Phosphorylated chitosan/poly(vinyl alcohol) based proton exchange membranes modified with propylammonium nitrate ionic liquid and silica filler for fuel cell applications

In our previous work, phosphorylated chitosan was modified through polymer blending with poly(vinyl alcohol) (PVA) polymer to produce N-methylene phosphonic chitosan/poly(vinyl alcohol) (NMPC/PVA) composite membranes. The aim of this work is to further investigate the effects of a propylammonium nitrate (PAN) ionic liquid and/or silicon dioxide (SiO₂) filler on the morphology and physical properties of NMPC/PVA composite membranes. The temperature-dependent ionic conductivity of the composite membranes with various ionic liquid and filler compositions was studied by varying the loading of PAN ionic liquid and SiO₂-PAN filler in the range of 5–20 wt%. As the loading of PAN ionic liquid increased in the NMPC/PVA membrane matrix, the ionic conductivity value also increased with the highest value of 0.53 × 10^?3 S cm^?1 at 25 °C and increased to 1.54 × 10^?3 S cm^?1 at 100 °C with 20 wt% PAN. The NMPC/PVA-PAN (20 wt%) composite membrane also exhibited the highest water uptake and ion exchange capacity, with values of 60.5% and 0.60 mequiv g^?1, respectively. In addition, in the single-cell performance test, the NMPC/PVA-PAN (20 wt%) composite membrane displayed a maximum power density, which was increased by approximately 14% compared to the NMPC/PVA composite membrane with 5 wt% SiO₂-PAN. This work demonstrated that modified NMPC/PVA composite membranes with ionic liquid PAN and/or SiO₂ filler showed enhanced performance compared with unmodified NMPC/PVA composite membranes for proton exchange membrane fuel cells.     

Highly stable nanocarbon supported Pt catalyst for fuel cell via a molten salt graphitization strategy

Proton exchange membrane fuel cells (PEMFCs) durability has been severely hindered by carbon support poor stability in the cathodic Pt-based catalyst. Herein, a high-surface-area nitrogen-doped graphitic nanocarbon (N-G-CA) with mesopores is developed as Pt support to address PEMFCs durability challenge. Resorcinol-formaldehyde aerogel pyrolyzed carbon aerogel is selected as N-G-CA raw material. Nitrogen atoms are introduced into carbon aerogel via NH₃ heat treatment. Then, nitrogen-doped carbon aerogel is transferred into N-G-CA via heating together with transition-metal salts (one of FeCl₃, FeCl₂, CoCl₂, or MnCl₂, etc.) at 1200 °C. As ORR catalyst, Pt/N-G-CA half-wave potential only lost 10 mV, after 30, 000 cycles accelerated aging test in the rotating-desk-electrode. Only 12 mV voltage loss at 1.5 A/cm2 is observed, after 5, 000 cycles for membrane electrode. Pt/N-G-CA exhibits superior durability and activity than commercial Pt/C. High durability of Pt/N-G-CA is due to N-G-CA high graphitization extent, as well as the interactions between doping nitrogen and Pt. N-G-CA is promising as stable support for durable Pt-based catalysts in PEMFCs, thanks to enhanced carbon corrosion resistance, uniformly dispersed Pt, and strong support-metals interaction.     

Identifying catalyst layer compositions of proton exchange membrane fuel cells through machine-learning-based approach

Membrane electrode assembly (MEA) is considered a key component of a proton exchange membrane fuel cell (PEMFC). However, developing a new MEA to meet desired properties, such as operation under low-humidity conditions without a humidifier, is a time- and cost-consuming process. This study employs a machine-learning-based approach using K-nearest neighbor (KNN) and neural networks (NN) in the MEA development process by identifying a suitable catalyst layer (CL) recipe in MEA. Minimum redundancy maximum relevance and principal component analysis were implemented to specify the most important predictor and reduce the data dimension. The number of predictors was found to play an essential role in the accuracy of the KNN and NN models although the predictors have self-correlations. The KNN model with a K of 7 was found to minimize the model loss with a loss of 11.9%. The NN model constructed by three corresponding hidden layers with nine, eight, and nine nodes can achieve the lowest error of 0.1293 for the Pt catalyst and 0.031 for PVA as a good additive blending in the CL of the MEA. However, even if the error is low, the prediction of PVA seems to be inaccurate, regardless of the model structure. Therefore, the KNN model is more appropriate for CL recipe prediction.     

Sputtered Ir–Ru based catalysts for oxygen evolution reaction: Study of iridium effect on stability

Magnetron sputtered low-loading iridium-ruthenium thin films are investigated as catalysts for the Oxygen Evolution Reaction at the anode of the Proton Exchange Membrane Water Electrolyzer. Electrochemical performance of 50 nm thin catalysts (Ir pure, Ir–Ru 1:1, Ir–Ru 1:3, Ru pure) is tested in a Rotating Disk Electrode. Corresponding Tafel slopes are measured before and after the CV-based procedure to compare the activity and stability of prepared compounds. Calculated activities prior to the procedure confirm higher activity of ruthenium-containing catalysts (Ru pure > Ir–Ru 1:3 > Ir–Ru 1:1 > Ir pure). However, after the procedure a higher activity and less degradation of Ir–Ru 1:3 is observed, compared to Ir–Ru 1:1, i.e. the sample with a higher amount of unstable ruthenium performs better. This contradicts the expected behavior of the catalyst. The comprehensive chemical and structural analysis unravels that the stability of Ir–Ru 1:3 sample is connected to RuO₂ chemical state and hcp structure. Obtained results are confirmed by measuring current densities in a single cell.     

