The Equation of State and Petrogenesis of Komatiite

(1) Equation of State of Komatiite

The equation of state (EOS) of a molten komatiite (27 wt% MgO) was detennined in the 5 to 36 GPa pressure range via shock wave compression from 1550°C and 0 bar. Shock wave velocity, U_S, and particle velocity, U_P, in km/s follow the linear relationship U_S = 3.13(±0.03) + 1.47(±0.03) U_P. Based on a calculated density at 1550°C, 0 bar of 2.745±0.005 glee, this U_S-U_P relationship gives the isentropic bulk modulus K_S = 27.0 ± 0.6 GPa, and its first and second isentropic pressure derivatives, K'_S = 4.9 ± 0.1 and K"_S = -0.109 ± 0.003 GPa^-1.

The calculated liquidus compression curve agrees within error with the static compression results of Agee and Walker [1988a] to 6 GPa. We detennine that olivine (FO₉₄) will be neutrally buoyant in komatiitic melt of the composition we studied near 8.2 GPa. Clinopyroxene would also be neutrally buoyant near this pressure. Liquidus garnet-majorite may be less dense than this komatiitic liquid in the 20-24 GPa interval, however pyropic-garnet and perovskite phases are denser than this komatiitic liquid in their respective liquidus pressure intervals to 36 GPa. Liquidus perovskite may be neutrally buoyant near 70 GPa.

At 40 GPa, the density of shock-compressed molten komatiite would be approximately equal to the calculated density of an equivalent mixture of dense solid oxide components. This observation supports the model of Rigden et al. [1989] for compressibilities of liquid oxide components. Using their theoretical EOS for liquid forsterite and fayalite, we calculate the densities of a spectrum of melts from basaltic through peridotitic that are related to the experimentally studied komatiitic liquid by addition or subtraction of olivine. At low pressure, olivine fractionation lowers the density of basic magmas, but above 14 GPa this trend is reversed. All of these basic to ultrabasic liquids are predicted to have similar densities at 14 GPa, and this density is approximately equal to the bulk (PREM) mantle. This suggests that melts derived from a peridotitic mantle may be inhibited from ascending from depths greater than 400 km.

The EOS of ultrabasic magmas was used to model adiabatic melting in a peridotitic mantle. If komatiites are formed by >15% partial melting of a peridotitic mantle, then komatiites generated by adiabatic melting come from source regions in the lower transition zone (≈500-670 km) or the lower mantle (>670 km). The great depth of incipient melting implied by this model, and the melt density constraint mentioned above, suggest that komatiitic volcanism may be gravitationally hindered. Although komatiitic magmas are thought to separate from their coexisting crystals at a temperature =200°C greater than that for modern MORBs, their ultimate sources are predicted to be diapirs that, if adiabatically decompressed from initially solid mantle, were more than 700°C hotter than the sources of MORBs and derived from great depth.

We considered the evolution of an initially molten mantle, i.e., a magma ocean. Our model considers the thermal structure of the magma ocean, density constraints on crystal segregation, and approximate phase relationships for a nominally chondritic mantle. Crystallization will begin at the core-mantle boundary. Perovskite buoyancy at > 70 GPa may lead to a compositionally stratified lower mantle with iron-enriched mangesiowiistite content increasing with depth. The upper mantle may be depleted in perovskite components. Olivine neutral buoyancy may lead to the formation of a dunite septum in the upper mantle, partitioning the ocean into upper and lower reservoirs, but this septum must be permeable.

(2) Viscosity Measurement with Shock Waves

We have examined in detail the analytical method for measuring shear viscosity from the decay of perturbations on a corrugated shock front The relevance of initial conditions, finite shock amplitude, bulk viscosity, and the sensitivity of the measurements to the shock boundary conditions are discussed. The validity of the viscous perturbation approach is examined by numerically solving the second-order Navier-Stokes equations. These numerical experiments indicate that shock instabilities may occur even when the Kontorovich-D'yakov stability criteria are satisfied. The experimental results for water at 15 GPa are discussed, and it is suggested that the large effective viscosity determined by this method may reflect the existence of ice VII on the Rayleigh path of the Hugoniot This interpretation reconciles the experimental results with estimates and measurements obtained by other means, and is consistent with the relationship of the Hugoniot with the phase diagram for water. Sound waves are generated at 4.8 MHz at in the water experiments at 15 GPa. The existence of anelastic absorption modes near this frequency would also lead to large effective viscosity estimates.

