. However, doping of cobalt might damage the mechanical stability of the perovskite membranes in the hydrogen-containing atmosphere.     

Preparation of a novel bimodal catalytic membrane reactor and its application to ammonia decomposition for COx-free hydrogen production

A novel bimodal catalytic membrane reactor (BCMR) consisting of a Ru/γ-Al₂O₃/α-Al₂O₃ bimodal catalytic support and a silica separation layer was proposed. The catalytic activity of the support was successfully improved due to enhanced Ru dispersion by the increased specific surface area for the γ-Al₂O₃/α-Al₂O₃ bimodal structure. The silica separation layer was prepared via a sol–gel process, showing a H₂ permeance of 2.6 × 10⁻⁷ mol Pa⁻¹ m⁻² s⁻¹, with H₂/NH₃ and H₂/N₂ permeance ratios of 120 and 180 at 500 °C. The BCMR was applied to NH₃ decomposition for CO_x-free hydrogen production. When the reaction was carried out with a NH₃ feed flow rate of 40 ml min⁻¹ at 450 °C and the reaction pressure was increased from 0.1 to 0.3 MPa, NH₃ conversion decreased from 50.8 to 35.5% without H₂ extraction mainly due to the increased H₂ inhibition effect. With H₂ extraction, however, NH₃ conversion increased from 68.8 to 74.4% due to the enhanced driving force for H₂ permeation through the membrane.     

Equilibrium shift of methylcyclohexane dehydrogenation in a thermally stable organosilica membrane reactor for high-purity hydrogen production

A high-performance organosilica membrane was prepared via sol–gel processing for use in methylcyclohexane (MCH) dehydrogenation to produce high-purity hydrogen. The membrane showed a high H₂ permeance of 1.29 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹, with extremely high H₂/C₃H₈ and H₂/SF₆ selectivities of 6680 and 48,900, respectively, at 200 °C. The extraction of hydrogen from the membrane reactor led to the MCH conversion higher than the thermodynamic equilibrium, with almost pure hydrogen obtained in the permeate stream without considering the effect of carrier gas and sweep gas in the membrane reactor, and the organosilica membrane reactor was very stable under the reaction conditions employed.     

Ceria-based electrolyte reinforced by sol–gel technique for intermediate-temperature solid oxide fuel cells

High performance solid oxide fuel cells (SOFCs) based on gadolinia-doped ceria (GDC) electrolyte are demonstrated for intermediate temperature operation. The inherent technical limitations of the GDC electrolyte in sinterability and mechanical properties are overcome by applying sol–gel coating technique to the screen-printed film. When the quality of the electrolyte film is enhanced by the additional sol–gel coating, the OCV and maximum power density increase from 0.73 to 0.90 V and from 0.55 to 0.95 W cm⁻², respectively, at 650 °C with humidified hydrogen (3% H₂O) as fuel and air as oxidant. The impedance analysis reveals that the reinforcement of the thin electrolyte with sol–gel coating significantly reduces the polarization resistance. Elementary reaction steps for the anode and cathode are analyzed based on the systematic impedance study, and the relation between the structural integrity of the electrolyte and the electrode polarization is discussed in detail.     

Preparation of PPO-silica mixed matrix membranes by in-situ sol–gel method for H2/CO2 separation

Poly(2,6-dimethyl-1,4-phenylene oxide)(PPO)-silica mixed matrix membranes (MMMs) were synthesized through the in-situ sol–gel method. The effects of the acid–base catalysis conditions and silica loading weight on the gas separation performance of the membranes were investigated. The functional groups, crystalline structure, thermal stability, and morphology of the MMMs were examined using Fourier transform-infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and thermogravimetric analysis (TGA), respectively. The results indicate that using the in-situ sol–gel method to synthesize PPO-silica MMMs is beneficial for improving the adhesion between the silica and polymer and for the dispersion of the silica. The additives significantly enhanced the thermal stability of the membranes. Compared with pure PPO membranes, the PPO-silica MMMs prepared with 10 wt.% acid-silica loading exhibited the best H₂/CO₂ separation properties: H₂ permeability was enhanced from 82.1 to 548.7 Barrer, and an H₂/CO₂ separation ratio of approximately 3.56 was observed.     

