High performance nitrile copolymers for polymer electrolyte membrane fuel cells

This paper reports the fuel cells (DMFC and PEMFC) performance using sulfonated poly(arylene ether ether nitrile) (SPAEEN) copolymers containing sulfonic acid group arranged in structurally different ways. The membrane electrode assembly (MEA) fabricated from SPAEEN containing 60 mol% of angled naphthalenesulfonic acid group (m-SPAEEN-60) had superior performance over those derived from pendent naphthalenesulfonic acid group (p-SPAEEN) or sulfonated hydroquinone (HQ-SPAEEN) in H₂/air and/or DMFC conditions. For example, the current density of the MEA using m-SPAEEN-60 at 0.5 V and 2.0 M methanol was 250 mA/cm², whereas the current densities of the MEAs using p-SPAEEN-50 and HQ-SPAEEN-56 were 185 and 190 mA/cm², respectively. In addition, compared with the sulfonated polysulfone (BPSH-35) and Nafion membranes, the copolymer containing nitrile group showed the improved cell performance. For example, the power density of the MEA using m-SPAEEN-60 at 250 mA/cm² and 2.0 M methanol was 125 mW/cm², whereas the power densities of the MEAs using sulfonated polysulfone (BPSH-35) and Nafion were 115 and 113 mW/cm², respectively. m-SPAEEN-60 showed stable cell performance during extended operation (>100 h).     

Perovskite membrane reactor for continuous and isothermal redox hydrogen production from the dissociation of water

The redox water splitting is one of the most promising routes for sustainable hydrogen production. Towards this goal, serious technological obstacles are set: (i) by the non-isothermal operation of the redox process, that causes serious reactor construction problems, and (ii) by the need for efficient high temperature oxygen/hydrogen separation technology which is a very challenging development. In this paper, perovskite materials having the formula La_0.3Sr_0.7FeO₃ were synthesized and subsequently tested for their high temperature oxidation/reduction behavior. The redox activity of the materials in relation to the water splitting reaction has been also investigated. Dense, disc shaped membranes of the materials were synthesized and placed in a membrane reactor. Experiments at 1133 K revealed the possibility of performing the reduction and oxidation steps simultaneously and isothermally on each side of the membrane reactor. A steady-state situation was thereby achieved where hydrogen was continuously produced on one side while the material was simultaneously regenerated on the other side. The created oxygen vacancy gradient formed the driving force for a continuous flux of vacancies from the membrane reduction surface to the membrane oxidation surface. The hydrogen production rate under the particular experimental conditions estimated to be ∼47.5 cm³ H₂ (STP) m⁻² min⁻¹. It could be increased by a factor of approximately 3, up to ∼145 cm³ H₂ (STP) m⁻² min⁻¹, if the membrane reduction was enhanced with a reductant such as carbon monoxide. This approach resulted in an efficient execution of the water gas shift reaction towards high purity hydrogen production.     

Facile fabrication of a novel high performance CO2 separation membrane: Immobilization of poly(amidoamine) dendrimers in poly(ethylene glycol) networks

Poly(amidoamine) (PAMAM) dendrimers showed high CO₂ separation properties and were successfully immobilized in a poly(ethylene glycol) (PEG) network upon photopolymerization of PEG dimethacrylate. The PAMAM dendrimer incorporation ratio was readily controlled, and a stable self-standing membrane containing up to 75 wt.% PAMAM dendrimer was obtained. The CO₂ separation properties over smaller H₂ were investigated by changing the PAMAM dendrimer content or generation and CO₂ partial pressure (ΔPCO₂$\mathrm{\Delta }{P}_{\text{C}{\text{O}}_2}$) under atmospheric conditions. Especially, a polymeric membrane containing 50 wt.% PAMAM dendrimer (0th generation) exhibited an excellent CO₂/H₂ selectivity of 500 with CO₂ permeability of 2.74 × 10⁻¹⁴ m³(STP)m/(m² s Pa) or 3.65 × 10³ barrer (1 barrer = 7.5 × 10⁻¹⁸ m³(STP)m/(m² s Pa)) when a mixture gas (CO₂/H₂: 5/95 by vol.) was fed at 25 °C and 100 kPa with 80% relative humidity. This polymeric materials are promising for a novel CO₂ separation membrane.     