(3) Equation of State of Molybdenum at 1400°C

Shock compression data to 96 GPa for pure molybdenum, initially heated to 1400°C, are presented. Finite strain analysis of the data gives a bulk modulus at 1400°C, K'_S. of 244±2 GPa and its pressure derivative, K'_OS of 4. A fit of shock velocity to particle velocity gives the coefficients of U_S = C_O+S U_P to be C_O = 4.77±0.06 km/s and S = 1.43±0.05. From the zero pressure sound speed, C_O, a bulk modulus of 232±6 GPa is calculated that is consistent with extrapolation of ultrasonic elasticity measurements. The temperature derivative of the bulk modulus at zero pressure, θK_OSθT|_P, is approximately -0.012 GPa/K. A thermodynamic model is used to show that the thermodynamic Grüneisen parameter is proportional to the density and independent of temperature. The Mie-Grüneisen equation of state adequately describes the high temperature behavior of molybdenum under the present range of shock loading conditions.

Catalisadores à base de platina frente a correntes de H2 contendo acetaldeído geradas via reforma do etanol

Devido ao efeito estufa, a produção de hidrogênio a partir da reação de reforma do bioetanol tem se tornado um assunto de grande interesse em catálise heterogênea. Os catalisadores à base de Pt são empregados nos processos de purificação de H2 e também em eletrocatalisadores das células a combustível do tipo membrana polimérica (PEMFC). O hidrogênio obtido a partir da reforma do etanol contém como contaminante o acetaldeído e pequenas quantidades de CO. Assim, pode-se prever que muitas reações podem ocorrer na presença de catalisadores de Pt durante o processo de purificação do H2 e mesmo no próprio eletrocatalisador. Desta forma, este trabalho tem como objetivo descrever o comportamento do acetaldeído na presença de catalisadores de Pt. Para tanto foram preparados dois catalisadores, Pt/SiO2 e Pt/USY, contendo 1,5% de metal em ambos. Também foi estudado um eletrocatalisador (comercial) de Pt suportado em carvão (Pt/C). Os catalisadores foram caracterizados através das técnicas de análise textural, difração de raios X (DRX), quimissorção de H2, reação de desidrogenação do ciclohexano, espectroscopia no infravermelho de piridina adsorvida, dessorção a temperatura programada de n-butilamina (TPD de n-butilamina), dessorção a temperatura programada de CO2 (TPD-CO2), análise termogravimétrica, microscopia eletrônica de varredura (MEV) e espectroscopia de dispersão de energia (EDS). Os testes catalíticos foram realizados entre as temperaturas de 50 e 350 C em corrente contendo acetaldeído, H2 e N2. Foi observado que as propriedades ácido-básicas dos suportes promovem as reações de condensação com formação de éter etílico e acetato de etila. O acetaldeído em catalisadores de Pt sofre quebra das ligações C-C e C=O. A primeira ocorre em uma ampla faixa de temperaturas, enquanto a segunda apenas em temperaturas abaixo de 200 C. A quebra da ligação C-C produz metano e CO. Já a quebra da ligação C=O gera carbono residual nos catalisadores, assim como espécies oxigênio, que por sua vez são capazes de eliminar o CO da superfície dos catalisadores. Nota-se que o tipo de suporte utilizado influencia na distribuição de produtos, principalmente a baixas temperaturas. Além disso, constatou-se que a descarbonilação não é uma reação sensível à estrutura do catalisador. Verificou-se também a presença de resíduos sobre os catalisadores, possivelmente oriundos não somente da quebra da ligação C=O, mas também de reações de polimerização

Modificación del sistema energético de la unidad móvil de donantes de osakidetza (CVTT)

[ES]Hoy en día los vehículos usados en la extracción de sangre utilizan un motor de combustión interna, no solamente para sus desplazamientos, sino también para generar electricidad con la que poder utilizar todos los aparatos del interior. Como consecuencia, el autobús es una fuente importante de ruidos y contaminación, ya que el motor diesel está funcionando durante las largas paradas en las que se realiza dicha actividad. El objetivo del proyecto es diseñar un sistema innovador basado en pilas de combustible que sirva para alimentar todos los equipos y dispositivos, evitando el ruido, las vibraciones y los gases contaminantes. Para ello y en primer lugar, será necesario estimar el consumo total del autobús. Tras esto, también se tomarán una serie de decisiones con el fin de mejorar la eficiencia energética del autobús. Finalmente, se hará un diseño del sistema energético, el cual debe incluir una pila de combustible, junto con todos sus sistemas asociados, y todas las especificaciones.

