Direct methanol fuel cells : Methanol crossover and its influence on single DMFC performance

In the present investigation, the methanol crossover rate through Nafion®-115 membrane at different temperatures and different concentrations had been investigated in a fuel cell test apparatus by using gas chromatography analysis. The singledirect methanol fuel cell (DMFC) tests were carried out to investigate the effect of the concentration of methanol aqueous solutions and cell temperature on methanol crossover and consequently, on the open circuit voltage and the cell performance of DMFC. It can be found that the methanol crossover rate through Nafion® membrane increases as methanol concentration and temperature increase. It can also be found that methanol crossover presented a negative effect on the open circuit voltage and the single DMFC performance. Single DMFC test results showed that an improved cell performance was obtained as temperature increased although the methanol crossover rate increased with temperature increment.     

Implication of the role of oxygen anions and oxygen vacancies for methanol decomposition over zirconia supported copper catalysts

The interaction of methanol with Cu, monoclinic ZrO₂, and Cu/m-ZrO₂ catalysts has been investigated by temperature programmed desorption (TPD) and reaction (TPRS) with the aim of understanding the nature of the surface sites and the mechanism involved in methanol decomposition. A synergetic effect has been detected since the combination of copper and ZrO₂ significantly facilitates the methanol decomposition with the facile evolution of H₂ and CO species at much lower desorption temperature. In conjunction with DRIFTS and H₂-TPD measurements of the Cu/ZrO₂ sample reduced at elevated temperatures, methanol decomposition over Cu/ZrO₂ is suggested to occur primarily on ZrO₂ with the aid of the presence of oxygen anions and oxygen vacancies generated by species-spillover between copper and zirconia. The interface between copper and zirconia is also evidenced to be crucial to the decomposition of methanol, with the main role of metallic Cu being to provide sites for H₂ removal by efficiently recombining the hydrogen atoms formed during the dehydrogenation of species located on zirconia.     

Pt/TiO2催化剂的载体结构对甲醇催化氧化性能的影响

二氧化钛载体包括二氧化钛纳米管阵列(TNTAs)和二氧化钛纳米线阵列(TNWAs)两种,载体的结构不同对催化性能有一定的影响。然而,Pt负载在TNTAs和TNWAs催化性能的比较鲜有报道。本文通过微波法制备了Pt/TNTAs和Pt/TNWAs两种催化剂,结果表明,Pt/TNTAs催化甲醇氧化效果要优于Pt/TNWAs。相较于Pt/TNWAs, Pt/TNTAs的优越催化性能可能与纳米管的限域效应有关。可见,载体的结构对催化剂的性能有很大的影响。     

Improved Pt/C electrocatalysts for methanol oxidation prepared by different reducing agents and surfactants and DFT studies on it

In this work, PtCl₄ as precursor; sodium borohydride (Cat I), hydrazinium hydroxide (Cat II), and formaldehyde (Cat III) as reducing agents; and 1-heptanamine (a), N-methyl-1-heptanamine (b), and N,N-dimethyl-1-heptanamine (c) as surfactants were used to prepare platinum nanoparticles which were then dispersed on carbon XC-72 for use as catalysts in the methanol oxidation reaction. XRD and TEM results indicate that the platinum has a face-centered cubic structure and is found as small and agglomerated particles in different shapes, sizes, and densities. Cat I comprises small (~?5 nm) cubic and formless agglomerated (~?20–~?300 nm) particles, Cat II is composed of small (~?5 nm) and a significant number of quite dense spherical agglomerated (~?20–~?150 nm) particles, and Cat III contains large number of small (~?5 nm) and a small number of spherical, less dense, and agglomerated (~?20–~?200 nm) particles. XPS data shows that the platinum exists in two different oxidation states Pt(0) (~?64.5–~?69.6%) and Pt(IV) (~?35.5–~?30.4%), and platinum surface also contains OH, H₂O, C–O, C=O, and carbon. DFT and FTIR show that the surfactants decompose to form partially crystalline carbon. Electrochemical studies reveal that performance order of the catalysts towards the methanol oxidation reaction is Cat II < Cat I < Cat III, and that Cat IIIc has the highest performance, which is 2.23 times larger than E-TEK catalysts. It was found that the performance of the catalysts depends on the kind of surfactant, reducing agent, electrochemical surface area, percent platinum utility, roughness factor, and I_f/I_r ratio.

