Preparation of hybrid thin film modified carbon nanotubes on glassy carbon electrode and its electrocatalysis for oxygen reduction

A hybrid thin film containing Pt nanoparticles and [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) modified multi-walled carbon nanotubes (MWNTs) on a glassy carbon (GC) electrode surface was fabricated. This hybrid film electrode exhibited remarkable electrocatalytic activity for oxygen reduction and high stability with promising applications in fuel cells.

An infrared study on Langmuir-Blodgett films of octadecylammonium octadecanoate: FWHM and the vibrational coupling

The monolayer of the mixture of octadecanoic acid and octadecylamine with molar ratio 1: 1 has been investigated at the air-water interface. It was found that the monolayer shows a rather stable state at the surface pressure of 30 mN/m and this monolayer can be transferred onto a CaF2 plate by Langmuir-Blodgett (LB) technique. The infrared spectra of LB films indicated that octadecyl ammonium octadecanoate is formed by an intermolecular proton exchange between adjacent carboxylic and aminic groups (COO- and NH3+). In three-layer LB film, the CH2 scissoring mode of the long hydrocarbon chains of octadecyl ammonium octadecanoate shows a broad band feature at about 1468 cm(-1) while this vibrational mode of three-layer LB film of the mixture (1: 1) of deuterated stearic acid and octadecylamine (octadecylammonium octadecanoate-d35, C18H37NH3+C17D35COO-) only shows a narrow band. The broad feature of the CH2 scissoring mode in octadecylammonium octadecanoate probably originates from the coupling between the chain of stearic acid and that of octadecylamine while this kind of coupling could be completely removed in octadecylammonium octadecanoate-d35.

In situ synthesis and characterization of multiwalled carbon nanotube/Au nanoparticle composite materials

An effective and facile in Situ reduction approach for the fabrication of carbon nanotube-supported Au nanoparticle (CNT/Au NP) composite nanomaterials is demonstrated in this article. Linear polyethyleneimine (PEI) is ingeniously used as both a functionalizing agent for the multiwalled carbon nanotubes (MWNTs) and a reducing agent for the formation of An NPs. This method involves a simple mixing process followed by a mild heating process. This approach does not need the exhaustive surface oxidation process of CNTs. The coverage of Au NPs on CNTs is tunable by varying the experimental parameters, such as the initial molar ratio of PEI to HAuCl4, the relative concentration of PEI and HAUCl(4) to MWNTs, and the temperature and duration of the heat treatment. More importantly, even the heterogeneous CNT/Au composite nanowires are obtainable through this method. TEM, XPS, and XRD are all used to characterize the CNT/Au composite materials. In addition, the optical and electrocatalytic properties are investigated.

Electrooxidation of methanol on carbon nanotubes supported Pt-Fe alloy electrode

The synthesis and characterization of catalysts based on bimetallic materials, Pt-Fe supported on multi-walled carbon nanotubes (MWNTs) for methanol electrooxidation is reported here. The catalyst was prepared by a spray-cooling process and characterized by TEM, EDS, ICP and XRD. The electrocatalytic properties of the Pt-Fe/MWNTs electrode for methanol oxidation have been investigated by cyclic voltammetry and chronoamperometry. It presented higher electrocatalytic activity and stability than a comparative Pt/ MWNTs catalyst. This may be attributed to the addition of Fe which leads to the small average particle size and high utilization of Pt in the Pt-Fe/MWNTs catalyst. The results imply that the Pt Fe/MWNTs composite has good potential applications in fuel cells.

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.

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.

Effect of borohydride as reducing agent on the structures and electrochemical properties of Pt/C catalyst

In this paper, we found that boron deposited on the surface of support when sodium borohydride used as reducing agent during the preparation of Pt/C catalyst. The deposition of boron markedly reduces particle size of Pt, raises electrochemical active surface (EAS) area of catalyst and electrochemical activity for hydrogen evolution or oxygen reduction reaction (ORR) compared with which prepared using other reducing agents (hydrogen and formaldehyde).