Instalaciones energéticas en edificios. viabilidad de las pilas de combustible en edificios de viviendas.

[ES]El siguiente proyecto analiza la viabilidad energética y económica que supone la instalación de una tecnología de pilas de combustible como cogeneración en una vivienda unifamiliar en Madrid. Al mismo tiempo, se compara dicha instalación con otra más desarrollada como es la combinación entre una caldera de condensación y la red eléctrica.

Efficient generation of one-group cross sections for coupled Monte Carlo depletion calculations

Coupled Monte Carlo depletion systems provide a versatile and an accurate tool for analyzing advanced thermal and fast reactor designs for a variety of fuel compositions and geometries. The main drawback of Monte Carlo-based systems is a long calculation time imposing significant restrictions on the complexity and amount of design-oriented calculations. This paper presents an alternative approach to interfacing the Monte Carlo and depletion modules aimed at addressing this problem. The main idea is to calculate the one-group cross sections for all relevant isotopes required by the depletion module in a separate module external to Monte Carlo calculations. Thus, the Monte Carlo module will produce the criticality and neutron spectrum only, without tallying of the individual isotope reaction rates. The onegroup cross section for all isotopes will be generated in a separate module by collapsing a universal multigroup (MG) cross-section library using the Monte Carlo calculated flux. Here, the term "universal" means that a single MG cross-section set will be applicable for all reactor systems and is independent of reactor characteristics such as a neutron spectrum; fuel composition; and fuel cell, assembly, and core geometries. This approach was originally proposed by Haeck et al. and implemented in the ALEPH code. Implementation of the proposed approach to Monte Carlo burnup interfacing was carried out through the BGCORE system. One-group cross sections generated by the BGCORE system were compared with those tallied directly by the MCNP code. Analysis of this comparison was carried out and led to the conclusion that in order to achieve the accuracy required for a reliable core and fuel cycle analysis, accounting for the background cross section (σ0) in the unresolved resonance energy region is essential. An extension of the one-group cross-section generation model was implemented and tested by tabulating and interpolating by a simplified σ0 model. A significant improvement of the one-group cross-section accuracy was demonstrated.

Cost-effectiveness of alternative powertrains for reduced energy use and CO2 emissions in passenger vehicles

This work analysed the cost-effectiveness of avoiding carbon dioxide (CO2) emissions using advanced internal combustion engines, hybrids, plug-in hybrids, fuel cell vehicles and electric vehicles across the nine UK passenger vehicles segments. Across all vehicle types and powertrain groups, minimum installed motive power was dependent most on the time to accelerate from zero to 96.6km/h (60mph). Hybridising the powertrain reduced the difference in energy use between vehicles with slow (t z - 60 > 8 s) and fast acceleration (t z - 60 < 8 s) times. The cost premium associated with advanced powertrains was dependent most on the powertrain chosen, rather than the performance required. Improving non-powertrain components reduced vehicle road load and allowed total motive capacity to decrease by 17%, energy use by 11%, manufacturing cost premiums by 13% and CO2 emissions abatement costs by 15%. All vehicles with advanced internal combustion engines, most hybrid and plug-in hybrid powertrains reduced net CO2 emissions and had lower lifetime operating costs than the respective segment reference vehicle. Most powertrains using fuel cells and all electric vehicles had positive CO2 emissions abatement costs. However, only vehicles using advanced internal combustion engines and parallel hybrid vehicles may be attractive to consumers by the fuel savings offsetting increases in vehicle cost within two years. This work demonstrates that fuel savings are possible relative to today's fleet, but indicates that the most cost-effective way of reducing fuel consumption and CO2 emissions is by advanced combustion technologies and hybridisation with a parallel topology. © 2014 Elsevier Ltd.