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The dependence of Co nanoparticle sizes on the ratio of surfactants and the influence of different crystal sizes on magnetic properties

Monodisperse cobalt nanoparticles were synthesized by high-temperature reduction of solution-phase cobalt chloride in the presence of a pair of surfactants, oleic acid and triphenylphosphine. Highly ordered two-dimensional superlattices of passivated cobalt nanoparticles were formed by a self-assembly technique. Analysis by X-ray diffraction, UV-vis absorption spectroscopy and transmission electron microscopy demonstrated that the size of the cobalt nanocrystals could be tuned by tailoring the concentration ratio of the two surfactants. In addition, the influence of different crystal sizes on magnetic properties of Co nanocrystals was also investigated. PACS 75.60.Nt; 75.50.Tt     

Carbon monoxide oxidation over well-defined Pt/ZrO2 model catalysts: Bridging the material gap

Four different Pt/ZrO₂/(C/)SiO₂ model catalysts were prepared by electron beam evaporation. The morphology of these samples was examined before and after the catalytic reaction by Rutherford back-scattering (RBS), transmission electron microscopy (TEM) and grazing-incidence small-angle scattering (GISAXS). The catalytic behavior of such model catalysts was compared to a conventional Pt/ZrO₂ catalyst in the CO oxidation reaction using different oxygen excess (λ = 1 and 2). The so-called material gap was observed: model catalysts were active at higher temperature (620-770 K) and resulted in higher activation energy values (E_a = 77-93 kJ mol⁻¹ at λ = 1 and 129-141 kJ mol⁻¹ at λ = 2) compared to the powdered Pt/ZrO₂ catalyst (370-470 K, E_a = 74-76 kJ mol⁻¹). This material gap is discussed in terms of diffusion limitations, reaction mechanism and apparent compensation effect. Diffusion processes seem to limit the reaction on planar samples in the reactor system that was shown to be appropriate for the evaluation of the catalytic activity of powder samples. Kinetic parameters obeyed the so-called apparent compensation effect, which is discussed in detail. Langmuir-Hinshelwood-type of reaction, between CO_ads and O_ads, was proposed as the rate-determining step in all cases. Pt particles deposited on planar structures can be used for modeling conventional powdered catalysts, even though some limitations must be taken into account.     

Analogous materials for studying spent nuclear fuel: The influence of particle size distribution on the specific surface area of irradiated nuclear fuel

Knowledge of the reactive surface that a given material presents to reactive species is one of the fundamental factors for the discussion of experimental data from the alteration of a solid at laboratory scale, or the extrapolation to different environmental conditions. The reactive surface depends on several factors such as the origin of the solid, for example, history of irradiation, the particle size distribution and the history of its reactive surface.Here we discuss the relation between the particle size distribution and the specific surface area for different uranium oxides, namely, irradiated fuel, SIMFUEL and several fresh - non-irradiated - uranium oxides. The analysis is made comparing our own data with values reported in the literature. Our analysis strongly suggests that it is necessary to establish the surface area time evolution in order to model its behaviour in different scenarios where the alteration process will happen. Moreover, this is required in both, dry and wet conditions. A first step to get this function is the determination of the particle size distribution dependence of the specific surface area.     

Electrocatalysis of oxygen reduction reaction on Nafion/platinum/gas diffusion layer electrode for PEM fuel cell

In this work a new membrane electrode based on Pt-coated Nafion membrane was fabricated. Chemical deposition process was used to coat platinum on Nafion 117 membrane and then Pt-coated Nafion membrane was hot pressed on gas diffusion layer (GDL) to make new membrane electrode. The electrochemical and chemical studies of the Pt-coated Nafions were investigated by electrochemical techniques, X-ray diffraction and scanning electron microscopy. The electrochemical results indicated that as the concentration of H₂PtCl₆ increased, the oxygen reduction reaction rate increased until the concentration was reached where the reduction reaction was limited by the problem of mass transport. The electrochemical results for oxygen reduction reaction showed that the new electrode which prepared by plating Nafion membrane with 0.06 M H₂PtCl₆ in electroless plating solution, has a higher performance than other electrodes. The XRD results showed that the average platinum particle size of the best sample was about 3 nm. The loading of platinum for this electrode was 0.153 mg cm⁻².     