Synthesis, characterization and electrical properties of the new solid electrolyte materials Ce6-xErxMoO15-delta (0.0 < x < 1.5)

A new series of oxides, Ce6-xErxMoO15-delta (0.0 less than or equal to x less than or equal to 1.5), was synthesized using wet-chemistry techniques. The precursors and resultant oxide powders were characterized by differential thermal analysis/thermogravimetry, x-ray diffraction, and IR, Raman and x-ray photoelectron spectroscopy. The formation temperature of the powders was found to be as low as 350degreesC. Ce6-xErxMoO15-delta crystallized to a fluorite-related cubic structure. The electrical conductivity of the samples was investigated by using ac impedance spectroscopy. This showed that the presence of Er was related to the oxygen-ion conductivity, and that the highest oxygen-ion conductivity was found in Ce6-xErxMoO15-delta (x = 0.4), ranging from 5.9 x 10(-5) S cm(-1) at 300degreesC to 1.26 x 10(-2) S cm(-1) at 700degreesC, respectively. This kind of material shows a potential application in intermediate-temperature solid oxide fuel cells.

Sol-gel synthesis and electrical properties of ceria-based solid electrolytes

A series of solid electrolytes (Ce0.8RE0.2)(1-x)MxO2-delta(RE: Rare earth, M: Alkali earth) were prepared by sol-gel methods. XRD indicated that a pure fluorite phase was formed at 800 degrees C. The synthesis temperature by the sol-gel methods was about 700 degrees C lower than by the traditional ceramic method. The electrical conductivity and impedance spectra were measured. XPS showed that the oxygen vacancy increased obviously by doping MO, thus, resulting in the increase of the oxygen ionic transport number and conductivity. The performance of ceria-based solid electrolyte was improved. The effects of RE2O3 and MO on the electrical properties were discussed. The conductivity and the oxygen ionic transport number of (Ce0.8Sm0.2)(1-0.05)Ca0.05O2-delta is 0.126 S.cm(-1) and 0.99 at 800 degrees C, respectively.

海洋生物膜的电活性及其在微生物燃料电池中的应用基础研究

海洋电活性微生物（又称电活性生物膜，electroactive biofilms, EABs）是自然界存在的一类功能性微生物，能够将代谢有机物产生的电子直接或间接传递给电极，人们对其在环境中的广泛性及其在生物防腐、生物能源和生物修复中的应用正在开展广泛的研究。 本论文着眼于海洋天然生物膜的电活性，从微生物腐蚀和微生物燃料电池的角度，考察研究了海洋天然生物膜对316L SS腐蚀行为的影响，发现海洋天然生物膜能抑制316L SS腐蚀，系统研究了海洋生物膜与石墨等电极的电子传递过程，提出了电活性生物膜（EABs）与电极间的电子传递机制，并初步研究了海洋电活性生物膜在微生物燃料电池(MFCs)中的应用。 对附着天然海洋生物膜的316L SS研究发现，生物膜使316L SS电位正移了500mV （vs. Ag/AgCl）。316L SS表面附着海洋生物膜后，其孔蚀电位由原来的50mV增加到540mV，孔蚀敏感性降低；同时，海洋生物膜的附着导致316L SS的阻抗增加，由此，我们明确提出海洋生物膜能够抑制316L SS腐蚀的发生。进一步研究了生物膜抑制腐蚀发生的可能机理。循环伏安实验表明，海洋生物膜与不锈钢电极之间存在电子传递过程。扫描电镜（SEM）及能谱（EDS）分析发现有钙盐的沉积生成。通过以上结果我们提出了生物膜对腐蚀的抑制机制假设，即在电极与电活性海洋生物膜间发生了电子传递，海洋生物膜能够将电子传递给不锈钢，316L SS作为电子接受体受到保护。 为进一步研究天然海洋生物膜的这种电活性，我们选择不会发生腐蚀的惰性电极材料石墨，玻碳，碳纸电极验证生物膜的电活性。 首次考察了天然海洋生物膜对石墨电极和玻碳电极的开路电位变化的影响，结果显示随电极在天然海水中浸泡时间，石墨电极正移50mV vs. Ag/AgCl，玻碳电极正移了300 mV （vs. Ag/AgCl）。与316L SS相似，三种电极的变正趋势相同，都经历了三个阶段，即初始缓慢变正期，随后的指数变正期和以后的稳定期，此与生物膜在固体表面形成的趋势相似。伏安曲线及阻抗实验结果表明，在石墨，玻碳和碳纸电极材料表面附着海洋生物膜后，电流密度增加，电荷转移电阻减小，说明生物膜与电极间存在电子传递，并能加速电子传递过程，不同材料表面生物膜的电活性能力由大到小为石墨＞316L SS＞碳纸＞玻碳。 进一步研究了海洋沉积物-海水生物膜微生物燃料电池，初步建立了相应的电极材料和微生物燃料电池结构。我们选择石墨阳极和石墨阴极或316L SS阴极组装海泥沉积物(阳极区)和海水（阴极区）MFC，316L SS代替石墨做阴极最大输出电量达9mW.m-2，约为后者的2倍。两种MFC输出电流和功率密度随时间的延长而增加的趋势相同，都可以分为三个阶段，即初期的缓慢增加阶段，中期的指数增长阶段，后期的平台稳定期阶段。这也与生物膜在固体表面形成的趋势相似。此研究也说明优化316L SS表面性质筛选活性海洋生物膜用于MFC有其潜在的应用价值。