The role of the sp2:sp3 substrate content in carbon supported nanotube growth

We report the growth of vertically-aligned nanotube forests, of up to 0.2 mm in height, on an 85:15 sp2:sp3 carbon support with Fe catalyst. This is achieved by purely-thermal chemical vapour deposition with the catalyst pretreated in inert environments. Pretreating the catalyst in a reducing atmosphere causes catalyst diffusion into the support and the growth of defective tubes. Other sp2:sp3 compositions, including graphite, tetrahedral amorphous carbon, and pure diamond, also lead to the growth of defective carbon morphologies. These results pave the way towards controlled growth of forests on carbon fibres. It could give rise to applications in enhanced fuel cell electrodes and better hierarchical carbon fibre-nanotube composites. © 2014 Elsevier Ltd. All rights reserved.

Enhanced Proton Conduction in Polymer Electrolyte Membranes as Synthesized by Polymerization of Protic Ionic Liquid-Based Microemulsions

Proton-conducting membranes were prepared by polymerization of microemulsions consisting of surfactant-stabilized protic ionic liquid (PIL) nanodomains dispersed in a polymerizable oil, a mixture of styrene and acrylonitrile. The obtained PIL-based polymer composite membranes are transparent and flexible even though the resulting vinyl polymers are immiscible with PIL cores. This type of composite membranes have quite a good thermal stability, chemical stability, tunability, and good mechanical properties. Under nonhumidifying conditions, PIL-based membranes show a conductivity up to the order of 1 x 10(-1) S/cm at 160 degrees C, due to the well-connected PIL nanochannels preserved in the membrane. This type of polymer conducting membranes have potential application in high-temperature polymer electrolyte membrane fuel cells.

The role of CeO2-ZrO2 as support in the ZnO-ZnCr2O4 catalysts for autothermal reforming of methanol

Autothermal reforming of methanol for hydrogen production was investigated over ZnO-ZnCr2O4 supported on a series of metal oxides (Al2O3, CeO2, ZrO2 and CeO2-ZrO2)CeO2-ZrO2 mixed oxides with Ce /Zr molar ratio of 4/1 was found to be the optimal support which showed significant effect on the catalytic activity and selectivity. The ZnO-ZnCr2O4/CeO2-ZrO2 and ZnO-ZnCr2O4 catalysts were characterized by XRD, TEM, H-2-TPR and XPS. The results show that CeO2-ZrO2 mixed oxides have significant effect on the catalytic performance and the supported catalyst shows more uniform temperature distribution in the catalyst bed which was mainly due to its reasonable redox properties.