Direct reaction of adsorbed molecular oxygen with hydrazine on a clean Pt(111) surface

The oxidation of hydrazine on the clean Pt(111) surface has been investigated by temperature-programmed reaction spectroscopy (TPRS) in the temperature range 130–800 K. Direct reaction of molecular oxygen is observed on the Pt(111) surface for the first time, as indicated by the desorption of nitrogen beginning at 130 K with a maximum rate at 145 K, below the molecular oxygen dissociation temperature. Direct reaction of hydrazine with adsorbed molecular oxygen results in the formation of water and nitrogen. With excess hydrazine, all surface oxygen is reacted, forming water. When only adsorbed atomic oxygen is present, the low-temperature nitrogen yield decreases by a factor of 3 and the peak nitrogen desorption temperature increases to 170 K. No high-temperature (450–650 K) nitrogen desorption characteristic of nitrogen atom recombination is seen, indicating that during oxidation the nitrogen-nitrogen bond in hydrazine remains intact, as observed previously for hydrazine decomposition on the Pt(111) surface and hydrazine oxidation on rhodium. Two water desorption peaks are observed, characteristic of desorption-limited (175 K) and reaction-limited (200 K) water evolution from the Pt(111) surface. For low coverages of hydrazine, only the reaction-limited water desorption is observed, previously attributed to water formed from adsorbed hydroxyl groups. When excess hydrazine is adsorbed, the usual hydrazine decomposition products, H₂, N₂ and NH₃, are also observed. No nitrogen oxide species (NO, NO₂ and N₂O) were observed in these experiments, even when excess oxygen was available on the surface.     

The influence of potassium and the role of coadsorbed oxygen on the chemisorptive properties of Pt(100)

The adsorption of K on Pt(100) has been followed by thermal desorption spectroscopy (TDS) and Auger electron spectroscopy (AES); carbon monoxide was used as a probe for the modification of the chemical properties of K promoted surfaces. The role of subsequent adsorption of oxygen on the K modified surfaces has also been measured. For low potassium coverage (θ_K = 0 to 0.35), the mass-28 TDS peak temperature of adsorbed CO increases continuously with the K coverage, indicating an increase of the adsorption energy of CO which has been explained by a substantial charge donation from K into the $\text{2π}{}^1$ orbitals of CO via long range interactions through the platinum substrate. No oxygen uptake was detected after oxygen exposure at room temperature. For high potassium content (θ_K = 0.45 to 1), the mass-28 TDS peak temperature of coadsorbed CO is very narrow and remains constant at 680 K. We propose the formation of a COKPt surface complex which decomposes at 680 K, since K desorption is detected concomitantly to CO. On such K covered surfaces, the oxygen uptake is promoted, and it cancels the modifications of the surface properties induced by potassium.     

Electrochemical promotion of the NO reduction by C2H4 on Pt/YSZ and by CO on Pd/YSZ

The effect of electrochemical promotion was investigated for the catalytic reduction of nitric oxide with ethylene and carbon monoxide on polycrystalline Pt and Pd, respectively, deposited on yttria-stabilized zirconia (YSZ). It was found in both cases that applying negative potentials and thus lowering the catalyst work function results in a pronounced increase in the catalytic rate and in the selectivity to nitrogen. A 7-fold increase was observed for the NO+C₂H₄ reaction on Pt while a 2-fold increase was obtained for the NO+CO reaction on Pd. The induced changes in catalytic rates were found to be 7 to 50 times higher than the rates of ion transfer from the catalyst surface. In both reactions, the observed electrophilic behavior can be attributed to the strengthening of the chemisorptive NO bond and concomitant enhanced dissociation of NO as the catalyst potential and work function is decreased. Forced periodic oscillations of the applied current was investigated and resulted in a enhanced production of CO₂, but an intermediate selectivity towards N₂, as compared to constant current application. The effect of the cycling waveform, frequency and amplitude was studied and provided evidence that the synergy observed during the cycling experiment results from a favorable transient coverage of adsorbed species on the catalyst surface as the catalyst potential oscillates from negative to positive values. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Effect of Fe state on electrocatalytic activity of Pd-Fe/C catalyst for oxygen reduction

