BLEND MEMBRANES FOR DIRECT METHANOL AND PROTON EXCHANGE MEMBRANE FUEL CELLS

Sulphonated polystyrene ethylene butylene polystyrene(SPSEBS)prepared with 35%sulphonation was found to be highly elastic and enlarged up to 300%-400%of its initial length.It absorbed over 110%of water by weight.A major drawback of this membrane is its poor mechanical properties which are not adequate for use as polymer electrolytes in fuel cells.To overcome this,SPSEBS was blended with poly(vinylidene fluoride)(PVDF),a hydrophobic polymer.The blend membranes showed better mechanical properties than the base polymer.The effect of PVDF content on water uptake,ion exchange capacity and proton conductivity of the blend membranes was investigated.This paper presents the results of recent studies applied to develop an optimized in-house membrane electrode assembly(MEA)preparation technique combining catalyst ink spraying and assembly hot pressing.Easy steps were chosen in this preparation technique in order to simplify the method,aiming at cost reduction.The open circuit voltage for the cell with SPSEBS is 0.980 V which is higher compared to that of the cell with Nafion 117(0.790 V).From this study,it is concluded that a polymer electrolyte membrane suitable for proton exchange membrane fuel cell(PEMFC)and direct methanol fuel cell(DMFC)application can be obtained by blending SPSEBS and PVDF in appropriate proportions.The methanol permeability and selectivity showed a strong influence on DMFC performance.     

A Luminescent Metal–Organic Framework Thermometer with Intrinsic Dual Emission from Organic Lumophores

A new mixed‐ligand metal–organic framework (MOF), ZnATZ‐BTB, has been constructed as a luminescent ratiometric thermometer by making use of the intrinsic dual emission at cryogenic temperatures. Its twofold interpenetrated network promotes the Dexter energy transfer (DET) between the mixed organic lumophores. The temperature‐dependent luminescent behavior arises from the thermal equilibrium between two separated excited states coupled by DET, which is confirmed by Boltzmann distribution fitting. The small excited‐state energy gap allows ZnATZ‐BTB to measure and visualize cryogenic temperatures (30–130 K) with significantly high relative sensitivity (up to 5.29 % K^?1 at 30 K). Moreover, it is the first example of a ratiometric MOF thermometer the dual emitting sources of which are widely applicable mixed organic ligands, opening up new opportunities for designing such devices.     

Micro-/Mesoporous conjugated polymer based on star-shaped triazine-functional triphenylamine framework as the performance-improved cathode of Li-organic battery

A novel organic conjugated polymer based on star-shaped triazine-functional triphenylamine framework poly[1,3,5-tris(4-diphenylamino-phenyl)triazine] (PTDAPTz) is designed and synthesized successfully by FeCl₃-catalysted chemical oxidative polymerization. The polymer PTDAPTz powder exhibits a compactly packed pleated skirt shape-like morphology with a high surface area (~930 m² g⁻¹) and a bimodal pore size distribution ranging from micropores (~0.55 nm) to small diameter mesopores (~2–6 nm). As explored as the cathode material, the obtained PTDAPTz presents the double charge–discharge process characteristics of both the free radical redox of triphenylamine unit and the bipolar redox of triazine unit in the polymer and a well-defined multistage charge/discharge voltage plateau (~3.8 V for p-doped and ~2.0 V for n-doped) during the charge–discharge process. Also, the PTDAPTz demonstrates an improved capacity (stabilized at 123 mA h g⁻¹ until 50th cycle) and the enhanced rate performance compared to polytriphenylamine (PTPAn). Specially, the discharge curve for the part of triphenylamine unit presents an obviously improved discharge plateau (~3.8 V for PTDAPTz compared to ~3.6 V for PTPAn) due to the electron-withdrawing effect of the triazine unit to triphenylamine. The elaborate structural design and created micro-/mesoporous morphology with the double charge–discharge process make PTDAPTz a potential candidate as the performance-improved cathode of Li-organic battery. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2574–2583     

Self‐assembly of metal–organic framework thin films containing metalloporphyrin and their photocatalytic activity under visible light

With [5,10,15,20‐tetra(4‐carboxyphenyl)porphyrin]Mn(III) and sterically controlled 2,2¢‐dimethyl‐4,4¢‐pyridine as the main raw materials, metal–organic framework thin films containing metalloporphyrin (MnPor‐MOF) with catalytically active sites were built up on functionalized quartz glass surfaces using a layer‐by‐layer self‐assembly method. Retaining active catalytic sites and having a porous reticular structure, the MnPor‐MOF films possessed remarkable photocatalytic activity for oxidative degradation of methylene blue in the presence of hydrogen peroxide under visible‐light irradiation. Most meaningfully, the MnPor‐MOF films were highly stable and simply and conveniently reusable, and are thus a potentially new organic material for photocatalytic wastewater treatment. Copyright © 2015 John Wiley & Sons, Ltd.     

