The preparation of high activity DMFC Pt/C electrocatalysts using a pre-precipitation method

It is suggested that a Pt/C cathodic catalyst for the direct methanol fuel cell (DMFC) can be prepared with a pre-precipitation method, in which, H2PtCl6 is precipitated onto the carbon black as (NH4)(2)PtCl6 before H2PtCl6 is reduced to Pt. The electrocatalytic activity of this Pt/C-A catalyst for oxygen reduction is excellent because the Pt/C catalyst prepared with this pre-precipitation method possesses a small average particle size, low relative crystalinity and a large electrochemically active surface area. In addition, the pre-precipitation method is simple and economical and it can be used to prepare a Pt/C catalyst on a large scale.

A new flow field and its two-dimension model for polymer electrolyte membrane fuel cells (PEMFCs)

A new flow field was designed to search flow fields fitting polymer electrolyte membrane fuel cells (PEMFCs) better due its extensible. There are many independent inlets and outlets in the new flow field. The new flow field we named NINO can extend to be more general when pressures at the inlet and outlet vary and some usual flow fields will be obtained. A new mathematical model whose view angle is obverse is used to describe the flow field.

Room temperature preparation of carbon supported Pt-Ru catalysts

A carbon supported Pt-Ru (Pt-Ru/C-T) catalyst can be prepared by a chemical reduction method in an aqueous solution with tetrahydrofuran (THF) at room temperature. The Pt-Ru particles possess high alloying, small average size and a low relative crystallinity. The electrocatalytic activity of the prepared Pt-Ru/C catalyst for methanol oxidation is much higher than that of commercial Pt-Ru/C (Pt-Ru/C-E) catalysts which have a similar average size and relative crystallinity, but the alloying extent is much lower than that in our Pt-Ru/C-T catalyst. The results illustrate that the alloying extent of Pt and Ru in the Pt-Ru/C catalyst plays an important role in the electrocatalytic activity of the Pt-Ru/C catalyst for methanol oxidation.

Preparation of a carbon supported Pt catalyst using an improved organic sol method and its electrocatalytic activity for methanol oxidation

The organic sol method for preparing ultrafine transition metal colloid particles reported for the first time by Bonnemann et al. [H. Bonnemann, W Brijoux, R. Brinkmann, E. Dinjus, T. Jou beta en, B. Korall, Angew. Chem. Int. Ed. Engl., 30 (1991) 1312] has been improved in this paper. The improved organic sol method uses SnCl2 as the reductant and methanol as the organic solvent. Thus, this method is very simple and inexpensive. It was found that the average size of the Pt particles in the Pt/C catalysts can be controlled by adjusting the evaporating temperature of the solvent. Therefore, the Pt/C catalysts prepared by the same method are suitable for evaluating the size effect of the Pt particles on electrocatalytic performance for methanol oxidation. The results of the X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that when the evaporating temperatures of the solvent are 65, 60, 50, 40, and 30 degrees C, the average sizes of the Pt particles in the Pt/C catalysts prepared are: 2.2, 3.2, 3.8, 4.3, and 4.8 nm, respectively. The X-ray photoelectron spectroscopic (XPS) results demonstrated that the small Pt particles are easily oxidized and the decomposition/adsorption of methanol cannot proceed on the surfaces of Pt oxides.

A carbon-supported Pd-P catalyst as the anodic catalyst in a direct formic acid fuel cell

In this paper, it is reported for the first time that a carbon-supported Pd-P (Pd-P/C) catalyst for the anodic catalyst in the direct formic acid fuel cell (DFAFC) can be prepared. The Pd-P/C catalyst shows that its electrocatalytic activity and especially its stability for the oxidation of formic acid are much higher than that of a Pd/C catalyst. Therefore, the Pd-P/C catalyst may have practical applications in DFAFCs.