The carbon-supported Pd-Fe catalyst (Pd-Fe/C) is prepared in the H₂O/tetrahydrofuran (THF) mixture solvent under the low temperature. The homemade Pd-Fe/C catalyst contains two forms of iron species, alloying and non-alloying Fe. The alloying Fe species is hardly dissolved in 0.5 M H₂SO₄ solution, while the non-alloying Fe species is easily dissolved in 0.5 M H₂SO₄ solution. The electrochemical measurements show the electrocatalytic activity of the Pd-Fe/C catalyst with the acid treatment for the oxygen reduction is higher than that of the Pd-Fe/C catalyst without the acid treatment, illustrating that the non-alloying Fe species suppresses the electrocatalytic activity of the Pd-Fe/C catalyst. In contrast, the alloying Fe species promotes the electrocatalytic activity of the Pd-Fe/C catalyst for the oxygen reduction, which is likely attributed to the change of the electron structure of Pd atom and/or bond length of Pd-Pd in the Pd-Fe/C catalyst.     

High-resolution DOSY NMR with spins in different chemical surroundings: influence of particle exchange

The effect of chemical exchange in the diffusion-ordered (DOSY) spectra of a two-site system in the slow-exchange limit with respect to the chemical shift is studied. The problem is addressed both theoretically and experimentally. The relationship between diffusion time (t) and mean lifetimes (tau) is studied by the simulation of the magnetization attenuations as a function of the gradient strength, under PFG conditions. The influence of the difference in populations and diffusion coefficients of the two sites is also considered. In analogy to the limiting cases of fast- and slow-exchange with respect to the chemical shift, limiting cases with respect to the diffusion dimension are defined. The slow-exchange limit in diffusion corresponds to the relation of t and tau that allows us to observe the two spins in exchange associated with the individual diffusion coefficients of the two sites when no exchange is present. The fast-exchange limit in diffusion is reached when the relation of t and tau is such that the two spins present the same apparent diffusion coefficient. By using a model system consisting of water/t-butanol it is shown that by recording several DOSY experiments with increasing diffusion times it is possible to estimate the value of the exchange rate.     

The influence of radiation heat exchange on characteristics of liquid fuel ignition by a heated metal particle

A complex of interrelated heat-mass transfer processes at gas-phase ignition of a typical liquid fuel by a hot metal particle immersed partially into a liquid is investigated numerically. The scale of influence of the radiation heat exchange at particle—liquid fuel and particle—gas—vapor mixture interfaces is found. Conditions under which the impact of this factor can be neglected are determined.     

直接模拟中不同边界条件的实施及对沉降规律的影响

在牛顿流体中, 对颗粒在4种不同边界的垂直通道中的沉降运动进行了直接数值模拟. 计算结果表明:通过计算区域随颗粒运动而移动构建的无限长通道能准确模拟颗粒自由下落到稳定沉降的发展过程; 周期性边界条件由于流场变化, 对颗粒沉降产生了影响, 不能模拟颗粒的自由沉降过程; 底部封闭边界适合模拟封闭容器内颗粒与固壁的相互作用过程, 若颗粒达到稳定沉降, 也能模拟无限长通道内的沉降过程; 流化边界适合模拟流化床内气固两相流动. 计算结果有助于更好地理解和使用不同边界条件. 关键词： 直接数值模拟 边界条件 沉降 任意拉格朗日-欧拉方法     

The effect of statistical variance of particle sizes on the properties of a metafilm

The spectral characteristics of a set of square planar arrays of spherical ferroelectric barium titanate particles embedded in extruded polysterene foam have been investigated. Considerable differences are observed between the measured transmission and reflection coefficients and the corresponding calculated values for a metafilm with identical particles. This discrepancy is caused by the statistical variance of the resonant frequencies of spherical particles. Good agreement with experimental data is obtained by statistical averaging of the calculated parameters of metafilms over an ensemble of ideal arrays.     