Proton conductivity and fuel cell performance of organic–inorganic hybrid membrane based on poly(methyl methacrylate)/silica

Organic–inorganic hybrid membranes based on poly(methyl methacrylate) (PMMA)/silica have been synthesized using a sol-gel technique for use in polymer electrolyte fuel cells (PEFCs). The properties of these membranes were characterized using X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The results indicate that these membranes are formed through hydrogen bonds between the carbonyl group of PMMA and the uncondensed alcohol functional groups of the inorganic clusters. The proton conductivity of these membranes is on the order of 10⁻¹ S cm⁻¹, and the 60PMMA–30SiO₂–10P₂O₅ membrane displays the highest proton conductivity of 3.85 × 10⁻¹ S cm⁻¹ at 90 °C and 50% RH. The performance of a fuel cell using these membranes was tested. A maximum power density of 370 mW cm⁻² is obtained at 80 °C, and the current density at 0.4 V remains almost unchanged during the 100-h test time under the test conditions. This class of hybrid membranes is an extremely promising material for use in PEFCs.     

BaZr0.2Ce0.8−xYxO3−δ solid oxide fuel cell electrolyte synthesized by sol–gel combined with composition-exchange method

This study reports the synthesis of proton-conducting BaZr_0.2Ce_0.8−xY_xO_3−δ (x = 0–0.4) oxides by using a combination of citrate-EDTA complexing sol–gel process and composition-exchange method. Compared to those oxides prepared from conventional sol–gel powders, the sintered BaZr_0.2Ce_0.8−xY_xO_3−δ pellets synthesized by sol–gel combined with composition-exchange method are found to exhibit improved sinterability, a higher relative density, higher conduction, and excellent thermodynamic stability against CO₂. Moreover, the Pt/electrolyte/Pt single cell using such a BaZr_0.2Ce_0.6Y_0.2O_3−δ electrolyte shows an obviously higher maximum powder density in the hydrogen-air fuel cell experiments. Based on the experimental results, we discuss the improvement mechanism in terms of calcined particle characteristics. This work demonstrates that the BaZr_0.2Ce_0.8−xY_xO_3−δ oxides synthesized by sol–gel combined with composition-exchange method would be a promising electrolyte for the use in H⁺-SOFC applications. More importantly, this new fabrication approach could be applied to other similar ABO₃-perovskite material systems.     

ZrO2–SiO2/Nafion composite membrane for polymer electrolyte membrane fuel cells operation at high temperature and low humidity

Recast Nafion^® composite membranes containing ZrO₂–SiO₂ binary oxides with different Zr/Si ratios are investigated for polymer electrolyte membrane fuel cells (PEMFCs) at temperatures above 100 °C. Fine particles of the ZrO₂–SiO₂ binary oxides, same as an inorganic filter, are synthesized from a sodium silicate and a carbonate complex of zirconium by a sol–gel technique. The composite membranes are prepared by blending a 10% (w/w) Nafion^®-water dispersion with the inorganic compound. All composite membranes show higher water uptake than unmodified membranes, and the proton conductivity increases with increasing zirconia content at 80 °C. By contrast, the proton conductivity decreases with zirconia content for the composite membranes containing binary oxides at 120 °C. The composite membranes are tested in a 9-cm² commercial single cell at both 80 °C and 120 °C in humidified H₂/air under different relative humidity (RH) conditions. Composite membrane containing the ZrO₂–SiO₂ binary oxide (Zr/Si = 0.5) give the best performance of 610 mW cm⁻¹ under conditions of 0.6 V, 120 °C, 50% RH and 2 atm.     

Electrochemical synthesis of ammonia from N2 and H2O based on (Li,Na,K)2CO3–Ce0.8Gd0.18Ca0.02O2−δ composite electrolyte and CoFe2O4 cathode

