质子交换膜燃料电池膜电极的结构优化

膜电极(membrane electrode assembly,MEA)是质子交换膜燃料电池(proton exchange membrane fuel cell,PEMFC)的核心部件,为PEMFC提供了多相物质传递的微通道和电化学反应场所。为了实现燃料电池商业化目标,需要制备高功率密度、低Pt载量、耐久性好的MEA。在MEA中除了催化剂以外,各功能层结构、层与层之间的界面都对MEA的性能具有重要影响。传统方法(CCS法和CCM法)制备的MEA在结构上有很多缺陷,明显制约了Pt的利用率和系统传质能力。通过优化各功能层结构消除缺陷,将有利于进一步提升PEMFC综合性能。本文从传统MEA结构存在的问题出发,梳理了近年来关于催化层、质子交换膜和气体扩散层结构优化方面的文献,归纳总结了各先进结构的制备方法、构效关系以及优缺点,对未来高性能、低成本和长寿命的MEA的开发具有指导意义。     

Salicylate-selective membrane electrode based on tin(IV) tetraphenylporphyrin

The response properties of a new solvent/polymeric membrane electrode with unique selectivity toward anionic salicylate are reported. The electrode is prepared by incorporating 5, 10, 15, 20-tetraphenyl(porphyrinato)tin(IV) dichloride (Sn[TPP]Cl2) into a plasticized poly(vinyl chloride) membrane. The resulting sensor exhibits an anti-Hofmeister selectivity pattern, with high specificity for salicylate over lipophilic inorganic anions (perchlorate, periodate, thiocyanate, iodide, etc.) and biological organic anions (citrate, lactate, acetate). Moderate selectivity over structural analogues of salicylate (3- and 4-hydroxybenzoate, benzoate) is also observed. Radiotracer uptake experiments using [14C]salicylate clearly show that the metal center of the metalloporphyrin is critical for selective salicylate transport in the membrane phase. Minimal response to chloride ions makes the new electrode potentially useful for estimating salicylate levels in biological samples.     

Studies of BaTiO3 thin films on different bottom electrode

BaTiO₃ (BT) thin films were prepared on Pt/Ti/SiO₂/Si and Ru/Ti/SiO₂/Si substrates by a modified sol-gel technique. The microstructure of the films was characterized by atomic force microscopy (AFM), X-ray diffraction (XRD) and Raman spectroscopy. The results showed that BT thin films crystallized with perovskite structure. Compared to BT film on Pt/Ti/SiO₂/Si substrate, BT thin film deposited on Ru electrode has similar dielectric constant, while it has higher dielectric loss. C–E curve for BT film on Pt/Ti/SiO₂/Si was more symmetrical around zero-bias field than C–E curve for BT film on Ru/Ti/SiO₂/Si substrate. The tunability was 52.02% for BT film on Pt electrode, which was 33.42% on Ru electrode, at 275 kV/cm and room temperature. The leakage current density of BT on Pt electrode was about an order of magnitude lower than BT film on Ru electrode at the applied electrical field below 150 kV/cm. The leakage conduction mechanism was investigated.     

Chromium(III) porphyrin as a selective ionophore in a salicylate-selective membrane electrode

The construction, potentiometric response properties, and applications of a novel ion-selective electrode with high selectivity toward salicylate are described. Chromium(III) tetraphenylporphyrin chloride was used as ion carrier into plasticized PVC membrane. This ionophore is capable of serving as both a positively charged and neutral carrier, depending on the pH of the sample solution. The influence of several variables was investigated to optimize the potentiometric response and selectivity of the electrode. The resulting electrode demonstrates a near-Nernstian response over a wide range of salicylate concentration (10(-6)-10(-1) M). This electrode has a fast response time and micromolar detection limit and could be used over a wide pH range (3-9). The proposed electrode showed very high selectivity for salicylate over a number of common inorganic and organic anions. The specific interaction of salicylate with the central metal of porphyrin is described based on UV-visible absorption spectra. The electrode was successfully applied to the determination of salicylate in pharmaceutical preparations and clinical samples.     