Direct pyrolysis and ultrasound assisted preparation of N,S co-doped graphene/Fe3C nanocomposite as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions

Bifunctional electrocatalysts to enable efficient oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential for fabricating high performance metal–air batteries and fuel cells. Here, a defect rich nitrogen and sulfur co-doped graphene/iron carbide (NS-GR/Fe₃C) nanocomposite as an electrocatalyst for ORR and OER is demonstrated. An ink of NS-GR/Fe₃C is developed by homogeneously dispersing the catalyst in a Nafion containing solvent mixture using an ultrasonication bath (Model-DC150H; power − 150 W; frequency − 40 kHz). The ultrasonically prepared ink is used for preparing the electrode for electrochemical studies. In the case of ORR, the positive half-wave potential displayed by NS-GR/Fe₃C is 0.859 V (vs. RHE) and for the OER, onset potential is 1.489 V (vs. RHE) with enhanced current density. The optimized NS–GR/Fe₃C electrode exhibited excellent ORR/OER bifunctional activities, high methanol tolerance and excellent long-term cycling stability in an alkaline medium. The observed onset potential for NS–GR/Fe₃C electrocatalyst is comparable with the commercial noble metal catalyst, thereby revealing one of the best low-cost alternative air–cathode catalysts for the energy conversion and storage application.     

热对流条件下固液密度比对颗粒沉降运动影响的直接数值模拟

本文应用任意拉格朗日-欧拉(ALE)算法对固液两相流流场中考虑热对流的非等温颗粒在竖直通道中的沉降运动进行了数值模拟.在牛顿流体中通过积分黏性应力和压力获得颗粒的受力跟踪颗粒运动,使用有限元方法数值求解流场的N-S方程和能量方程,模型不需经验假设.通过模拟来研究颗粒沉降的运动规律和热对流下固液密度比对固液两相流的影响作用.结果表明随着固液密度比的增加,颗粒经历了稳定沉降、周期性摆动,不规则摆动等过程;热对流使颗粒的摆动幅度和沉降速度发生变化;热对流对颗粒的影响作用随着固液密度比的增加而减小.     

The adsorption of hydrogen and the reaction of hydrogen with oxygen on Pt (100)

The adsorption of hydrogen on Pt (100) was investigated by utilizing LEED, Auger electron spectroscopy and flash desorption mass spectrometry. No new LEED structures were found during the adsorption of hydrogen. One desorption peak was detected by flash desorption with a desorption maximum at 160 °C. Quantitative evaluation of the flash desorption spectra yields a saturation coverage of 4.6 × 10¹⁴ atoms/cm² at room temperature with an initial sticking probability of 0.17. Second order desorption kinetics was observed and a desorption energy of 15–16 kcal/mole has been deduced. The shapes of the flash desorption spectra are discussed in terms of lateral interactions in the adsorbate and of the existence of two substates at the surface. The reaction between hydrogen and oxygen on Pt (100) has been investigated by monitoring the reaction product H₂O in a mass spectrometer. The temperature dependence of the reaction proved to be complex and different reaction mechanisms might be dominant at different temperatures. Oxygen excess in the gas phase inhibits the reaction by blocking reactive surface sites. At least two adsorption states of H₂O have to be considered on Pt (100). Desorption from the prevailing low energy state occurs below room temperature. Flash desorption spectra of strongly bound H₂O coadsorbed with hydrogen and oxygen have been obtained with desorption maxima at 190 °C and 340 °C.     

Investigation on thermal conductivity of graphene/Si heterostructure with different defect ratios and sizes

The thermal conductivity (TC) of graphene/Si heterostructures with different defect ratios and sizes was investigated using the molecular dynamics method. As the defect ratio of heterostructure increased, the TC decreased first sharply and then slowly under a high temperature stage. The TC of heterostructure also showed a significant size effect. This phenomenon was explained by phonon dispersion and flip competition. The phonon density of states for the graphene heterostructure with different defect ratios and sizes was obtained to understand the thermal transport mechanism. Analysis showed that with the increase in the defect ratio and when the flexural modes of the heterostructure became weak, the longitudinal and transverse modes gradually dominated the phonon transport. This phenomenon can be explained that the Si atom vibration was harder in the vertical plane than that of graphene. The vibration mode hindered the heat carrier of graphene and affected heat transport to the heterostructure.