Electrochemical synthesis of ammonia from water vapour and nitrogen was investigated using an electrolytic cell based on CoFe₂O₄–Ce0_.8Gd_0.18Ca_0.02O_2−δ (CFO-CGDC), CGDC-ternary carbonate composite and Sm_0.5Sr_0.5CoO_3−δ–Ce_0.8Gd_0.18Ca_0.02O_2−δ (SSCo-CGDC) as cathode, electrolyte and anode respectively. CoFe₂O₄, CGDC and SCCo were prepared via a combined EDTA-citrate complexing sol–gel and characterised by X-ray diffraction (XRD). The AC ionic conductivities of the CGDC-carbonate composite were investigated under three different atmospheres (air, dry O₂ and wet 5% H₂–Ar). A tri-layer electrolytic cell was fabricated by a cost-effective one-step dry-pressing and co-firing process. Ammonia was successfully synthesised from water vapour and nitrogen under atmospheric pressure and the maximum rate of ammonia production was found to be 6.5 × 10⁻¹¹ mol s⁻¹ cm⁻² at 400 °C and 1.6 V which is two orders of magnitude higher than that of previous report when ammonia was synthesised from N₂ and H₂O at 650 °C.     

Application of phosphoric acid and phytic acid-doped bacterial cellulose as novel proton-conducting membranes to PEMFC

Novel proton-conducting polymer electrolyte membranes have been prepared from bacterial cellulose by incorporation of phosphoric acid (H₃PO₄/BC) and phytic acid (PA/BC). H₃PO₄ and PA were doped by immersing the BC membranes directly in the aqueous solution of H₃PO₄ and PA, respectively. Characterizations by FTIR, TG, TS and AC conductivity measurements were carried out on the membrane electrolytes consisting of different H₃PO₄ or PA doping level. The ionic conductivity showed a sensitive variation with the concentration of the acid in the doping solution through the changes in the contents of acid and water in the membranes. Maximum conductivities up to 0.08 S cm⁻¹ at 20 °C and 0.11 S cm⁻¹ at 80 °C were obtained for BC membranes doped from H₃PO₄ concentration of 6.0 mol L⁻¹ and, 0.05 S cm⁻¹ at 20 °C and 0.09 S cm ⁻¹ at 60 °C were obtained for BC membranes doped from PA concentration of 1.6 mol L⁻¹. These types of proton-conducting membranes share not only the good mechanical properties but also the thermal stability. The temperature dependences of the conductivity follows the Arrhenius relationship at a temperature range from 20 to 80 °C and, the apparent activation energies (E_a) for proton conduction were found to be 4.02 kJ mol⁻¹ for H₃PO₄/BC membrane and 11.29 kJ mol⁻¹ for PA/BC membrane, respectively. In particular, the membrane electrode assembly fabricated with H₃PO₄/BC and PA/BC membranes reached the initial power densities of 17.9 mW cm⁻² and 23.0 mW cm⁻², which are much higher than those reported in literature in a real H₂/O₂ fuel cell at 25 °C.     

Synthesis and characterization of non-noble nanocatalysts for hydrogen production in microreactors

Nanoscale Co and Ni catalysts in silica were synthesized using sol–gel method for hydrogen production from steam reforming of methanol (SRM) in silicon microreactors with 50 μm channels. Silica sol–gel support with porous structure gives specific surface area of 452.35 m² g⁻¹ for Ni/SiO₂ and 337.72 m² g⁻¹ for Co/SiO₂. TEM images show the particles size of Ni and Co catalysts to be <10 nm. The EDX results indicate Co and Ni loadings of 5–6 wt.% in silica which is lower than the intended loading of 12 wt.%. The DTA and XRD data suggest that 450 °C is an optimum temperature for catalyst calcination when most of the metal hydroxides are converted to metal oxides without significant particle aggregation to form larger crystallites. SRM reactions show 53% methanol conversion with 74% hydrogen selectivity at 5 μL min⁻¹ and 200 °C for Ni/SiO₂ catalyst, which is higher than that for Co/SiO₂. The activity of the metal catalysts decrease significantly after SRM reactions over 10 h, and it is consistent with the magnetization (VSM) results indicating that ∼90% of Co and ∼85% of Ni become non-ferromagnetic after 10 h.     