直接甲醇燃料电池阳极催化剂及甲醇氧化稀土助催化剂剂研究

燃料电池以其高效、环境友好的发电方式，被誉为21世纪的能源技术。其中，直接甲醇燃料电池（DMFC）更以燃料甲醇来源丰富，价格低廉，储存、携带方便而成为近年的研究热点。但是，DMFC在其实用化之前还需要解决一些重要问题，其中的关键之一就是高性能的贵金属催化剂的研究。我们知道，甲醇的电化学活性要低于氢气三个数量级；而且甲醇在R表面进行电化学氧化时，其中间解离吸附产物会造成贵金属催化剂中毒，显著降低了催化剂的活性。因此，要使DMFC具有相当高的电流密度和运行稳定性，就需要对贵金属催化剂制备进行不断的研究和改进。在本文的工作中，主要从Pt/C催化剂的制备方法、新型碳纳米管载体、稀土助催化剂等三个方面进行了研究和探索，取得的具体结果如下：1．Pt／C催化剂制备方法的研究与改进（1）在本组已有的研究结果基础上，对预沉积还原法进行了一些改进，采用原子吸收光谱（AAS）进行表征，发现Pt的利用率得到了明显的提高。采用X射线衍射。（RD）、透射电子显微镜（TEM）和BET表征铂的粒径、晶态结构和催化剂特性，分析表明，经过改进的预沉积还原法制备的催化剂仍然具有良好的分散性、较小的粒径、较低的晶态结构和良好的催化剂特性，电化学测试证明其性能要优于同等的E-TEK催化剂。（2）借鉴冶金学中的相关技术，提出了一种新的Pt/C催化剂制备方法一程序升温焙烧法。该方法的具体步骤增强了金属催化剂粒子和碳载体之间的相互作用力，提高了碳载体的导电性，并且形成了部分有利于催化反应进行的活性晶态结构。得到的R／C催化剂获得了近似E-TEK催化剂的催化活性，在具体方法上仍有改进的潜力。采用了同（1）的催化剂表征方法。2．甲醇电化学氧化稀土助催化剂研究在直接甲醇燃料电池Pt/C催化剂的研究过程中，一个重要的方面就是助催化剂的研究，并且已经得到了较好的结果。本工作选用了稀土元素为研究对象，因为稀土元素属于过渡金属，具有丰富的d电子轨道，易于和金属形成强的类化学键的吸附作用，并且能够和有机小分子形成多种配位化合物。经过初步的工作，发现了有些稀土离子如Sm3+能够在Pt表面吸附并且对甲醇电化学氧化具有较稳定的促进作用，采用循环伏安法，计时电流，交流阻抗等电化学方法进行了表征。根据实验结果，对其反应机理进行了初步的探讨。3．碳纳米管（CNTs）作为贵金属催化剂载体的研究碳纳米管（CNTs）由于其结构上的特殊性（径向尺寸为纳米量级，轴向尺寸为微米量级）而表现出典型的一维量子材料，同时具有较高的机械强度和超常的电学性能，能够为化学反应提供纳米级的反应场所，因此受到了化学界包括电化学研究人员的极大关注。已经在作为贵金属催化剂载体方面进行了一些研究，本工作的主要内容就是针对Pt/CNTs催化剂对碳纳米管的要求，对其预处理方法进行了改进，采用了如（1）中的催化剂表征方法和（2）中的相关电化学方法进行测定，发现碳纳米管作为贵金属催化剂载体时，对它的纯化处理方法的不同明显地影响了其载体性质和催化剂的活性。