Structure-activity relationship of surfactant for preparing DMFC anodic catalyst

Three kinds of surfactants as stabilizer were applied to the preparation of electrocatalysts for direct methanol fuel cell (DMFC). The catalysts have been characterized by examining their catalytic activities, morphologies and particle sizes by means of cyclic voltammetry, chronoamperometry, X-ray diffraction and transmission electron microscopy (TEM). It is found that the surfactants with different structures have a significantly influence on the catalyst shape and activity. The catalysts prepared with non-ionic surfactants as the stabilizer show higher activity for direct oxidation of methanol. The structure-activity relationship (SAR) analysis has been explored and the effect of hydrophile-lipophile balance (HLB value) has also been discussed.

Effect of cations in solution on the oxidation of methanol on the surface of platinum electrode

The effect of metal cations in solution on the oxidation of methanol on the electrode surface of platinum is a neglected aspect to direct methanol fuel cell (DMFC). In this paper, a smooth platinum electrode absorbing metal cations as the working electrode was applied to investigate the methanol oxidation with the cyclic voltammetry (CV) in 1.0 mol L-1 H2SO4. From the analysis of experiment, it is found that the cations, Li+, Ce4+, Mn2+, Ni2+, Cu2+, have some negative effect on the catalytic oxidation of methanol on the surface of platinum. The degree of the effect from different cations was analyzed.

Study on mechanism of interaction between Eu3+ and microperoxidase-11

The interaction mechanism between Eu3+ and microperoxidase-II (MP-11) in the aqueous solution was investigated using the UV-vis absorption spectroscopy, cyclic voltammetry and electrospray ionization mass spectrometry. It was found that one Eu3+ ion can coordinate with two carboxyl oxygen of two propionic acid groups of the heme group in the MP-11 molecule, leading the increase in the nonplanarity of the porphyrin ring and exposure degree of Fe(III) in the heme group. Therefore, the reversibility of the electrochemical reaction and the electrocatalytic activity of MP-11 for the reduction of oxygen are increased.

Preparation and simulation of an additional catalyst layer for direct methanol fuel cell

An additional anode catalyst layer with PtRu/C was hot pressed between two Nafion (R) 112 membranes and a conventional direct methanol fuel cell (DMFC) cathode/membrane/anode assembly with the above membranes as separator was fabricated. The additional catalyst layer formed an assistant cell with the cathode to prevent methanol crossover. A simple one-dimensional mathematical model was presented to describe the performance of this new type of membrane electrode assembly system. As seen from both experimental result and model analysis, the additional catalyst layer can not only effectively prevent the methanol crossover, but also generate electrical power with the crossover methanol. The percentage of output power of the assistant cell to the total power analyzed by the model is about 40% under usual condition, which is much higher than that from experimental result, indicating the potential of the development in the DMFC designing. It was also discovered that the electrical power generated from the assistant cell with crossover methanol could take higher percentage in total electrical power when the main DMFC current density became lower.

Physical and electrochemical characterizations of PtRu/C catalysts by spray pyrolysis for electrocatalytic oxidation of methanol

In this paper, it was reported that the carbon-supported Pt-Ru(Pt-Ru/C) catalyst used as the anodic catalyst in the direct methanol fuel cell (DMFC) was synthesized with a two-step spray pyrolysis (SP) method using the Pt and Ru metal salt as the precursors and polyethylene glycol (PEG) with the different molecular weights (Mw= 200,600,and 1000 analytical reagent) as cosolvent. PEG as a cosolvent plays a crucial role in producing PtRu/C catalysts. It was found that the Mw of PEG could affect the electrocatalytic activity of Pt-Ru and the morphology of the Pt-Ru particles in the Pt-Ru/C catalysts prepared with this method. When the Mw of PEG is 600, the Pt-Ru particles in the Pt-Ru/C catalyst prepared with this method possess the small average size, narrow size distribution, uniform dispersion, and high electrochemically active specific surface area. The electrocatalytic activity of the Pt-Ru/C catalyst prepared with this method using the cosolvent PEG with Mw = 600 for the methanol oxidation is much higher than that of the commercial E-TEK Pt-Ru/C catalyst. Therefore, the two-step SP method is an excellent method for the preparation of the Pt-Ru/C catalyst used in DMFCs.