Studies of a membrane aerated bioreactor for wastewater treatment

This study was undertaken specifically to collect engineering and process performance information on the behaviour of a membrane supported bio-film in a well-characterised bioreactor. A novel membrane aerated bioreactor has been tested in the laboratory on synthetic sewage, and also piloted for the treatment of primary effluent at a local municipal wastewater treatment plant. The reactor's design employs gas-permeable, hollow-fibre membranes that are submerged in the wastewater. Air is blown through the inside of the fibres. Aeration costs for such a reactor are likely to be lower than conventional systems because gas compression is not required. Thick bio-films grow on the outside of the fibres and effectively treat the wastewater. The bio-films grown in this manner are capable of biological oxygen demand (BOD) removal, nitrification, denitrification, and simultaneous sludge digestion. The character of the bio-film is very different from conventional bio-films grown on inert surfaces, since in this case the bio-film receives its oxygen and the wastewater components from different directions. In pilot studies, a reactor having a hydraulic residence time of 6.5 h and equipped with no sedimentation tank achieved 70–75% BOD and nitrogen removal, and produced an effluent containing less than 30 mg/l total suspended solids.     

Disposable planar reference electrode based on carbon nanotubes and polyacrylate membrane

In this technical note, we report a new all-solid-state planar reference electrode based on single-walled carbon nanotubes and photocured poly(n-butylacrylate) (poly(nBA)) membrane containing the Ag/AgCl/Cl(-) ion system. Single-walled carbon nanotubes functionalized with octadecylamide (SWCNT-ODA) and deposited by drop-casting onto a disposable screen-printed electrode are an excellent all-solid-state transducer. The novel potentiometric planar reference electrode shows low potential variability (calibration slopes inferior to 2 mV/dec) for a wide range of chemical species (i.e., ions, small molecules, proteins) in a wide calibration range, redox pairs, changes in pH, and changes in ambient light. Potentiometric medium-term signal stability (-0.9 ± 0.2 mV/h) and electrochemical impedance characterization confirm the correct solid contact between the SWCNT-ODA layer and photocured poly(nBA) membrane. Overall, the materials used and the simple fabrication by screen-printing and drop-casting enable a high throughput and highly parallel and cost-effective mass manufacture of the new disposable reference electrode. Moreover, the reference electrode has a long shelf life, a characteristic that can be of special interest in decentralized and multiplexing potentiometric analysis.     

Fabrication of a nanosize-Pt-embedded membrane electrode assembly to enhance the utilization of Pt in proton exchange membrane fuel cells

A procedure to locate the Pt nanostructure inside the hydrophilic channel of a Nafion membrane was developed in order to enhance Pt utilization in PEMFCs. Nanosize Pt-embedded MEA was constructed by Cu electroless plating and subsequent Pt electrodeposition inside the hydrophilic channels of the Nafion membrane. The metallic Pt nanostructure fabricated inside the membrane was employed as an oxygen reduction catalyst for a PEMFC and facilitated effective use of the hydrophilic channels inside the membrane. Compared to the conventional MEA, a Pt-embedded MEA with only 68% Pt loading showed better PEMFC performance.     

微型支撑双层类脂膜pH电极的研制

把对氢质子敏感的四氯对位苯醌 (TCPBQ)置于在不锈钢丝末端的双层类脂膜 (s -BLM)里 .然后将这种固体支撑的s -BLM作为工作电极 ,Ag -AgCl电极作为参比电极 ,在各种pH水溶液里测得的电动势与pH的关系符合Nernst公式 .这种s -BLM电极易于制备 ,尺寸很小 (直径只有 0 .2mm) ,能在两天内保持稳定 .用这种电极对常规pH计难以测定的水包油型乳状液的pH作了测定 ,得到较好的结果 .     