直接甲醇燃料电池甲醇替代燃料的研究

论文主要研究了直接甲醇燃料电池（DMFC）中三种甲醇替代燃料，二甲氧基甲烷（DMM）、乙醇和乙二醇及导致阳极催化剂中毒的吸附CO（COad）在光滑R电极及几种新的R基催化剂电极上的电氧化行为。结合对催化剂的X射线光电子能谱（xPS）、X衍射(XRD)、扫描电子显微镜（SEM）和热重分析（TG）表征，初步探讨了几种新催化剂对三种甲醇替代燃料的电催化活性要高于碳载R（PtC）催化剂的原因。另外，还研究了用表面活化处理来提高阳极催化剂对甲醇氧化的电催化活性的方法。本论文得到的主要结果如下：1．在研究DMM在不同条件下，在不同R基催化剂电极上的电化学氧化行为的基础上，发现碳载R和TiO2（Pt-TiO2／C）复合催化剂对DMM氧化的电催化活性要优于Pt/C电极。而Pt-TiO2／C催化剂在吸附Ho3+(Pt-TiO2-Ho3+/C)或Eu3＋（Pt-TiO2-Eu3＋/C）后，对DMM氧化的电催化活性比Pt-TiO2／C电极高。表明TiO2、Eu3+和Ho3+对DMM的氧化都有很好的促进作用，这主要是它们都能为DMM的氧化在电极表面提供更多的含氧物种。由于DMM本身在这些催化剂电极上的氧化性能不好，而且DMM容易在酸性溶液中水解，生成甲醇和甲醛，因此，DMM不是一种好的甲醇替代燃料。2．无论在中性介质中还是在酸性介质中，Eu3＋和Ho3＋对乙醇在R／C电极上的电化学氧化反应都有较好的促进作用，而Eu3＋的促进作用要大于H3+，Eu3＋和H3+在酸性溶液中的促进作用要大于在中性溶液中。无论是中性溶液还是酸性溶液中，吸附CO（COad）在Pt／C催化剂电极上在较正的电位处有一个很大的氧化峰，而在R-Eu3＋／C或R-H3＋／C催化剂电极上在较负电位处有两个小的氧化峰，表明吸附的Eu3＋和Ho3+对cood在R／C催化剂电极上的氧化都有很好的促进作用，主要表现在使Cood的吸附强度降低和吸附量减少。XPs测量表明，当R／C电极表面吸附了Eu3＋或H了十后，使催化剂中Pt和c土的电子云密度变小，因此使Pt对coad的吸附强度减弱。由于Eu3＋或H03＋在电极上吸附不是物理吸附，而是化学吸附，因此，它们与Pt的结合具有相对的稳定性。乙醇电氧化的中间产物，如COad等能强烈地吸附在R上，因此会使R中毒。而Eu3＋或H矿"能降低Coad在R上地吸附强度，因此，Eu3＋或H3+能促进乙醇在Pt／C电极上的电化学氧化反应。Pt-TiO2／C催化剂对乙醇氧化的电催化活性要高于R／C催化剂，表明TiO2对乙醇在R／C电极上的电化学氧化反应也有较好的促进作用。XPS的测量表明，TiO2的加入并不改变Pt的电子状态，因此，TiO2能促进乙醇电氧化反应的主要原因是TIOZ能为乙醇氧化提供含氧物种。实验结果表明，Eu3＋或H3+对乙醇在R-TiO2／C电极上的电化学氧化反应也有一定的促进作用。这是由于Eu3＋或H3+改变了R的电子状态，降低了乙醇电氧化中间产物，COod在Pt上的吸附强度，而TIOZ提供了COod的氧化所必须的含氧物种。3．无论是酸性溶液中还是中性溶液中，乙二醇在R-TiO2／C电极上的氧化活性比在R／C电极上高。这表明TIOZ能促进乙二醇在Pt上的电氧化反应。进一步的实验表明，TIOZ对COad在Pt催化剂电极上氧化的促进作用并不明显。XPS测量表明，这是由于TIOZ并不改变R的电子状态。所以，TiO2对乙二醇在Pt上的电氧化的促进作用只是基于提供乙二醇电氧化所需的含氧物种。无论是酸性溶液中还是中性溶液中，乙二醇在R-WO3／C电极上的氧化活性都比在R／C电极上高。这表明W03能促进乙二醇在R上的电氧化反应。进一步的实验表明，R-WO3／C电极对Coad氧化的电催化活性也要高于R／C电极，XPS测量表明，WO3会降低Pt的电子云密度。所以，WO3对乙二醇在R上的电氧化的促进作用除了提供含氧物种外，还由于它能降低R的电子云密度而降低了乙二醇电氧化中间产物。4．用四氢吠喃和丙酮混合溶液浸泡法对电极进行表面处理后能使Pt／C和Pt-WO3／C电极对乙醇和乙二醇氧化的电催化活性有很大的提高。其原因可能是Pt／C和Pt一w03／C电极在经表面处理后，在电极制备过程中带来的表面活性剂等杂质由于溶解在混合溶液中而被除去，Nafion也可能在用混合溶液浸泡后会发生一定程度的结构变化，因此，使活性中心的位点增加，从而增加了催化剂的电催化活性。另外，经表面处理后，Pt／C和Pt-WO3／C电极的活性中心的结构有一定的变化，使COad的吸附强度降低而容易氧化，降低了COad对催化剂的毒化作用，因而提高了电极对乙醇和乙二醇氧化的电催化活性。

