Low-Field NMR Relaxation Analysis of High-Pressure Ethane Adsorption in Mesoporous Silicas

Understanding the behaviour of short-chain hydrocarbons confined to porous solids informs the targeted extraction of natural resources from geological features, and underpins rational developments in separation, storage and catalytic conversion processes. Herein, we report the application of low-field (12.7 MHz) ¹H nuclear magnetic resonance (NMR) relaxation measurements to characterise ethane dynamics within mesoporous silica materials exhibiting mean pore diameters between 6 and 50 nm. Our measurements provide NMR-based adsorption isotherms within the range 25–50 bar and at ambient temperature, incorporating the ethane condensation point (40.7 bar at our experimental temperature of 23.6 °C). The quantitative nature of the acquired data is validated via a direct comparison of NMR-derived excess adsorption capacities with ex situ gravimetric ethane adsorption measurements, which are demonstrated to agree to within 0.2 mmol g⁻¹ of the observed ethane capacity. NMR relaxation time distributions are further demonstrated as a means to decouple interparticle and mesopore dominated adsorption phenomena, with unexpectedly rapid relaxation rates associated with interparticle ethane gas confirmed via a direct comparison with NMR self-diffusion analysis.     

Simultaneous determination of copper and lead in ethanol fuel by anodic stripping voltammetry

The presence of trace metals in car fuels plays an important role in the engine maintenance. In addition, these metals contribute for the environmental contamination in big cities and their control is necessary. Square Wave Stripping Voltammetry (SWSV) is a very sensitive technique for elemental trace determination and was applied for ethanol fuel analysis. The first studies were done searching for the best conditions for copper determination in alcoholic medium, utilizing gold electrodes. During these studies, the possibility of the simultaneous determination of copper and lead in the same experiment was observed. Two procedures for the analysis of these metals were adopted: The direct quantification of metals in alcohol–water mixtures and a second way that involves the evaporation of the organic solvent and re-suspension of the ions with water+electrolyte. Good recovery values were obtained for synthetic samples spiked with known amounts of metals. The results obtained for the two methods were in good agreement. The detection limits for copper and lead in 75% ethanol–water ratio solution were calculated as 120 and 235 ng l⁻¹, respectively, for 15-min deposition time.     

Reactivity and characterisation of various rank turkish bituminous coal chars

A set of seven bituminous coal chars has been characterised by IR spectroscopy (FTIR), thermogravimetry (TG) and elemental analysis. FTIR study provided suitable information to establish differences between coal samples according to their chemical compositions. The reactivity of these samples was also studied and correlated with the coal parameters of mean vitrinite reflectance, fuel ratio and H/C ratio. The data suggest that reactivity as determined can be correlated with the mean vitrinite reflectance, fuel ratio and H/C ratio (0.90). The order of reactivity of samples were; Amasra (S1) (R _m= 0.65)>Azdavay (S4) (R _m=0.99)»Armutcuk (S2) (R _m=0.81)»Acenta (S3) (R _m=0.92)>Ac2l2k (S6) (R _m=1.11) Cay (S5) (R _m=1.03)>Sogutozu (S7) (R _m=2.14).     

Study of transition metal oxide doped LaGaO3 as electrode materials for LSGM-based solid oxide fuel cells

Transition metal oxide doped lanthanum gallates, La_0.9Sr_0.1Ga_0.8M_0.2O₃ (where M=Co, Mn, Cr, Fe, or V), are studied as mixed ionic-electronic conductors (MIECs) for electrode applications. The electrochemical properties of these materials in air and in H₂ are characterized using impedance spectroscopy, open cell voltage measurement, and gas permeation measurement. Three single cells based on La_0.9Sr_0.1Ga_0.8 Mg_0.2O₃ (LSGM) electrolyte (1.13 to 1.65 mm thick) but with different electrode materials are studied under identical conditions to characterize the effectiveness of the lanthanum gallate-based MIECs for electrode applications. At 800 °C, a single cell using La_0.9Sr_0.1- Ga_0.8Co_0.2O₃ as the cathode and La_0.9Sr_0.1Ga_0.8Mn_0.2O₃ as the anode shows a maximum power density of 88 mW/cm², which is better than that of a cell using Pt as both electrodes (20 mW/cm²) and that of a cell using La_0.6Sr_0.4CoO₃ (LSC) as the cathode and CeO₂-Ni as the anode (61 mW/cm²) under identical conditions. The performance of LSGM-based fuel cells with MIEC electrodes may be further improved by reducing the electrolyte thickness and by optimizing the microstructures of the electrodes through processing. Received: 9 January 1998 / Accepted: 1 May 1998     

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     

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.     

Microwave assisted low temperature synthesis of sodium zirconium phosphate (NaZr<Subscript>2</Subscript>P<Subscript>3</Subscript>O<Subscript>12</Subscript>)

Sodium zirconium phosphate [NaZr₂P₃O₁₂], a potential ceramic matrix for fixation of high level nuclear waste, was synthesized by heating the mixture of sodium carbonate [Na₂CO₃], zirconyl nitrate hydrate [ZrO(NO₃)₂·5H₂O] and ammonium dihydrogen phosphate [NH₄H₂PO₄] in air, in a resistance heated furnace and a microwave heating system respectively in the temperature range 450 to 650°C. The mixture heated for 1 h in a resistance furnace at 450°C yielded a poorly crystalline NaZr₂P₃O₁₂ [NZP]. Increasing the temperature to 650°C produced a highly crystalline product. The same mixture heated in a microwave oven at 450°C for 1 h however, yielded the most crystalline NZP.In an alternate method, the mixture of sodium dihydrogen phosphate (NaH₂PO₄), zirconium dioxide (ZrO₂) and diammonium hydrogen phosphate [(NH₄)₂HPO₄] heated in resistance furnace at 650°C for the same period did not react in air. It also did not yield the pure product at 450°C when heated in microwave assembly for 1 h.The authors thank the Board of Research in Nuclear Sciences (BRNS) of the Department of Atomic Energy (DAE) for the financial support for this work under the project No. 2000/37/19/BRNS/1959 dtd09-02-02.     

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。     

月光花素甲(Ⅰ)、(Ⅱ)整体分子结构的测定

本文对月光花素甲(Calonyctin A)的整体分子结构分析加以完善并进行总结。前文报道月光花素甲是两个分子量相差28a.m.u的糖甙类同系物分子的混合物。这两个分子(简称M_1和M_2)分别称为月光花素甲(Ⅰ)与月光花素甲(Ⅱ)(Calonyctm A_1,CalonyctinA_2),分子量分别为938与910。它们分别含