The use of 1H NMR microscopy to study proton-exchange membrane fuel cells.

To understand proton-exchange membrane fuel cells (PEMFCs) better, researchers have used several techniques to visualize their internal operation. This Concept outlines the advantages of using 1H NMR microscopy, that is, magnetic resonance imaging, to monitor the distribution of water in a working PEMFC. We describe what a PEMFC is, how it operates, and why monitoring water distribution in a fuel cell is important. We will focus on our experience in constructing PEMFCs, and demonstrate how 1H NMR microscopy is used to observe the water distribution throughout an operating hydrogen PEMFC. Research in this area is briefly reviewed, followed by some comments regarding challenges and anticipated future developments.     

cotpp-pt/c作直接甲醇燃料电池阴极催化剂

四苯基钴卟啉;pt催化剂;直接甲醇燃料电池;氧还原     

Thermodynamic characteristics of solvation of individual ions in ethanol at −50 to 55°C

Experimentally determined are the enthalpies of solution of 12 electrolytes (LiBr, LiI, NaBr, NaI, NaBPh₄, Et₄NCl, Et₄NBr, Pr₄Br, Bu₄NBr, Am₄NBr, Ph₄PCl, Ph₄PBr) in ethanol at –50 to 55°C. _sH^o values obtained on the basis of four different extrapolation equations are analyzed. The effect of temperature changes on the thermodynamic parameters of solvation indindividual ions are calculated using thermodynamic data for the salt crystals (lattice) with the assumption that _solvC _p ^o (Ph₄P⁺)=_solvC _p ^o (Ph₄P^-).     

Thermodynamic parameters of interaction of HC1 with alcohols in water Ⅲ.HCl-ethanol-water system at 278.15-318.15 K

Pt,H2(g,p0)HCl(mE)|AgCl-AgPt, H2(g, p0)|HCl(mE), EtOH(mN)|AgCl-Ag have been measured at 10 degree intervals from 278.15 to 318.15 K, where EtOH refers to ethanol, mE=0.005-0.1 mol.kg-1, mN=0.4-1.0 mol.kg-1. The salting constant kS of EtOH by HCl and the thermodynamic parameters of interaction, fEN(gEN> hEN, sEN] cP,EN)> of EtOH with HCI in water have been evaluated. It has been shown that kS>0, gEN>0,hEN>0, SEN>0 ,and cp,EN<0.The signs of these parameters and the temperature dependence of them have been discussed on the basis of structural interaction and the group additivity models.     

An NMR study of methanol diffusion in polymer electrolyte fuel cell membranes

Methanol diffusion in two polymer electrolyte membranes, Nafion 117 and BPSH 40 (a 40% disulfonated wholly aromatic polyarylene ether sulfone), was measured using a modified pulsed field gradient NMR method. This method allowed for the diffusion coefficient of methanol within the membrane to be determined while immersed in a methanol solution of known concentration. A second set of gradient pulses suppressed the signal from the solvent in solution, thus allowing the methanol within the membrane to be monitored unambiguously. Over a methanol concentration range of 0.5–8 M, methanol diffusion coefficients in Nafion 117 were found to increase from 2.9 × 10⁻⁶ to 4.0 × 10⁻⁶ cm² s⁻¹. For BPSH 40, the diffusion coefficient dropped significantly over the same concentration range, from 7.7 × 10⁻⁶ to 2.5 × 10⁻⁶cm² s⁻¹. The difference in diffusion behavior is largely related to the amount of solvent sorbed by the membranes. Increasing the methanol concentration results in an increase in solvent uptake for Nafion 117, while BPSH 40 actually excludes the solvent at higher concentrations. In contrast, diffusion of methanol measured via permeability measurements (assuming a partition coefficient of 1) was lower (1.3 × 10⁻⁶ and 6.4 × 10⁻⁷ cm² s⁻¹ for Nafion 117 and BPSH 40 respectively) and showed no concentration dependence. The differences observed between the two techniques are related to the length scale over which diffusion is monitored and the partition coefficient, or solubility, of methanol in the membranes as a function of concentration. For the permeability measurements, this length is equal to the thickness of the membrane (178 and 132 μm for Nafion 117 and BPSH 40 respectively) whereas the NMR method observes diffusion over a length of approximately 4–8 μm. Regardless of the measurement technique, BPSH 40 is a greater barrier to methanol permeability at high methanol concentrations.     