Thin Pd–23%Ag/stainless steel composite membranes: Long-term stability,life-time estimation and post-process characterisation

The long-term stability of Pd–23%Ag/stainless steel composite membranes has been examined in H₂/N₂ mixtures as a function of both temperature and feed pressure. During continuous operation, the membrane shows a good stability at 400 °C while the N₂ leakage increases very slowly at a temperature of 450 °C (P_feed = 10 bar). After 100 days of operation (P_feed = 5–20 bar, T = 350–450 °C), the N₂ permeance equals 7.0 × 10⁻⁹ mol m⁻² s⁻¹ Pa⁻¹, which indicates that the H₂/N₂ permselectivity still lies around 500, based on a H₂ permeance equal to 3.0 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹. Despite the generation of small pinholes, a membrane life-time of several (2–3) years (T ≤ 425 °C) is estimated for the experimental conditions employed based on long-term stability tests over 100 days. Post-process characterisation shows a considerable grain growth and micro-strain relaxation in the Pd–23%Ag membrane after the prolonged permeation experiment. Changes in surface area are relatively small. In addition, segregation of Ag to the membrane surfaces is observed. The formation of pinholes is identified as the main source for the increased N₂ leakage during testing at higher temperature.     

Hydrogen purification using a SAPO-34 membrane

A SAPO-34 membrane separated CO₂/H₂ and H₂/CH₄ mixtures at feed pressures up to 1.7 MPa. Strong CO₂ adsorption inhibited H₂ adsorption and decreased H₂ permeances significantly, especially at low temperatures, so that CO₂ preferentially permeated and CO₂/H₂ selectivities were higher at low temperatures. At 253 K, CO₂/H₂ separation selectivities were greater than 100 with CO₂ permeances of 3 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹. The CO₂/H₂ separation exceeded the upper bounds (selectivity–permeability plot) for polymer membranes. The SAPO-34 membrane separated H₂ from CH₄ because CH₄ is close to the SAPO-34 pore size and has a lower diffusivity than H₂. The H₂/CH₄ separation selectivity had a small maximum with temperature, and decreased slightly with feed pressure and CH₄ feed concentration.     

Calorimetric determination of enthalpy changes for the proton ionization of glycine, N,N-bis(2-hyroxyethyl)glycine (“bicine”) and N-tris(hydroxymethyl)methylglycine (“tricine”) in water-methanol mixtures

Enthalpies for the two proton ionizations of glycine, N,N-bis(2-hyroxyethyl)glycine (“bicine”) and N-tris(hydroxymethyl)methylglycine (“tricine”) were obtained in water-methanol mixtures with methanol mole fraction (X_m) from 0 to 0.360. With increasing methanol the ionization enthalpy for the first proton (ΔH₁) of glycine increased from 4.4 to 9.4 kJ mol⁻¹ with a minimum of 4.1 kJ mol⁻¹ at X_m = 0.059. The ionization enthalpy of the second proton (ΔH₂) for glycine decreased from 46.3 to 38.1 kJ mol⁻¹. ΔH₁ of bicine increased from 3.5 to 7.6 kJ mol⁻¹ at X_m = 0.273 before dropping to 4.1 kJ mol⁻¹ at X_m = 0.360. ΔH₂ of bicine increased from 24.9 to 29.4 kJ mol⁻¹. For tricine, ΔH₁ increased from 6.7 to 9.8 kJ mol⁻¹ at X_m = 0.194 then dropped to 7.4 kJ mol⁻¹ at X_m = 0.360. ΔH₂ for tricine first dropped from 30.8 to 28.5 kJ mol⁻¹ at X_m = 0.059 before increasing to 33.3 kJ mol⁻¹ at X_m = 0.273. The solvent composition was selected so as to include the region of maximum structure enhancement of water by methanol. The results were interpreted in terms of solvent-solvent and solvent-solute interactions.     