New membrane for copper-selective electrode incorporating a new thiophosphoril-containing macrocycle as neutral carrier

The new macrocycles 4-phenyl-11-(1-oxodecyl)-1,7-dithia-11-aza-4-phosphacyclotetradecane (III) and 4-phenyl-4-sulfide-11-(1-oxodecyl)-1,7-dithia-11-aza-4-phosphacyclotetradecane (IV) have been synthesised and characterised. Through their use as ionophore in an all-solid state poly(vinylchloride) matrix membrane electrode, the ability of IV as cation receptor has been studied. The electrode exhibits a Nernstian response towards copper (II) ions with a cationic slope of 30.7 ± 1.7 mV per decade, over the concentration range 3.0 × 10^− 6 to 1.0 × 10^− 2 M and the potential response remains almost unchanged over the pH range 3.9–6.4. The electrode can be used for at least seven months without a considerable alteration in its potential.     

A comparative study on fabrication of Mn2 + selective polymeric membrane electrode and coated graphite electrode

Poly(vinyl chloride)-based membranes of two ligands 2,4-bis(2-acetoxybenzylamino)-6-phenyl-1,3,5-triazine (L₁) and N2,N4-di(cyanoethyl)-2,4-bis(2-acetoxybenzylamino)-6-phenyl-1,3,5-triazine (L₂) were fabricated and explored as Mn^2 + ion selective electrodes. The performance of the polymeric membranes electrodes of ionophores with different plasticizers (dibutylphthalate, benzoic acid, o-nitrophenyloctyl ether, 1-chloronapthalene and tri-n-butylphosphate) and anion excluders (sodium tetraphenylborate and potassium tetrakis p-(chloro phenyl)borate) was looked in to and the better results were obtained with the membrane having composition L₂: NaTPB: DBP: PVC as 6: 3: 56: 35 (w/w; mg). The coated graphite electrode (CGE) with same composition was also fabricated and investigated as Mn^2 + selective electrode. It was found that CGE showed better response characteristics than PME. The potentiometric response of CGE was independent of pH in the range 3.0–9.0 exhibiting the Nernstian slope 29.5 ± 0.3 mV decade^? 1 of activity and working concentration range 4.1 × 10^? 7–1.0 × 10^? 1 mol L^? 1 with a limit of detection 6.7 × 10^? 8 mol L^? 1. The electrode showed a fast response time of 12 s with a shelf life of 105 days. The proposed CGE could be successfully used for the determination of Mn^2 + ions in different water, soil, vegetables and medicinal plants also used as an indicator electrode in potentiometric titration with EDTA.     

基膜活化对β-PbO2-SPE复合膜电极制备过程的影响

基膜活化过程由净化过程和溶胀过程两部分组成,是以Nafion324为基膜制备β-PbO2-SPE复合膜电极的重要环节.实验确定出了基膜净化过程的顺序和方法,并借助于具体的β-PbO2沉积过程,通过SEM,EDS,DC照片和XRD分析,证明在3.0 mol/L NaOH溶液中浸泡25天可以使基膜充分溶胀,更有利于β-PbO22沉积.实验结果同时显示,按上述方法活化基膜可以得到β-PbO2沉积量多,致密,表面积大,性能较为优良的复合膜电极.     

正渗透膜用于橙汁浓缩及其污染研究

正渗透因其低能耗及低污染等优点,已在越来越多的领域得到应用.利用自制的醋酸纤维素正渗透膜应用于橙汁的浓缩,主要考察了不同汲取液、膜方位对浓缩过程的影响,并且研究了浓缩过程中的膜污染现象.结果表明,采用3 mol/L葡萄糖+2 mol/L NaCl混合溶质所配制的汲取液的通量较高,同时盐的反向渗透通量明显降低,浓缩14 h后总可溶物由11.5°Brix上升到40.5°Brix;同时还发现,FO模式下产生的稀释的内浓差极化对水通量的影响要小于PRO模式下产生的浓缩的内浓差极化.在浓缩过程中存在较轻的膜污染,清洗之后通量基本恢复,每6h清洗一次,浓缩25 h后总可溶物可从11.5°Brix达到48.0°Brix.     