Effect of treatment temperature on the performance of RuO2 anode electrocatalyst for high temperature proton exchange membrane water electrolysers

Ruthenium oxide catalysts were prepared by a sol–gel technique and calcined at different temperatures e.g., 400 °C, 500 °C and 600 °C. The catalysts performance for the oxygen evolution reaction was studied using cyclic voltammetry and their performance in a high temperature proton exchange membrane water electrolyser (PEMWE) examined. Physio-chemical characterization was carried out to study the thermal stability, oxygen-metal bond formation, crystallinity phase and crystallite size, particle size and elemental analysis by TGA, FTIR, XRD, TEM and EDX respectively. The electrolyte used for electrochemical characterisation was 1.0 M H₃PO₄ and 0.5 M H₂SO₄. Additionally, the effect of calcination and electrolyte temperature on oxygen evolution reaction of RuO₂ catalysts was studied and the apparent activation energy was determined using chronoamperometry. The prepared RuO₂ were tested as anode catalyst in PEMWE in the temperature range of 120–150 °C using phosphoric acid doped polybenzimidazole membrane electrolyte. The physio-chemical and electrochemical characterization results indicate that RuO₂ calcined at 500 °C gave the best performance with a current density of 0.875 A cm⁻² at 1.8 V in a PEMWE operated at 150 °C.     

Synthesis of nano-crystalline Sr2MgMoO6−δ anode material by a sol–gel thermolysis method

Nano-crystalline Sr₂MgMoO_6−δ (SMMO) powders were synthesized successfully by a novel sol–gel thermolysis method using a unique combination of polyvinyl alcohol (PVA) and urea. The decomposition behavior of gel precursor was studied by thermogravimetric-differential thermal analysis (TG/DTA) and the results showed that the double-perovskite phase of SMMO began to form at 1000 °C. The microstructure of the samples had been investigated by X-ray diffraction (XRD), transmission electron microscope (TEM), selected area electron diffraction (SAED), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). XRD patterns confirmed that well-crystalline double-perovskite SMMO powders were obtained by calcining at 1450 °C for 12 h. TEM morphological analysis showed that SMMO powders had a mean particle size around 50–100 nm. The SAED pattern and Raman spectroscopy showed that the SMMO powders were nano-polycrystalline well-developed A(B′_0.5B″_0.5)O₃ type perovskite material. The XPS results demonstrated that the Mo ions in SMMO had been reduced after exposure to H₂. The electric property was studied by four-probe method. The results showed that conductivity was 8.64 S cm⁻¹ in 5.0% H₂/Ar at 800 °C and the activation energies at low temperatures (400–640 °C) and high temperatures (640–800 °C) are about 21.43 and 6.59 kJ mol⁻¹, respectively.     

Y2O3-promoted NiO/SBA-15 catalysts highly active for CO2/CH4 reforming

A series of Y₂O₃-promoted NiO/SBA-15 (9 wt% Ni) catalysts (Ni:Y weight ratio = 9:0, 3:1, 3:2, 1:1) were prepared using a sol–gel method. The fresh as well as the catalysts used in CO₂ reforming of methane were characterized using N₂-physisorption, XRD, FT-IR, XPS, UV, HRTEM, H₂-TPR, O₂-TPD and TG techniques. The results indicate that upon Y₂O₃ promotion, the Ni nanoparticles are highly dispersed on the mesoporous walls of SBA-15 via strong interaction between metal ions and the HO–Si-groups of SBA-15. The catalytic performance of the catalysts were evaluated at 700 °C during CH₄/CO₂ reforming at a gas hourly space velocity of 24 L g_cat⁻¹ h⁻¹(at 25 ^°C and 1 atm) and CH₄/CO₂molar ratio of 1. The presence of Y₂O₃ in NiO/SBA-15 results in enhancement of initial catalytic activity. It was observed that the 9 wt% Y–NiO/SBA-15 catalyst performs the best, exhibiting excellent catalytic activity, superior stability and low carbon deposition in a time on stream of 50 h.     

Improvement of hydrogen-separating performance by on-stream catalytic cracking of silane over hollow fiber MFI zeolite membrane

MFI zeolite membranes were synthesized on porous α-alumina hollow fibers by in-situ hydrothermal synthesis. The membranes were further modified for H₂ separation by on-stream catalytic cracking deposition of methyldiethoxysilane (MDES) in the zeolitic pores. The separation performance of the modified membranes was characterized by separation of H₂/CO₂ gas mixture at 500 °C. Activation of MFI zeolite membranes by air at 500 °C was found to promote catalytic cracking deposition of silane in the zeolitic pores effectively, which resulted in significant improvement of H₂-separating performance. The H₂/CO₂ separation factor of 45.6 with H₂ permeance of 1.0 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹ was obtained at 500 °C for a modified hollow fiber MFI zeolite membrane. The as-made membranes showed good thermochemical stability for the separation of H₂/CO₂ gas mixture containing H₂O and H₂S, respectively.     