无介体双室微生物燃料电池产电性能初步研究

本文对无介体双室微生物燃料电池的产电性能进行了初步研究，并根据不同运行阶段产电性能的优劣，对其中微生物的差异性进行了比较分析。全文分为两个部分： 第一部分：以乙酸钠为阳极原料构建双室微生物燃料电池（MFC），研究不同阴极受体、外接电阻、乙酸钠浓度和pH等因素对电池产电性能的影响，研究结果表明：在500mL的阴阳极反应体系中，选用乙酸钠作为阳极底物，质量浓度为6.46 g/L， pH 7.0，接入500Ω外电阻，阴极电子受体选择高锰酸钾的情况下，微生物燃料电池产电性能最好，最大电功率密度达到294.72 mW/m2，库伦效率能达到25.87%。在确定最适外接电阻阻值的同时对MFC内阻进行测定，阻值为871.87Ω。 第二部分：微生物燃料电池运行中，比较以厌氧污泥作为接种源的第一阶段和只接入附着有大量微生物电极的第二阶段的产电性能，得出第二阶段产电性能优于第一阶段，最大电功率密度达到353.57mW/m2，比第一阶段提高58.85 mW/m2；库伦效率为39.35%，增幅达52％左右；针对微生物燃料电池运行过程中，底物CH3COONa可能存在其它的代谢途径，本实验进行了第二阶段产电性能与CH3COONa消耗率关系以及阳极液面上方气体成分和含量的研究，发现第二阶段50h前CH3COONa的大量消耗主要用于微生物的生长，在整个运行过程中，阳极液面上方含有CH4和CO2；对气体测定的同时还发现，振荡能增强电功率密度的输出；通过对电极上和污泥中微生物差异性分析得出，δ-变形菌纲、β-变形菌纲和拟杆菌门的菌种更适应微生物燃料电池的运行环境，能在电极上大量富集，提高电池的产电性能，只接入附着有大量微生物的电极能有效降低热袍菌纲的菌种数量，降低了CH3COONa的无为消耗，有效提高了电池的库伦效率。 Electricity production in the mediator-less two-chambered microbial fuel cell(MFC) was researched. Based on the result in the different operation phase in the MFC, the microbial diversity was analysed. The paper involved two parts: Part 1: A two-chambered microbial fuel cell (MFC) was constructed with high-concentration sodium acetate as fuel in the anode. The influence of different electron acceptors in the cathode, external resistance value, pH value and concentration of sodium acetate on electricity generation in MFC was investigated. The result showed that the maximum power density of 294.72 mW/m2 and the coulombic efficiency of 25.87% was achieved at sodium acetate concentration of 6.46 g/L, pH 7.0, external resistance 500Ωin the anode and when using potassium permanganate as electron acceptor in the cathode. While decided the value of resistor, we found that shaking has effect on electricity production in the MFC. Part 2: Comparing the electricity production in different operation phases when using anaerobic sludge as inoculum in the first phase and microbes in the anodic electrode as inoculum in the second phase, the result showed that electricity production in the second phase was more than that in the first phase, the maximum power density of 353.57 mW/m2 and the coulombic efficiency of 39.35% was achieved, 58.85 mW/m2 and 52％ more than that in the first phase, respectively. According to the fact that CH3COONa might be metabolized in other pathway in the running process in the MFC, we determining the relationship between electricity production and CH3COONa consumption, and the gas content in the anode, we found that CH3COONa was mainly used for microbe growth before 50h, and the anode contained CH4 and CO2. At the same time, we found that shaking could improve power density. The analysis on diversity of microbe in the anodic electrode and anaerobic sludge showed that δ-proteobacterium, β-proteobacterium and Bacteroidetes adapted themselves to the running environment of MFC. The anode could enrich them to improve the electricity production while reduced the quantity of Thermotogales, which were obligately anaerobic organotrophs with a fermentative metabolism, to increase the coulombic efficiency effectively.

Effects of treatment in different atmosphere on Pt3Sn/C electrocatalysts for ethanol electro-oxidation

Pt3Sn/C catalyst was prepared by a modified polyol process and treated in air, H-2/Ar, and Ar atmosphere, respectively. XRD analyses indicate that all of these catalysts have face-centered cubic (fcc) crystal structure. Temperature-programmed reduction (TPR) experiments show that more Sn exists in zero-valence in the Ar-treated PtSn catalyst than in the others. Cyclic voltammetry (CV), chronoamperometry (CA) experiments, and the performance tests of direct ethanol fuel cell (DEFC) indicate that the catalytic activity of PtSn/C for ethanol oxidation was affected significantly by the chemical state of Sn in catalyst particles. The as-prepared PtSn/C gives the higher power density, while Ar-treated PtSn/C shows the lower cell performance. It seems that the multivalence Sn rather than the zero-valence Sn in the PtSn catalyst is the favorable form for ethanol oxidation. Energy dispersion X-ray analysis (EDX) of the PtSn/C-as prepared and PtSn/C (after stability test) shows the active species (platinum, tin, and oxygen) composition changed to a different extent. Further attempt to improve the catalyst stability is needed.