A study on methanol steam reforming to CO2 and H2 over the La2CuO4 nanofiber catalyst

The La₂CuO₄ crystal nanofibers were prepared by using single-walled carbon nanotubes as templates under mild hydrothermal conditions. The steam reforming of methanol (SRM) to CO₂ and H₂ over such nanofiber catalysts was studied. At the low temperature of 150 °C and steam/methanol=1.3, methanol was completely (100%, 13.8 g/h g catalyst) converted to hydrogen and CO₂ without the generation of CO. Within the 60 h catalyst lifespan test, methanol conversion was maintained at 98.6% (13.6 g/h g catalyst) and with 100% CO₂ selectivity. In the meantime, for distinguishing the advantage of nanoscale catalyst, the La₂CuO₄ bulk powder was prepared and tested for the SRM reaction for comparison. Compared with the La₂CuO₄ nanofiber, the bulk powder La₂CuO₄ showed worse catalytic activity for the SRM reaction. The 100% conversion of methanol was achieved at the temperature of 400 °C, with the products being H₂ and CO₂ together with CO. The catalytic activity in terms of methanol conversion dropped to 88.7% (12.2 g/h g catalyst) in 60 h. The reduction temperature for nanofiber La₂CuO₄ was much lower than that for the La₂CuO₄ bulk powder. The nanofibers were of higher specific surface area (105.0 m²/g), metal copper area and copper dispersion. The in situ FTIR and EPR experiments were employed to study the catalysts and catalytic process. In the nanofiber catalyst, there were oxygen vacancies. H₂-reduction resulted in the generation of trapped electrons [e] on the vacancy sites. Over the nanofiber catalyst, the intermediate H₂CO/HCO was stable and was reformed to CO₂ and H₂ by steam rather than being decomposed directly to CO and H₂. Over the bulk counterpart, apart from the direct decomposition of H₂CO/HCO to CO and H₂, the intermediate H₂COO might go through two decomposition ways: H₂COO=CO+H₂O and H₂COO=CO₂+H₂.     

Hydrogen gas mixture separation by CVD silica membrane

In this work we investigate the performance of high flux chemical vapour deposition (CVD) silica membranes for the separation of gas mixtures containing H₂ and CO₂ at various temperatures. The membranes were prepared by a counter diffusion CVD method where tetraethyl orthosilicate (TEOS) and O₂ were used as reactants. Single gas permeation resulted in activated transport for the smaller kinetic diameter gases (H₂ and He) whilst the larger kinetic diameter gases (CO₂ and N₂) showed negative activation energy. The single gas permeation of H₂ increased from 5.1 × 10⁻⁷ to 7.0 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ in the temperature range 100–400 °C, and H₂/CO₂ and H₂/N₂ selectivities reached 36 and 57 at 400 °C, respectively. The H₂ purity in the permeate stream also increased with temperature for H₂:CO₂ binary gas mixture, thus being beneficial for H₂ diffusion. H₂ competitively permeated through the membrane at a several range of gas mixtures, and a saturation level was achieved at H₂:CO₂ 60:40 feed concentration, where the diffusion of CO₂ molecules became negligible delivering ∼99% H₂ purity in the permeate stream. These results substantiate that the counter diffusion CVD method produced thin silica film membranes with a very precise pore size control, in particular suggesting a narrow pore distribution with average pore radius of about 3.1 Å.     

Thermodynamic properties of hydrated sodium l-threonate Na(C4H7O5)·H2O(s)

Low-temperature heat capacities of the compound Na(C₄H₇O₅)·H₂O(s) have been measured with an automated adiabatic calorimeter. A solid-solid phase transition and dehydration occur at 290-318 K and 367-373 K, respectively. The enthalpy and entropy of the solid-solid transition are Δ_transH_m = (5.75 ± 0.01) kJ mol⁻¹ and Δ_transS_m = (18.47 ± 0.02) J K⁻¹ mol⁻¹. The enthalpy and entropy of the dehydration are Δ_dH_m = (15.35 ± 0.03) kJ mol⁻¹ and Δ_dS_m = (41.35 ± 0.08) J K⁻¹ mol⁻¹. Experimental values of heat capacities for the solids (I and II) and the solid-liquid mixture (III) have been fitted to polynomial equations.     

