Sulfonated poly(arylene ether nitrile)-based composite membranes enhanced with Ca2+ bridged carbon nanotube-graphene oxide networks

As the core component of proton exchange membrane fuel cell, proton exchange membranes (PEM) have attracted much attention of researchers. To trade-off the proton conduction, dimensional stability and anti-oxidation ability, graphene oxide (GO) and acidized multi-walled carbon nanotubes (MWCNT) using calcium ion as coordination bridge (GO-Ca2+-MWCNT) was synthesized, and then incorporating into sulfonated poly(arylene ether nitrile) (SPEN) to fabricate SPEN/GO-Ca2+-MWCNT organic-inorganic composite membranes by solution-casting method and explore the influence of varying loading on performances as PEM. It was found that the proton conductivity of the composite membranes was higher than that of SPEN, while maintaining better dimensional stability, excellent anti-oxidation ability and good mechanical properties. All of these were attributed to the formation of three-dimensional structure between GO and MWCNT bridged by Ca2+. Particularly, the SPEN/GO-Ca2+-MWCNT-1 composite membrane exhibited excellent tensile strength of 71.45 MPa, better thermal stability as well as high proton conductivity (0.054 S/cm at 30 ℃, and 0.193 S/cm at 90 ℃), above 10-2 S/cm, satisfying the requirement of fuel cells. All in all, the results indicate that the filler with three-dimensional network structure can effectively improve the performances of SPEN, and the prepared composite membranes show potential applications in many fields.

Sodium-Ion Conductivity and Humidity-Sensing Properties of Na2O-MoO3-P2O5 Glass-Ceramics

A series of glass-ceramics were prepared by heat-treatments of 40Na2O-30MoO3-30P2O5 (in mol%) glass in a temperature range from 380 (Tg) to 490 °C (Tc) and for 1–24 h. The prepared glass-ceramics contain from 2 to 25 wt.% of crystalline NaMoO2PO4. The sodium-ion conductivity in these materials decreases up to one order of magnitude with an increase in the degree of crystallization due to the immobilization of sodium ions in crystalline NaMoO2PO4. The transport of sodium ions in these materials occurs primarily through the dominant continuous glassy phase, and it is weakly affected by the sporadically distributed crystalline grains. However, the prepared glass-ceramics exhibit high proton conductivity in a humid atmosphere and remarkable humidity-sensing properties; this could be related to crystalline NaMoO2PO4, which provides sites for water adsorption. The glass-ceramic prepared at 450 °C for 24 h shows the best humidity-sensing performance among all samples, showing an increase in proton conductivity for more than seven orders of magnitude with the increase in relative humidity from 0% to 95%. Under a highly humid atmosphere (95% relative humidity and 25 °C), the proton conductivity of this glass-ceramic reaches 5.2 × 10−3 (Ω cm)−1. Moreover, the electrical response of these materials on the change in the relative humidity is linear and reversible in the entire range of the relative humidity, which indicates that they are novel promising candidates for application as humidity sensors.

The Effect of Sulfated Zirconia and Zirconium Phosphate Nanocomposite Membranes on Fuel-Cell Efficiency

To investigate the effect of acidic nanoparticles on proton conductivity, permeability, and fuel-cell performance, a commercial Nafion® 117 membrane was impregnated with zirconium phosphates (ZrP) and sulfated zirconium (S-ZrO2) nanoparticles. As they are more stable than other solid superacids, sulfated metal oxides have been the subject of intensive research. Meanwhile, hydrophilic, proton-conducting inorganic acids such as zirconium phosphate (ZrP) have been used to modify the Nafion® membrane due to their hydrophilic nature, proton-conducting material, very low toxicity, low cost, and stability in a hydrogen/oxygen atmosphere. A tensile test, water uptake, methanol crossover, Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and scanning electron microscopy (SEM) were used to assess the capacity of nanocomposite membranes to function in a fuel cell. The modified Nafion® membrane had a higher water uptake and a lower water content angle than the commercial Nafion® 117 membrane, indicating that it has a greater impact on conductivity. Under strain rates of 40, 30, and 20 mm/min, the nanocomposite membranes demonstrated more stable thermal deterioration and higher mechanical strength, which offers tremendous promise for fuel-cell applications. When compared to 0.113 S/cm and 0.013 S/cm, respectively, of commercial Nafion® 117 and Nafion® ZrP membranes, the modified Nafion® membrane with ammonia sulphate acid had the highest proton conductivity of 7.891 S/cm. When tested using a direct single-cell methanol fuel cell, it also had the highest power density of 183 mW cm−2 which is better than commercial Nafion® 117 and Nafion® ZrP membranes.

A Dual-Function Cobalt Metal-Organic Framework for High Proton Conduction and Selective Luminescence Sensing of Histidine

Proton exchange membrane (PEM) is a key component of proton exchange membrane fuel cells (PEMFCs). In recent years, metal organic framework (MOF) and its composite membranes have become the research hotspots. [Co(L-Glu)(H2O)•H2O]n (Co-MOF, L-Glu = L-glutamate) was synthesized by hydrothermal method. Co2+ ions are coordinated with L-Glu ligands and water molecules to form one-dimensional chains extending along the a-axis, which are further bridged by L-Glu ligands to form a three-dimensional network structure. AC impedance analysis shows that the proton conductivity of Co-MOF reaches 3.14×10-4 S•cm-1 under 98% relative humidity (RH) and 338 K. To improve proton conductivity, different contents of Co-MOF were added in chitosan (CS) to form composite membranes Co-MOF@CS-X (mass fraction X= 5%, 10%, 15% wt). The results show the proton conductivity of the Co-MOF@CS-10 composite membrane is 1.73×10-3 S•cm-1 at 358 K and 98% RH, which is more than 5 times that of Co-MOF. As far as we known, this is the first composite made of amino acid MOFs and CS as proton exchange membrane. Furthermore, Co-MOF has an obvious quenching effect on L-histidine in aqueous solution, which can detect the content of L-histidine in water with high sensitivity, and the detection limit is 1×10-7 M.

A confinement of N-heterocyclic molecules in a metal–organic framework for enhancing significant proton conductivity

A series of N-heterocyclic⊂VNU-23 materials have been prepared via the impregnation procedure of N-heterocyclic molecules into VNU-23.

PANa/Covalent Organic Framework Composites with Improved Water Uptake and Proton Conductivity

It is a challenge to effectively load proton carriers in COFs to improve their proton conductivity. Herein, we report a series of COF-based composites, PANa@UCOF-x (PANa: sodium polyacrylate, x: weight...