Comb-shaped sulfonated poly(aryl ether sulfone) proton exchange membrane for fuel cell applications

Structure design is the primary strategy to acquire suitable ionomers for preparing proton exchange membranes (PEMs) with excellent performance. A series of comb-shaped sulfonated fluorinated poly(aryl ether sulfone) (SPFAES) membranes are prepared from sulfonated fluorinated poly(aryl ether sulfone) polymer (SPFAE) and sulfonated poly(aryl ether sulfone) oligomer (SPAES-Oligomer). Chemical structures of the comb-shaped membranes are verified by ¹H nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectra. The comb-shaped SPFAES membranes display more continuous hydrophilic domains for ion transfer, because the abundant cations and flexible side-chains structure possess higher mobility and hydrophilicity, which show significantly improved proton conductivity, physicochemical stability, mechanical property compared to the linear SPFAE membranes. In a H₂/O₂ single-cell test, the SPFAES-1.77 membrane achieves a higher power density of 699.3 mW/cm² in comparison with Nafion® 112 (618.0 mW/cm²) at 80 °C and 100% relative humidity. This work offers a promising example for the synthesis of highly branched polymers with flexible comb-shaped side chains for high-performance PEMs.     

High performance H2 sensor based on rGO-wrapped SnO2–Pd porous hollow spheres

Hydrogen (H₂) sensors based on metal oxide semiconductors (MOS) are promising for many applications such as a rocket propellant, industrial gas and the safety of storage. However, poor selectivity at low analyte concentrations, and independent response on high humidity limit the practical applications. Herein, we designed rGO-wrapped SnO₂–Pd porous hollow spheres composite (SnO₂–Pd@rGO) for high performance H₂ sensor. The porous hollow structure was from the carbon sphere template. The rGO wrapping was via self-assembly of GO on SnO₂-based spheres with subsequent thermal reduction in H₂ ambient. This sensor exhibited excellently selective H₂ sensing performances at 390 °C, linear response over a broad concentration range (0.1–1000 ppm) with recovery time of only 3 s, a high response of ～8 to 0.1 ppm H₂ in a minute, and acceptable stability under high humidity conditions (e. g. 80%). The calculated detection limit of 16.5 ppb opened up the possibility of trace H₂ monitoring. Furthermore, this sensor demonstrated certain response to H₂ at the minimum concentration of 50 ppm at 130 °C. These performances mainly benefited from the special hollow porous structure with abundant heterojunctions, the catalysis of the doped-PdO_x, the relative hydrophobic surface from rGO, and the deoxygenation after H₂ reduction.     

Characterization of a Tryptophan 6-Halogenase from Streptomyces albus and Its Regioselectivity Determinants

Tryptophan halogenases are found in diverse organisms and catalyze regiospecific halogenation. They play an important role in the biosynthesis of halogenated indole alkaloids, which are biologically active and of therapeutic importance. Here, a tryptophan 6-halogenase (SatH) from Streptomyces albus was characterized by using a whole-cell reaction system in Escherichia coli. SatH showed substrate specificity for chloride and bromide ions, leading to regiospecific halogenation at the C6-position of l -tryptophan. In addition, SatH exhibited higher performance in bromination than that of previously reported tryptophan halogenases in the whole-cell reaction system. Through structure-based protein mutagenesis, it has been revealed that two consecutive residues, A78/V79 in SatH and G77/I78 in PyrH, are key determinants in the regioselectivity difference between tryptophan 6- and 5-halogenases. Substituting the AV with GI residues switched the regioselectivity of SatH by moving the orientation of tryptophan. These data contribute to an understanding of the key residues that determine the regioselectivity of tryptophan halogenases.     

Hydrocarbon-based electrode ionomer for proton exchange membrane fuel cells

The electrode ionomer is a key factor that significantly affects the catalyst layer morphology and fuel cell performance. Herein, sulfonated poly(arylene ether sulfone)-based electrode ionomers with polymers of various molecular weights and alcohol/water mixtures were prepared, and those comprising the alcohol/water mixture showed a higher performance than the ones prepared using higher boiling solvents, such as dimethylacetamide; this is owing to the formation of the uniformly dispersed ionomer catalyst layer. The relation between ionomer molecular weight for the same polymer structure and the sulfonation degree was investigated. Because the chain length of polymer varies with molecular weight and chain entanglement degree, its molecular weight affects the electrode morphology. As the ionomer covered the catalyst, the agglomerates formed were of different morphologies according to their molecular weight, which could be deduced indirectly through dynamic light scattering and scanning electron microscopy. Additionally, the fuel cell performance was confirmed in the current-voltage curve.     

Sulphur-doped graphene as metal-free carbocatalysts for the solventless aerobic oxidation of styrenes

Pyrolysis of λ-carrageenan at 1000 °C and subsequent exfoliation lead to a S-doped graphene [(S)G]. Increasing pyrolysis temperature to 1200 °C or the use of other carrageenans with lower sulphate content results in the failure of S doping. XPS confirms the presence of S atom (4.5%) with environments alike sulphide and sulphoxide. (S)G promotes the aerobic oxidation of styrenes to their corresponding benzaldehydes accompanied by lesser amounts of styrene oxide. In contrast, under the same experimental conditions reduced graphene oxide exhibits a negligible activity. (S)G was reused with almost coincident catalytic performance.     

Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)

It was well known that solvent effect plays a very important role in the catalytic reaction. There are many theoretical studies on the solvent effect in homogeneous catalysis while there are few theoretical studies on the solvent effect in the heterogeneous catalytic reaction and there has been no work to investigate the solvent effect on furfural transformation in heterogeneous catalysis. In the present work, both the density functional calculations and the microkinetic analysis were performed to study the selective hydrogenation of furfural over Pt(111) in the presence of methanol as well as toluene and compared with that in the gas condition. The present results indicated that the methanol can enhance the adsorption strength of furfural and other oxygen-containing reaction species due to its relatively strong polarity properties and this can be a main reason for solvent-induced high activity and selectivity. Another reason is that reaction paths study showed that the presence of methanol solvent makes the dehydrogenation of furfural less thermochemical due to the fact that furfural is more stabilized than that of dehydrogenation species, and methanol also has an inhibition effect on the dehydrogenation of furfural in the kinetic aspect, and further energetic span theory proves highest activity and selectivity for hydrogenation in methanol solvent of vapor, methanol and toluene. Moreover, microkinetic model simulation demonstrated that the activity and selectivity of hydrogenation in methanol is both higher than that in vapor and toluene. The much higher activity in methanol is due to the stabilized adsorbed reactants in the surface, which leads to a higher surface coverage of furfural. It might be proposed based on the present work that a solvent with relatively strong polarity may be favorable for the high selective hydrogenation of furfural.     

Advances in the in vitro digestion and fermentation of polysaccharides

In vitro digestion models are widely used to study the structural changes, digestion and release of food components under simulated gastrointestinal conditions. As compared to the in vivo digestion tests, the in vitro digestion reflects the digestion and utilisation of food after ingestion and has the advantages of being time consuming, inexpensive, reproducible and free from moral and ethical restrictions. This study reviewed the current research studies on the in vitro simulated digestion of polysaccharides conducted in the last 5 years and focused on the oral, gastric and intestinal digestion models, with the aim of providing a basis for the further testing of changes in the content, structure and active ingredients of polysaccharides before and after digestion.     

Three-dimensional crumpled graphene-based platinum–gold alloy nanoparticle composites as superior electrocatalysts for direct methanol fuel cells

High performance of electrocatalysts for direct methanol fuel cells was demonstrated by three-dimensional (3D) graphene (GR) decorated with platinum (Pt)–gold (Au) alloy nanoparticles (3D-GR/PtAu). The 3D-GR/PtAu composite with a morphology like a crumpled paper ball was synthesized from a colloidal mixture of GR and Pt–Au alloy nanoparticles with aerosol spray drying. The 3D-GR/PtAu had a high specific surface area and electrochemical surface area of up to 238 and 325 m²/g(Pt), respectively, and the electrocatalytic applications of the 3D-GR/PtAu were examined through methanol oxidation reactions. The 3D-GR/PtAu had the highest electrocatalytic activity for methanol oxidation reactions compared with commercial Pt–carbon black and Pt-GR. The 3D-GR/PtAu was also highly sensitive electrocatalytic activity in the methanol oxidation reaction compared with the 2D-GR/Pt–Au. Furthermore, the electrocatalytic activity of the 3D-GR/PtAu had the highest performance among the catalysts containing Pt, Au, and GR for the methanol oxidation reactions. The increased electrocatalytic activity is attributed to the high specific surface area of the 3D formation and the effective surface structure of the Pt–Au alloy nanoparticles.     

Enhancing cation exchange capacity of chars through ozonation

The use of ozone to increase the cation exchange capacity (CEC) of two chars produced from pyrolysis of Douglas fir (Pseudotsuga menziessii) and a control bituminous coal activated carbon (AC) is reported. Chars were produced from the wood fraction of Douglas fir (DFWC) and the bark (DFBC) at 500 °C using an auger driven reactor with a nitrogen sweep gas under mild vacuum. Five ozone treatment times, ranging from 5 min to 60 min, were investigated. The initial properties of each char were found to differ significantly from the other samples in terms of surface area, proximate composition, and elemental composition. DFWC did not show significant mass loss or temperature variation during ozone treatment; however, after 1 h of oxidation both DFBC and AC samples resulted in 20% and 30% mass loss, respectively, and reactor temperatures in excess of 60 °C. Analysis of the pore size distribution of each treatment shows that ozone treatment did not significantly affect small micropores after 30 min of treatment for any material, but did reduce the apparent surface area of mesopores. Increases in carboxylic groups were identified with ozone treatment and found to correlate strongly with changes in measured CEC. The formation of lactone was found to correlate positively with reactor temperature during oxidation. These results indicate that the properties of chars, including surface area, pore structure, and chemical composition, as well as reactor conditions strongly affect the ozone oxidation of chars.     

Self-terminated electrodeposition of platinum on titanium nitride for methanol oxidation reaction in acidic electrolyte

The development of high-performance electrocatalysts for methanol oxidation is an urgent task to enhance the efficiency of direct methanol fuel cells. We report a simple and controllable method to fabricate Pt-decorated TiN electrocatalysts using self-terminated electrodeposition at room temperature and ambient pressure. Under optimized deposition parameters such as electrolyte pH, TiN substrate pretreatment, and pulsed deposition potential, quenching of the Pt electrodeposition facilitates obtaining an extremely low Pt mass loading (0.93 μg/cm²) on the TiN substrate. Repeated deposition potential pulses enable a gradual increase in Pt loading, with a precise control of the loaded Pt mass. Maximum intrinsic and mass activities for the methanol oxidation reaction are achieved for the catalyst with a Pt loading mass of 55.0 μg/cm², prepared by 20 deposition pulses. The maximum intrinsic activity achieved with the Pt-decorated TiN electrocatalyst is five times higher than that obtained with bulk Pt. The present results thus provide a facile method for the fabrication of cost-effective electrocatalysts.