Cerium and zinc: Dual-doped LiMn2O4 spinels as cathode material for use in lithium rechargeable batteries

Pristine spinel lithium manganese oxide (LiMn₂O₄) and zinc- and cerium-doped lithium manganese oxide [LiZn_xCe_yMn_2−x−yO₄ (x = 0.01–0.10; y = 0.10–0.01)] are synthesized for the first time via the sol–gel route using p-amino benzoic acid as a chelating agent to obtain micron-sized particles and enhanced electrochemical performance. The sol–gel route offers shorter heating time, better homogeneity and control over stoichiometry. The resulting spinel product is characterized through various methods such as thermogravimetic and differential thermal analysis (TG/DTA), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrochemical galvanostatic cycling studies. Charge–discharge studies of LiMn₂O₄ samples heated at 850 °C exhibit a discharge capacity of 122 mAh g⁻¹ and a corresponding 99% coulombic efficiency in the 1st cycle. The discharge capacity and cycling performance of LiZn_0.01Ce_0.01Mn_1.98O₄ is found to be superior (124 mAh g⁻¹), with a low capacity fade (0.1 mAh g⁻¹ cycle⁻¹) over the investigated 10 cycles.     

Composite membranes based on a sulfonated poly(arylene ether sulfone) and proton-conducting hybrid silica particles for high temperature PEMFCs

The organic-inorganic composite membranes are prepared by inserting poly(styrene sulfonate)-grafted silica particles into a polymer matrix of sulfonated poly(arylene ether sulfone) copolymer. The first step consisted in using atom transfer radical polymerization method to prepare surface-modified silica particles grafted with sodium 4-styrenesulfonate, referred to as PSS-g-SiO₂. Ion exchange capacities up to 2.4 meq/g are obtained for these modified silica particles. In a second step, a sulfonated poly(arylene ether sulfone) copolymer is synthesized via nucleophilic step polymerization of sulfonated 4,4′-dichlorodiphenyl sulfone, 4,4′-dichlorodiphenyl sulfone and phenolphthalin monomers in the presence of potassium carbonate. The copolymer is blended with various amounts of silica particles to form organic-inorganic composite membranes. Esterification reaction is carried out between silica particles and the sulfonated polymer chains by thermal treatment in the presence of sodium hypophosphite, which catalyzed the esterification reaction. The water uptake, proton conductivity, and thermal decomposition temperature of the membranes are measured. All composite membranes show better water uptake and proton conductivity than the unmodified membrane. Moreover, the membranes are tested in a commercial single cell at 80 °C and 120 °C in humidified H₂/air under different relative humidity conditions. The composite membrane containing 10%(w/w) of PSS-g-SiO₂ particles, which have ester bonds between polymer chains and silica particles, showed the best performance of 690 mA cm⁻² at 0.6 V, 120 °C and 30 %RH, even higher than the commercial Nafion^® 112 membrane.     

Photocatalytic hydrogen generation by splitting of water from electrospun hybrid nanostructures

MWCNT-TiO₂ hybrid nanostructures are prepared using sol–gel and electrospinning followed by post annealing of as-spun nanofibers at 450 °C per 1 h in air. These hybrid nanostructures composed of MWCNTs varied from 0 to 20% (w/w) and are characterized by SEM, TEM, XRD, and FT-IR analysis. MWCNT-TiO₂ hybrid structures are utilized in commercially available Methylene blue (MB) dye degradation and found that 2% of MWCNT exhibit superior kinetic constant 6.379 × 10⁻³ min⁻¹ extracted. In addition, we demonstrate that the doping of MWCTs within TiO₂ leads to a significant enhancement of the UV–vis light assisted photocatalytic activity is optimized in comparison with higher (5, 10 and 20%) compositions. UV–vis assisted photocatalytic hydrogen is evolved by photoelectrolytic splitting of water by using MWCNT-TiO₂ hybrid nanostructures as electrode.