Stripping analysis of nanomolar perchlorate in drinking water with a voltammetric ion-selective electrode based on thin-layer liquid membrane

A highly sensitive analytical method is required for the assessment of nanomolar perchlorate contamination in drinking water as an emerging environmental problem. We developed the novel approach based on a voltammetric ion-selective electrode to enable the electrochemical detection of "redox-inactive" perchlorate at a nanomolar level without its electrolysis. The perchlorate-selective electrode is based on the submicrometer-thick plasticized poly(vinyl chloride) membrane spin-coated on the poly(3-octylthiophene)-modified gold electrode. The liquid membrane serves as the first thin-layer cell for ion-transfer stripping voltammetry to give low detection limits of 0.2-0.5 nM perchlorate in deionized water, commercial bottled water, and tap water under a rotating electrode configuration. The detection limits are not only much lower than the action limit (approximately 246 nM) set by the U.S. Environmental Protection Agency but also are comparable to the detection limits of the most sensitive analytical methods for detecting perchlorate, that is, ion chromatography coupled with a suppressed conductivity detector (0.55 nM) or electrospray ionization mass spectrometry (0.20-0.25 nM). The mass transfer of perchlorate in the thin-layer liquid membrane and aqueous sample as well as its transfer at the interface between the two phases were studied experimentally and theoretically to achieve the low detection limits. The advantages of ion-transfer stripping voltammetry with a thin-layer liquid membrane against traditional ion-selective potentiometry are demonstrated in terms of a detection limit, a response time, and selectivity.     

聚四氟乙烯中空纤维膜的制备

通过聚四氟乙烯(PTFE)树脂糊料挤出和拉伸烧结成型方法,制备PTFE中空纤维膜.考察了拉伸倍数、温度和速度等拉伸工艺和烧结工艺对PTFE中空纤维膜的结构和性能的影响.实验结果表明,制膜参数中,随着拉伸倍数和温度的增加,平均孔径和孔隙率增加,泡点降低;随拉伸速度增大,膜平均孔径变小,泡点增加,拉伸速度对孔隙率的影响则呈现无规律变化;烧结可提高PTFE中空纤维膜的强度,孔径和孔隙率增加.PTFE中空纤维膜具有明显的非对称结构.     

PVC超滤膜处理生活污水及膜污染控制研究

为了研究PVC中空纤维超滤膜直接处理高浓度污水的能力以及膜污染的控制方法,实验将PVC超滤膜采用错流过滤直接处理某污水处理厂生活污水,并采用脉冲进料控制膜污染.结果表明,生活污水经三级过滤后,相关指标达到一级A排放标准:污水浊度降到0.1NTU以下:CODr由120.97 mg/L降到47.34 mg/L,去除率为60.9％;DOC由8.95 mg/L降到4.08 mg/L,去除率为54.4％;细菌截留率为99.6％.实验研究表明,采用低频脉冲进料可以有效提高膜表面的剪切力,缓解超滤膜的污染,与连续运行方式相,低频脉冲进料能提高膜的平衡通量近2倍.     

Voltammetric heparin-selective electrode based on thin liquid membrane with conducting polymer-modified solid support

A novel, solid-supported voltammetric ion-selective electrode to detect anticoagulant/antithrombotic heparin at polarizable poly(vinyl chloride) (PVC) membrane/water interfaces was developed. An approximately 3-4.5-microm-thick PVC membrane plasticized with 2-nitrophenyl octyl ether was supported on a gold electrode modified with a poly(3-octylthiophene) (POT) film as an ion-to-electron transducer. Charge transport through the PVC-covered POT film is electrochemically reversible, as demonstrated by cyclic voltammetry with nonpolarizable membrane/water interfaces. In addition to the fast charge transport, adequate redox capacity of the POT film and a small ohmic potential drop in the thin PVC membrane enable ion transfer voltammetry at polarizable macroscopic membrane/water interfaces in a standard three-electrode cell. Reversible ClO4- transfer at the interfaces coupled with oxidation of a neutral POT film was examined by cyclic voltammetry to determine the distribution of the applied potential to the two polarizable interfaces by convolution technique. Interfacial adsorption and desorption of heparin facilitated by octadecyltrimethylammonium were studied also by cyclic voltammetry and convolution technique to demonstrate that the processes are electrochemically irreversible. Stripping voltammetry based on the interfacial processes gives a low detection limit of 0.005 unit/mL heparin in a saline solution, which is slightly lower than the detection limit of most sensitive heparin sensors reported so far (0.01 unit/mL).