Anomalous charge transport in CeB6

The comprehensive study of conductivity σ, Hall coefficient R_H and Seebeck coefficient S has been carried out on high-quality single crystals of CeB₆ in a wide range of temperatures 1.8-300 K. An anomalous behavior of all transport characteristics (σ, R_H, S) was found for the first time in the vicinity of T^*≈80 K. The strong decrease of conductivity σ as well as the unusual asymptotic behavior of Seebeck coefficient S(T)∼−ln T observed below T^* allowed us to conclude in favor of crossover between different regimes of charge transport in CeB₆. The pronounced change of Hall mobility μ_H, which diminishes from the maximum value of 20 cm²/(V s) at T^* to the values of ∼6 cm²/(V s) at T∼10 K, seems to be attributed to the strong enhancement of charge carriers scattering due to fast spin fluctuations on Ce-sites. The low-temperature anomalies of the charge transport characteristics are compared with the predictions of the Kondo-lattice model.     

Synthesis and coordination chemistry of fluorinated xanthate ligands

Alkali metal, copper, nickel and rhodium complexes of alkylated [S₂COC₈H₁₇] and fluoroalkylated xanthate ligands [S₂COC_mH_2mC_nF_2n+1] (m = 2, n = 4, 6; m = 3, n = 1, 8) have been prepared in high yields and characterised by elemental analysis, mass spectrometry, IR and NMR spectroscopies. The structures of [Cu(S₂COC₈H₁₇)(PPh₃)₂], [Cu(S₂COC₃H₆CF₃)(PPh₃)₂], [Ni(S₂COC₃H₆CF₃)₂], [Cp^*RhCl(S₂COC₈H₁₇)] and [Cp^*RhCl(S₂COC₃H₆CF₃)] have been determined by single crystal X-ray diffraction.     

Calorimetric determination of enthalpy changes for proton ionization of N-[2-hydroxyethyl]piperazine-N′-[2-ethane sulfonic acid] (HEPES) and N-[2-hydroxyethyl]piperazine-N′-[2-hydroxypropane sulfonic acid] (HEPPSO) in water-methanol mixtures

Enthalpies for the two proton ionizations of the biochemical buffers N-[2-hydroxyethyl]piperazine-N′-[2-ethane sulfonic acid] (HEPES) and N-[2-hydroxyethyl]piperazine-N′-[2-hydroxypropane sulfonic acid] (HEPPSO) were obtained in water-methanol mixtures with methanol mole fraction (X_m) from 0 to 0.360. With increasing methanol, the ionization enthalpy for the first proton (ΔH₁) of HEPES increased steadily from 8.4 to 15.3 kJ mol⁻¹ whereas that for HEPPSO rose to a maximum of 21.0 kJ mol⁻¹ at X_m = 0.123 before dropping to 18.4 kJ mol⁻¹ at X_m = 0.360. The ionization enthalpy for the second proton (ΔH₂) of HEPES varied from 20.8 kJ mol⁻¹ in water to 13.6 kJ mol⁻¹ at X_m = 0.360 with a maximum of 24.8 kJ mol⁻¹ at X_m = 0.194. For HEPPSO, ΔH₂ increased steadily from 23.4 to 29.2 kJ mol⁻¹. The solvent composition was selected so as to include the region of maximum structure enhancement of water by methanol. The results were interpreted in terms of solvent-solvent and solvent-solute interactions.     

Hydrogen permeability of 2.5 μm palladium–silver membranes deposited on ceramic supports

The permeability of hydrogen selective Pd-based membranes was tested in different experimental conditions. The membranes were obtained by depositing palladium–silver films onto ceramic porous supports, with film composition of about 20 wt% of silver and thicknesses of about 2.5 μm. Their permeance was measured at 400 °C at total trans-membrane pressures between 0.2 and 6 bar, using pure feeds of H₂ and N₂, as well as H₂/N₂ and H₂/CO mixtures; the temperature dependence of permeability was investigated using pure H₂ feeds at 300, 400 and 500 °C. The membranes exhibit a very attractive behavior, maintaining a virtually infinite selectivity throughout the testing, with permeance values among the highest values reported in literature for similar membranes. Permeation of pure hydrogen accurately follows Sieverts’ law and confirms the presence of a chemisorption–dissociation–diffusion mechanism, characterised by the transport of atomic hydrogen through the Pd–Ag layer as the limiting step. In the case of H₂/N₂ mixtures, the high membrane permeance originates also significant concentration polarization phenomena resulting in apparent deviations from Sieverts’ behavior; the presence of CO in the feed may reduce hydrogen permeability even by 75%, although this effect is shown to be fully reversible after a subsequent air treatment at 400 °C. The temperature dependence of the membrane permeability is of Arrhenius type, with an activation energy of about 17 kJ/mol, that is, close to what is reported for Pd–Ag membranes following Sieverts’ behavior.     