吸热型碳氢燃料在银、镧改性混合分子筛上的裂解研究

为进一步提高吸热型碳氢燃料的吸热能效，考察了吸热型碳氢燃料NNJ－150在USHY和HZSM－5混合分子筛以及银、镧改性混合分子筛催化剂上的催化裂解。结果表明，在Ag-LaUSY Ag-LaZSM-5(75:25)混合分子筛催化NNJ－150裂解反应中，低碳烯烃选择性较高，催化剂寿命较长。采用此催化剂，能较好满足吸热型碳氢燃料裂解的需要。     

Pervaporative transport modelling in a ternary system: ethyltertiarybutylether/ethanol/polyurethaneimide

The study deals with the analysis of diffusion and mass transfer modelling during pervaporation in a true ternary system involving a polar liquid mixture (ETBE/EtOH) and a polar block copolymer (polyurethaneimide or PUI). A survey of methods of pervaporative transfer modelling in ternary systems is first developed. From differential permeation experiments carried out with both pure liquids, it appears that both permeants obey a Fickian law. Moreover, the diffusional behaviour is consistent with Long's model, which has thus been assumed for the related ternary system. An extension of the Brun's model is then derived, which takes into account the diffusion coupling as well the significant deviation from sorption ideality. From a practical point of view, the calculated values of fluxes show generally good agreement with the experimental results, although a small deviation occurs for mixtures of low ethanol content. Diffusion coefficients of both pure solvents corresponding to transient or steady state are compared. A very good agreement is found for the aprotic permeant (ETBE). whereas the diffusion coefficient of ethanol in transient state is only the quarter of the value corresponding to steady state. The results are discussed in comparison with related investigations in the literature, involving specific liquid-polymer interactions.     

Dielectric Relaxation Study of Liquids Having Chloro Group with Associated Liquids. I. Chlorobenzene with Methanol, Ethanol, and 1-Propanol

The complex permittivity for chlorobenzene–alcohol binary mixtures have been determined over the frequency range of 10 MHz to 20 GHz, at 15, 25, 35, and 45°C, using the time-domain reflectometry (TDR) method for 11 concentrations of each chlorobenzene–alcohol system. The alcohols used were methanol, ethanol, and 1-propanol. The values of static dielectric constant, relaxation time, the corresponding excess properties, the Redlich–Kister coefficients up to the third order, the Kirkwood correlation factor, and thermodynamic parameters of the mixtures have been determined. The excess permittivity is found to be negative for chlorobenzene–methanol and chlorobenzene–ethanol, whereas it is positive in the 1-propanol rich region. The excess inverse relaxation time is negative for all the systems studied here. The Kirkwood effective correlation factor increases with an increasing in the molecular size of the alcohol, but decreases with increasing temperature.     

高密度燃料HDF-1与橡胶的相容性研究

报道了在室温和70 ℃下橡胶材料G402氟硅胶、丁腈胶5171、丁腈胶4170、贮囊橡胶用合成的高密度燃料HDF-1浸泡后性能如伸长率、邵尔硬度、重量、面积体积的变化，并与采用3号喷气燃料（RP-3）实验结果进行对照。用红外光谱测定了燃料浸泡前后橡胶组成的变化。实验结果表明，G402氟硅胶和贮囊对于HDF-1和RP-3有相近的相容性，丁腈胶5171对HDF-1的相容性比对RP-3的相容性稍差，丁腈胶4170对HDF-1的相容性比对RP-3的相容性更差的结果。因此，丁腈胶5171和丁腈胶4170不能用于HDF-1储存和输送，原使用RP-3系统的橡胶密封件不能直接使用HDF-1。     

高分散直接甲醇燃料电池Pt／C阴极电催化剂的制备过程机理与表征

 通过调变的多元醇法制备了40％Pt／C直接甲醇燃料电池阴极电催化剂，应用透射电镜（TEM）及X射线衍射（XRD）方法表征催化剂．结果表明，由该制备方法可得到高分散，金属粒子粒径分布窄的高载量贵金属催化剂．TEM统计结果表明，调变多元醇法制备的40％Pt／C催化剂的金属粒子平均粒径约为2．9nm．直接甲醇燃料电池单池性能测试表明，该方法制得的40％Pt／C的电催化氧还原能力比同型商品催化剂更好．另外，利用UV－Vis光谱研究了催化剂的制备过程．结果表明，在调变的多元醇法中，Pt4＋的还原是一步完成的．