Effect of valence of copper in La2-xThxCuO4 on NO decomposition reaction

NO decomposition reaction was investigated over La2-xThxCuO4, in which the valence of copper was controlled by Th substitution and was characterized by XPS measurement. A close correlation between the valence of copper and the activity was observed. The activity increased with the decrease of the average oxidation number of copper, and increased with the increase of Cu+ content, suggesting that the transition metal with low valence (Cu+) is active for the reaction in the present cases.

硫堇与寡核苷酸结合序列选择性的光谱研究

用UV-Vis吸收光谱、荧光光谱、圆二色谱以及核磁共振光谱等手段研究了硫堇(TH)与两个不同序列寡核苷酸的作用。TH与寡核苷酸作用后的吸收光谱和荧光光谱产生了明显的减色红移和荧光猝灭效应。分别计算了TH与[oligo d(GC)]2和[oligo d(AT)]2作用的荧光猝灭常数和结合常数,结果表明TH与GC序列的结合能力比与AT序列更强。通过TH与[oligo d(GC)]2作用后双螺旋链构象变化以及TH质子的1HNMR谱峰明显变宽,进一步说明TH与寡核苷酸结合的序列选择性。

Preparation and luminescence properties of ormosil hybrid materials doped with Tb(Tfacac)(3)phen complex via a sol-gel process

In this paper, silica-based transparent organic-inorganic hybrid materials were prepared via the sol-gel process. Tetraethoxysilane (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) were used as the inorganic and organic precursors, respectively. The terbium complex, Tb(Tfacac)(3)phen (Tfacac = 1,1,1-trifluoroacetylacetone, phen = 1, 10-phenanthroline) was successfully doped into organically modified silicate (ormosil) matrix derived from TEOS and GPTMS, and the luminescent properties of the resultant ormosil composite phosphors [ormosil/Th(Tfacac)(3)phen] were investigated compared with those of the Tb(Tfacac)(3)phen incorporated into SiO2 derived from TEOS (labeled as silica/Tb(Tfacac)(3)phen). Both kinds of the materials show the characteristic green emission of Tb3+ ion. The luminescence behavior of the resultant composite products was dependent on the matrix composition. The optimized lanthanide complex concentration in the ormosil/Tb(Tfacac)(3)phen was increased compared with in silica/Tb(Tfacac)(3)phen. Furthermore, the lifetime of Tb3+ in Tb(Tfacac)(3)phen, silica/Tb(Tfacac)(3)phen and ormosil/Tb(Tfacac)(3)phen follows the sequence: onmosil/Tb(Tfacac)(3)phen>silica/Tb(Tfacac)(3)phen>pure Tb(Tfacac)(3)phen.

Microperoxidase-11 modified electrode and its electrocatalytic activity on the reduction of O-2 and H2O2

Microperoxidase-11 (MP-11) was immobilized on the surface of a silanized glass carbon electrode by means of the covalent bond with glutaraldehyde. The measurements of cyclic voltammetry demonstrated that the formal redox potential of immobilized MP-11 was -170 mV. which is significantly more positive than that of MP-11 in a solution or immobilized on the surface of electrodes prepared with other methods. This MP-11 modified electrode showed a good electrocatalytic activity and stability for the reduction of oxygen and hydrogen peroxide.

溶液pH对硫堇与DNA相互作用方式的影响

用电化学和光谱方法研究了溶液pH对硫堇(TH)与小牛胸腺脱氧核糖核酸(CT-DNA)相互作用方式的影响。电化学测量结果表明,在pH 7.2的磷酸盐缓冲溶液中,TH与CT-DNA之间的作用方式以嵌入结合为主,在pH6.5的磷酸盐缓冲溶液中,TH与CT-DNA之间的作用方式既存在嵌入结合也存在静电作用。荧光光谱测量结果表明,TH与DNA结合后其荧光发生猝灭,通过Stern-Volmer方程计算得到pH 6.5时TH-DNA体系的猝灭常数高于pH 7.2时的值,表明在pH 6.5的溶液中两者相互作用更强。圆二色谱(CD)实验结果也证实了这一结论。