Heterogeneous zirconocene catalyst on magnesium support MgCl2(THF)2 modified by AlEt2Cl for ethylene polymerisation

The heterogeneous bis(cyclopentadienyl)zirconium(IV) dichloride catalyst of the composition MgCl₂(THF)/(AlEt₂Cl)_0.34/(Cp₂ZrCl₂)_0.01 as determined by FTIR, XRD, and AAS analyses was synthesised and, after activation by MAO, applied for ethylene polymerisation. The catalyst turned out to be stable and more active than those magnesium supported catalysts already known from the literature. The polyethylene produced has a relatively high molecular weight (M_w > 200,000 g/mol), a narrow and monomodal molecular weight distribution (MWD = 2.4), a bulk density of about 180 g/dm³, and monomodal particle size distribution. Application of a ternary Al(i-Bu)₃/MAO/B(C₆F₅)₃ activator decreased the amount of MAO needed and increased catalyst activity, but did not change the reaction mechanism.     

Solid-phase microextraction—Gas chromatography to determine volatile organic sulfur compounds in the air at sewage treatment plants

Solid-phase microextraction (SPME) was applied to the determination of 7 volatile organic sulfur compounds (VOSCs), which were analysed by gas chromatography-mass spectrometry. The compounds studied were ethyl mercaptan (CH₃CH₂SH), dimethyl sulfide ((CH₃)₂S), carbon disulfide (CS₂), propyl mercaptan (C₃H₈S), butyl mercaptan (C₄H₁₀S), dimethyl disulfide ((CH₃)₂S₂) and 1-pentanethiol (C₅H₁₂S). Temperature and time conditions of SPME extraction were optimised and the method was validated, with good linearity in a calibration range between 0.1 and 1000 μg m⁻³. Method detection limits ranged between 0.01 and 0.08 μg m⁻³ and method quantification limits were between 0.10 and 0.25 μg m⁻³, allowing real samples taken from several different areas of a sewage treatment plant to be analysed. Repeatability of the method between samples went from 5.6% for pentanethiol up to 14.2% for carbon disulfide, and concentrations of total target compounds were found between 18 and 529 μg m⁻³, depending on the sampling site.     

Shape selective oxidation by a microporous platinum-polyoxometalate

Shape selective catalytic behaviour of a platinum-promoted polyoxometalate, 0.5 wt% Pt−Cs_2.1H_{0 9}PW₁₂O₄₀, has been studied for complete oxidation of methane and benzene. The pore size of this catalyst determined by adsorptions of n-butane and isobutane was close to the molecular size of n-butane (0.43 nm). Ar and N₂ porosimetries demonstrated that 0.5 wt% Pt−Cs_{2 1}H_{0 9}PW₁₂O₄₀ possesses unimodal distribution of pores in ultramicropore region. External surface area was estimated to be less than 3% that of the total surface area (61 m² g⁻¹) of the catalyst. Owing to the restricted pores, this exhibited efficient shape selectivity; methane (molecular size; 0.38 nm) was readily oxidized, while the oxidations of the larger molecule such as benzene (0.59 nm) were greatly suppressed. These results indicate that 0.5 wt% Pt−Cs_{2 1}H_{0 9}PW₁₂O₄₀ is a promising microporous catalyst.     