Mixed reforming of heptane to syngas in the Ba0.5Sr0.5Co0.8Fe0.2O3 membrane reactor

Fuel cells are recognized as the most promising new power generation technology, but hydrogen supply is still a problem. In our previous work, we have developed a LiLaNiO/gamma-Al2O3 catalyst, which is excellent not only for partial oxidation of hydrocarbons, but also for steam reforming and autothermal reforming. However, the reaction needs pure oxygen or air as oxidant. We have developed a dense oxygen permeable membrane Ba0.5Sr0.5Co0.8Fe0.2O3 which has an oxygen permeation flux around 11.5 ml/cm(2) min at reaction conditions. Therefore, this work is to combine the oxygen permeable membrane with the catalyst LiLaNiO/gamma-Al2O3 in a membrane reactor for hydrogen production by mixed reforming of heptane. Under optimized reaction conditions, a heptane conversion of 100%, a CO selectivity of 91-93% and a H-2 selectivity of 95-97% have been achieved. (c) 2005 Elsevier B.V. All rights reserved.

Ethanol crossover phenomena and its influence on the performance of DEFC

In the present work, Nafion (R) membrane porosity changes were determined in aqueous ethanol solutions with different concentrations by weighing vacuum-dried and ethanol aqueous solution equilibrated membranes at room temperature. The ethanol crossover rate through Nafion (R)-115 membrane at different temperatures and different concentrations had been investigated in a fuel cell test apparatus by using membrane gets higher as ethanol solution gas chromatography analysis. The experimental results show that the swelling degree of Nafion (R) concentration increases. The ethanol crossover rate increases with ethanol concentration and temperature increment. The single direct ethanol fuel cell (DEFC) tests were carried out to investigate the effect of ethanol concentration on ethanol crossover and consequently, on the open circuit voltage and the cell performance of DEFC. It can be found that ethanol crossover presented a negative effect on the OCV and the cell performance of DEFC. It can also be found that an improved DEFC performance was obtained as temperature increased although the ethanol crossover rate increased with temperature increment. (c) 2005 Elsevier B.V. All rights reserved.

Structure and chemical composition of supported Pt-Sn electrocatalysts for ethanol oxidation

Carbon supported PtSn alloy and PtSnOx particles with nominal Pt:Sn ratios of 3:1 were prepared by a modified polyol method. High resolution transmission electron microscopy (HRTEM) and X-ray microchemical analysis were used to characterize the composition, size, distribution, and morphology of PtSn particles. The particles are predominantly single nanocrystals with diameters in the order of 2.0-3.0 nm. According to the XRD results, the lattice constant of Pt in the PtSn alloy is dilated due to Sn atoms penetrating into the Pt crystalline lattice. While for PtSnOx nanoparticles, the lattice constant of Pt only changed a little. HRTEM micrograph of PtSnOx clearly shows that the change of the spacing of Pt (111) plane is neglectable, meanwhile, SnO2 nanoparticles, characterized with the nominal 0.264 nm spacing of SnO2 (10 1) plane, were found in the vicinity of Pt particles. In contrast, the HRTEM micrograph of PtSn alloy shows that the spacing of Pt (111) plane extends to 0.234 nm from the original 0.226 nm. High resolution energy dispersive X-ray spectroscopy (HR-EDS) analyses show that all investigated particles in the two PtSn catalysts represent uniform Pt/Sn compositions very close to the nominal one. Cyclic voltammograms (CV) in sulfuric acid show that the hydrogen ad/desorption was inhibited on the surface of PtSn alloy compared to that on the surface of the PtSnOx catalyst. PtSnOx catalyst showed higher catalytic activity for ethanol electro-oxidation than PtSn alloy from the results of chronoamperometry (CA) analysis and the performance of direct ethanol fuel cells (DEFCs). It is deduced that the unchanged lattice parameter of Pt in the PtSnOx catalyst is favorable to ethanol adsorption and meanwhile, tin oxide in the vicinity of Pt nanoparticles could offer oxygen species conveniently to remove the CO-like species of ethanolic residues to free Pt active sites. (C) 2005 Elsevier Ltd. All rights reserved.