Coil‐Type Asymmetric Supercapacitor Electrical Cables

Cable‐shaped supercapacitors (SCs) have recently aroused significant attention due to their attractive properties such as small size, lightweight, and bendability. Current cable‐shaped SCs have symmetric device configuration. However, if an asymmetric design is used in cable‐shaped supercapacitors, they would become more attractive due to broader cell operation voltages, which results in higher energy densities. Here, a novel coil‐type asymmetric supercapacitor electrical cable (CASEC) is reported with enhanced cell operation voltage and extraordinary mechanical‐electrochemical stability. The CASECs show excellent charge–discharge profiles, extraordinary rate capability (95.4%), high energy density (0.85 mWh cm⁻³), remarkable flexibility and bendability, and superior bending cycle stability (≈93.0% after 4000 cycles at different bending states). In addition, the CASECs not only exhibit the capability to store energy but also to transmit electricity simultaneously and independently. The integrated electrical conduction and storage capability of CASECS offer many potential applications in solar energy storage and electronic gadgets.     

Secure lightweight password authenticated key exchange for heterogeneous wireless sensor networks

Several three-party password authenticated key exchange (3-PAKE) protocols have recently been proposed for heterogeneous wireless sensor networks (HWSN). These are efficient and designed to address security concerns in ad-hoc sensor network applications for a global Internet of Things framework, where a user may request access to sensitive information collected by resource-constrained sensors in clusters managed by gateway nodes. In this paper we first analyze three recently proposed 3-PAKE protocols and discuss their vulnerabilities. Then, based on Radio Frequency Identification technologies we propose a novel 3-PAKE protocol for HWSN applications, with two extensions for additional security features, that is provably secure, efficient and flexible.     

（S）-噻吗洛尔半水合物的合成及表征

为了开发β受体阻断剂新药（S）-噻吗洛尔半水合物，采用3-吗啉-4-氯-1，2，5-噻二唑为起始原料，经水解反应得到中间体1（3-吗啉-4-羟基-1，2，5-噻二唑）。中间体1与R-环氧氯丙烷发生醚化反应，经后处理及重结晶得到中间体2 {（R）-4-［4-（环氧乙烷-2-基甲氧基）-1，2，5-噻二唑-3-基］吗啉}。中间体2经胺化反应、马来酸成盐及重结晶得到（S）-马来酸噻吗洛尔。（S）-马来酸噻吗洛尔经游离、纯水转晶得到符合药典标准的（S）-噻吗洛尔半水合物，总收率14.05%且e.e.值为99.66%。最终成品经IR、1H-NMR、13C-NMR、MS、TGA、DSC表征，并优化各步反应条件。结果表明:以三乙胺为醚化反应缚酸剂75 ℃反应最佳；以乙醇为胺化反应溶剂46 ℃反应16 h最佳；S-噻吗洛尔的转晶拆分以水作溶剂，比传统不对称合成工艺安全稳定，操作简单，适合工业化生产。     

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.     

Preparation and physical properties of the layered niobate Cu0.5Nb3O8: Application to photocatalytic hydrogen evolution

The new layered niobate Cu_0.5Nb₃O₈ is synthesized by soft chemistry in aqueous electrolyte via Cu²⁺→H⁺ exchange between copper nitrate and HNb₃O₈·H₂O. The characterization of the exchanged product is made by means of thermal gravimetry, chemical analysis, X-ray diffraction and IR spectroscopy. Thermal analysis shows a conversion to anhydrous compound above 500 °C. The oxide displays a semiconductor like behavior; the thermal variation of the conductivity shows that d electrons are strongly localized and the conduction is thermally activated with activation energy of 0.13 eV. The temperature dependence of the thermopower is indicative of an extrinsic conductivity; the electrons are dominant carriers in conformity with an anodic photocurrent. Indeed, the Mott–Schottky plot confirms n-type conduction from which a flat band potential of −0.82 V_SCE, an electronic density of 8.72×10¹⁹ m⁻³ and a depletion width of 4.4 nm are determined. The upper valence band, located at ~5.8 eV below vacuum is made up predominantly of Cu²⁺: 3d with a small admixture of O²⁻: 2p orbitals whereas the conduction band consists of empty Nb⁵⁺: 5s level. The energy band diagram shows the feasibility of the oxide for the photocatalytic hydrogen production upon visible light (29 mW cm⁻²) with a rate evolution of 0.31 mL g⁻¹ min⁻¹.