Effect of ring substituents on crystal packing and H-bonding in a series of halobis(phen)copper(II) arylphosphonic acid complexes

The synthesis and crystal structures of five new analogues of the supramolecular copper(II) organophosphonate [Cu^II(phen)₂Cl][(C₆H₅PO(OH)₂)((OH)O₂PC₆H₅)] (1) are presented. The structures contain substituted phenylphosphonic acids, and are of the general formula [Cu^II(phen)₂Cl][(XPO(OH)₂)((OH)O₂PX)] · Z, where X = o-CH₃(C₆H₅) (2); X = p-CH₃(C₆H₅), Z = H₂O · 2CH₃CH₂OH (4); X = o-NO₂(C₆H₅), m-NO₂(C₆H₅) (5); X = m-NO₂(C₆H₅) (6); X = C₁₀H₇ (7).     

Ni-based amorphous alloy membranes for hydrogen separation at 400 °C

Amorphous alloy membranes composed primarily of Ni and early transition metals (ETMs) are an inexpensive alternative to Pd-based alloy membranes, and these materials are therefore of particular interest for the large-scale production of hydrogen from carbon-based fuels. Catalytic membrane reactors can produce hydrogen directly from coal-derived synthesis gas at 400 °C, by combining a commercial water–gas-shift (WGS) catalyst with a hydrogen-selective membrane. In order to explore the suitability of Ni-based amorphous alloys for this application, the thermal stability and hydrogen permeation characteristics of Ni–ETM amorphous alloy membranes has been examined. A fundamental limitation of these materials is that hydrogen permeability is inversely proportional to the thermal stability of the alloy. Alloy design is therefore a compromise between hydrogen production rate and durability. Amorphous Ni₆₀Nb_40−XZr_X membranes have been tested at 400 °C in pure hydrogen, and in simulated coal-derived gas streams with high steam, CO and CO₂ levels, without severe degradation or corrosion-induced failure. Ni–Nb–Zr amorphous alloys are therefore prospective materials for use in a catalytic membrane reactor for coal-derived syngas.     

Bioimprinted protein exhibits glutathione peroxidase activity

A strategy for design of bioimprinted proteins with glutathione peroxidase (GPX) activity has been proposed. The proteins imprinted with a glutathione derivative were converted into selenium-containing proteins by chemical modifying the reactive hydroxyl groups of serines followed by sodium hydrogen selenide displacement. These selenium-containing proteins exhibited remarkable GPX activities and the GPX activities of reduction of H₂O₂ by glutathione (GSH) were found to be 101-817 U μmol⁻¹, which approaches the activity of a selenium-containing catalytic antibody elicited by a hapten similar to our template. The steady state kinetic study for imprinted protein catalysis revealed Michaelis-Menten kinetics for both H₂O₂ and GSH, e.g. the pesudo-first-order rate constant k_cat (H₂O₂) and the apparent Michaelis constant K_m (H₂O₂) at 1 mM GSH were calculated to be 784 min⁻¹ and 1.24×10⁻³ M, respectively, and the apparent second-order rate constant k_cat (H₂O₂)/K_m (H₂O₂) was determined to be 6.33×10⁵ (M min)⁻¹. The kinetics and the template inhibition showed that the strategy might be a remarkably efficient one for generating artificial enzyme with GPX activity.     

Fluorometric method for the determination of hydrogen peroxide and glucose with Fe3O4 as catalyst

In this paper, we utilized the instinct peroxidase-like property of Fe₃O₄ magnetic nanoparticles (MNPs) to establish a new fluorometric method for determination of hydrogen peroxide and glucose. In the presence of Fe₃O₄ MNPs as peroxidase mimetic catalyst, H₂O₂ was decomposed into radical that could quench the fluorescence of CdTe QDs more efficiently and rapidly. Then the oxidization of glucose by glucose oxidase was coupled with the fluorescence quenching of CdTe QDs by H₂O₂ producer with Fe₃O₄ MNPs catalyst, which can be used to detect glucose. Under the optimal reaction conditions, a linear correlation was established between fluorescence intensity ratio I₀/I and concentration of H₂O₂ from 1.8 × 10⁻⁷ to 9 × 10⁻⁴ mol/L with a detection limit of 1.8 × 10⁻⁸ mol/L. And a linear correlation was established between fluorescence intensity ratio I₀/I and concentration of glucose from 1.6 × 10⁻⁶ to 1.6 × 10⁻⁴ mol/L with a detection limit of 1.0 × 10⁻⁶ mol/L. The proposed method was applied to the determination of glucose in human serum samples with satisfactory results.