功率对氘代辉光放电聚合物结构和力学性能的影响

采用射频辉光放电聚合技术,在低压等离子体聚合装置上开展在5~20 W功率下氘代辉光放电聚合物薄膜的制备及性能研究。利用傅里叶变换红外吸收光谱仪表征薄膜的化学结构,讨论了功率变化对其官能团结构的影响规律。利用元素分析仪和纳米压痕仪表征薄膜中氘原子的相对含量和薄膜的力学性能。研究表明:随着功率的升高,薄膜中的氘含量先升高后降低,在10W时达到最大,薄膜中SP3 CD的相对含量增加,SP3 CD2的相对含量减小;聚合物薄膜的硬度和杨氏模量均随功率的增加而减小。     

Multifunctional triphenylamine polymers synthesized via direct (hetero) arylation polymerization

The design rules for creating multifunctional organic electronic materials are currently limited. By copolymerizing twisted triphenylamine (TPA) and electron rich dioxythiophene (XDOT) monomers via Direct (Hetero) Arylation Polymerization (DHAP), a set of polymers are obtained that perform as yellow to transmissive electrochromic (EC) films with up to 45% contrast, as well as in electroluminescent (EL) applications, achieving a luminance of ∼450 cd/m² in yellow‐green polymer light‐emitting diodes (PLEDs). In addition, polymerizing TPA with a donor‐acceptor‐donor monomer results in a low‐bandgap polymer that achieves power conversion efficiencies up to 2.5% when blended with PC₇₁BM in conventional organic photovoltaic (OPV) devices. Incorporation of TPA units into the polymer backbone largely breaks any aggregation and ordering in the solid‐state, leading to highly soluble materials that form smooth, reproducible thin films. The TPA unit also serves to break conjugation throughout the polymer backbone, providing precise control over optical and electronic properties through choice of comonomer. These results suggest that TPA copolymers can be useful for achieving multi‐functionality without sacrificing facile solution processability, making them promising candidates for multifunctional devices like dual EC/EL displays. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 147–153     

Degradation performance of polyglutamic acid and its application of calcium supplement

Degradable biopolymers with functional groups play a crucial role in the biomedical field. In this case, the influences of temperature and pH values on the degradation performance of poly (γ‐glutamic acid) (γ‐PGA) were fully explored by gel permeation chromatography. Further, γ‐PGA‐Ca was prepared by using calcium chloride to react with the low molecular weight γ‐PGA and characterized by Fourier transform infrared, differential scanning calorimetry test, gel permeation chromatography, atomic absorption spectrophotometric, Ca²⁺ release in vivo, and cytotoxicity experiments. Furthermore, Caco‐2 cell model was constructed to study the mechanism of γ‐PGA‐Ca intestinal absorption. Results indicated that low pH value and high temperature are the suitable conditions for the degradation of γ‐PGA. It also suggested that γ‐PGA‐Ca can be used as calcium supplements due to its high rate of absorption.     

Optimizing Optoelectronic Properties of Pyrimidine‐Based TADF Emitters by Changing the Substituent for Organic Light‐Emitting Diodes with External Quantum Efficiency Close to 25 % and Slow Efficiency Roll‐Off

A series of green butterfly‐shaped thermally activated delayed fluorescence (TADF) emitters, namely PXZPM , PXZMePM , and PXZPhPM , are developed by integrating an electron‐donor (D) phenoxazine unit and electron‐acceptor (A) 2‐substituted pyrimidine moiety into one molecule via a phenyl‐bridge π linkage to form a D –π–A–π–D configuration. Changing the substituent at pyrimidine unit in these emitters can finely tune their emissive characteristics, thermal properties, and energy gaps between the singlet and triplet states while maintaining frontier molecular orbital levels, and thereby optimizing their optoelectronic properties. Employing these TADF emitters results in a green fluorescent organic light‐emitting diode (OLED) that exhibits a peak forward‐viewing external quantum efficiency (EQE) close to 25 % and a slow efficiency roll‐off characteristic at high luminance.