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.

GENESI: Wireless sensor networks for structural monitoring

The GENESI project has the ambitious goal of bringing WSN technology to the level where it can provide the core of the next generation of systems for structural health monitoring that are long lasting, pervasive and totally distributed and autonomous. This goal requires embracing engineering and scientific challenges never successfully tackled before. Sensor nodes will be redesigned to overcome their current limitations, especially concerning energy storage and provisioning (we need devices with virtually infinite lifetime) and resilience to faults and interferences (for reliability and robustness). New software and protocols will be defined to fully take advantage of the new hardware, providing new paradigms for cross-layer interaction at all layers of the protocol stack and satisfying the requirements of a new concept of Quality of Service (QoS) that is application-driven, truly reflecting the end user perspective and expectations. The GENESI project will develop long lasting sensor nodes by combining cutting edge technologies for energy generation from the environment (energy harvesting) and green energy supply (small form factor fuel cells); GENESI will define models for energy harvesting, energy conservation in super-capacitors and supplemental energy availability through fuel cells, in addition to the design of new algorithms and protocols for dynamic allocation of sensing and communication tasks to the sensors. The project team will design communication protocols for large scale heterogeneous wireless sensor/actuator networks with energy-harvesting capabilities and define distributed mechanisms for context assessment and situation awareness. This paper presents an analysis of the GENESI system requirements in order to achieve the ambitious goals of the project. Extending from the requirements presented, the emergent system specification is discussed with respect to the selection and integration of relevant system components.The resulting integrated system will be evaluated and characterised to ensure that it is capable of satisfying the functional requirements of the project

Harvesting life's energy: increase in the aerotolerence of the electrogenic anaerobe geobacter sulfurreducens due to over-expression of superoxide dismutase and catalase

Gemstone Team iGEM

Miniaturization of heterogeneous catalytic reactors: Prospects for new developments in catalysis and process engineering

This paper gives an overview of the research done since 1999 at Eindhoven University of Technology in the Netherlands in the field of miniaturization of heterogeneous catalytic reactors. It is described that different incentives exist for the development of these microstructured reaction systems. These include the need for efficient research instruments in catalyst development and screening, the need for small-scale reactor devices for hydrogen production for low-power electricity generation with fuel cells, and the recent quest for intensified processing equipment and novel process architectures (as in the fine chemicals sector). It is demonstrated that also in microreaction engineering, catalytic engineering and reactor design go hand-in-hand. This is illustrated by the design of an integrated microreactor and heat-exchanger for optimum performance of a highly exothermic catalytic reaction, viz. ammonia oxidation. It is argued that future developments in catalytic microreaction technology will depend on the availability of very active catalysts (and catalyst coating techniques) for which microreactors may become the natural housing.

Enhancing the Activity and Tuning the Mechanism of Formic acid Oxidation at Tetrahexahedral Pt Nanocrystals by Au Decoration

Tetrahexahedral Pt nanocrystals (THH Pt NCs), bound by high index facets, belong to an emerging class of nanomaterials that promise to bridge the gap between model and practical electrocatalysts. The atomically stepped surfaces of THH Pt NCs are extremely active for the electrooxidation of small organic molecules but they also readily accommodate the dissociative chemisorption of such species, resulting in poisoning by strongly adsorbed CO. Formic acid oxidation is an ideal reaction for studying the balance between these competing catalyst characteristics, since it can proceed by either a direct or a CO mediated pathway. Herein, we describe electrochemical and in situ FTIR spectroscopic investigations of formic acid electrooxidation at both clean and Au adatom modified THH Pt NC surfaces. The Au decoration leads to higher catalytic currents and enhanced CO2 production in the low potential range. As the CO oxidation behaviour of the catalyst is not changed by the presence of the Au, it is likely that the role of the Au is to promote the direct pathway. Beyond their fundamental importance, these results are significant in the development of stable, poison resistant anodic electrocatalysts for direct formic acid fuel cells.