直接甲醇燃料电池阳极催化剂的研究进展

阳极催化剂是影响直接甲醇燃料电池（DMFC）性能及成本的主要因素之一,从催化剂载体选择、复合催化剂的制备、非贵金属催化剂研究三方面综述了DMFC阳极催化剂国内外研究现状,并进行了简要分析,展望了其应用前景。     

直接甲醇燃料电池阳极催化剂研究进展

直接甲醇燃料电池（direct methanol fuel cells, DMFC）由于其高效、清洁等优点,成为替代化石能源的理想新能源装置。催化剂作为DMFC中重要的组成部分,通过降低反应活化能,解决甲醇需要高过电势才能被电氧化的问题。但是目前DMFC阳极催化剂存在催化活性低、抗CO毒性差以及成本较高等问题,限制了DMFC的商业化。本文介绍了甲醇的催化电氧化原理,从Pt基催化剂、非Pt基催化剂、催化剂载体三个方面对DMFC阳极催化剂国内外研究进展进行了综述。介绍了通过选择合适晶面、添加助催化剂、制备特殊形貌、选择合适的载体4种方法对提高催化剂性能、降低催化剂成本的研究现状。甲醇在Pt（100）晶面上的催化活性较好但是抗CO毒性较弱;根据双功能理论和电子调变理论,制备的Pt-M合金催化剂具有更高的抗CO毒性和甲醇催化活性;非Pt基催化剂的制备为降低催化剂成本提供了研究思路;选择合适的催化剂载体,利用载体与催化剂之间的相互作用,也成为解决DMFC阳极催化剂目前面临的易中毒、活性低、成本高等问题的解决方法。     

直接甲醇燃料电池阳极催化剂的制备

直接甲醇燃料电池（DMFC）阳极催化剂是DMFC的关键材料之一,其电化学活性的大小对燃料电池的输出性能及成本起着关键作用。不同催化剂的制备技术决定了催化剂电化学活性的高低。介绍了DMFC阳极催化剂的几种制备方法,并对这些方法进行了评述,对制备DMFC阳极催化剂具有很好的参考价值。     

燃料电池多组分阳极催化剂的最新研究进展

介绍了近年来适用于质子交换膜燃料电池(PEMFC)和直接甲醇燃料电池(DMFC)的阳极催化剂的国内外研究情况,着重介绍了一些近年来发展起来的制备方法和新的多组分催化剂体系,特别是一些表现出了良好的活性和抗CO中毒性能的新催化体系。     

DMFC阳极多元合金催化剂的研究进展

介绍了直接甲醇燃料电池(DMFC)阳极Pt基三元、四元合金催化剂和非Pt基催化剂的制备方法,综述了甲醇催化氧化性能和相关反应机理的发展现状，讨论了DMFC多元合金电催化剂的发展趋势,研究结果表明,不同的合金组成和不同的催化剂载体对阳极催化剂的催化活性有着直接的影响。     

直接甲醇燃料电池阳极非铂催化剂的研究进展

介绍了直接甲醇燃料电池(DMFC)的特点及其阳极催化剂存在的主要问题。综述了DMFC阳极非铂催化剂的研究进展及非铂催化剂对甲醇氧化的催化活性和抗CO等中间物毒化能力等性能,提出了DMFC阳极非铂催化剂存在的问题以及发展趋势。     

合成气制混合醇催化剂研究进展

将我国丰富的煤炭资源经合成气转化为混合醇,作为合成气化学重要的研究领域,该技术的突破对于提高煤化工产品品味、实现煤炭清洁利用、降低醇类化学品石油依赖度具有重要意义,受到了国内外工业界和学术界的广泛关注。制约合成气制混合醇发展的瓶颈在于高效能催化剂的开发,合成气制混合醇催化剂包括贵金属催化剂、改性甲醇合成催化剂、改性费托合成催化剂和钼基催化剂,对以上催化剂逐一进行介绍,详细阐述了国内外最新研究进展,并对各类催化剂性能做出简要评价,为合成气制混合醇早日实现工业应用提供借鉴。     

葡萄糖加氢催化剂研究现状及发展趋势

介绍了葡萄糖加氢生产山梨醇用催化剂的国内外研究和发展现状;分析了各类催化剂的葡萄糖催化加氢性能和使用条件,指出了各类催化剂的优缺点;提出了催化剂的发展趋势是由Raney镍催化剂向改性多元Raney镍催化剂发展,由多元改性Raney镍催化剂向负载型贵金属催化剂发展,由晶态催化剂向非晶态催化剂发展。     

高岭石改性及其对流化催化裂化催化剂性能的影响

综述了高岭石的改性方法及其对高岭石理化性能和流化催化裂化(FCC)催化剂性能的影响。FCC催化剂的主要活性中心是表面酸位,主要裂化场所是催化剂的孔隙及表面。高岭石的酸改性或热改性增加了高岭石比表面积和表面酸量,改变了高岭石表面酸位种类以及孔结构,进而提高了高岭石基FCC催化剂的催化裂化性能。对国内外高岭石改性研究进行系统总结,可为高岭石的改性及其在FCC催化剂中的应用提供参考。     

蒽醌法生产过氧化氢用催化剂研究进展

论述了过氧化氢的生产方法及工艺技术,详述了催化剂载体特别是氧化铝的国内外研制现状,指出添加助剂对氧化铝载体进行改性,可以制得性能优良的载体.经过对催化剂制备方法的国内外研究情况进行分析指出,蒽醌法生产过氧化氢用催化剂的制备常采用浸渍法,国内外大多在载体预处理、添加助催化剂、浸渍条件等方面进行了研究,以提高催化剂的综合应...     

DMFC electrode preparation,performance and proton conductivity measurements

A method that involves stenciling electrodes using dry powders for fuel cells is described and compared to anodes and cathodes prepared by the traditional spraying method using catalyst inks. Methods to determine the proton conductivity of the DMFC anode layer are also discussed. The stenciling method allows for the preparation of highly reproducible membrane electrode assemblies (MEAs) utilizing little waste material. MEAs can be prepared in a controlled manner using the stenciling technique. The resulting morphology of the as-prepared electrodes is observed to be dependent on the preparation method, while the thickness of the once hot-pressed catalyst layers appears to be independent of the preparation method. Stenciled anodes of the same catalyst loading were found to show a lower proton resistance (R_p) than sprayed anodes. However, the lower R_p value was not sufficient to result in a measurable increase in the performance of a direct methanol fuel cell (DMFC); as in fact, the average steady-state DMFC performance was found to be the same using sprayed or stenciled electrodes. The DMFC performance was found to be strongly dependent on the Nafion content and large increases in the Nafion content were needed to increase the DMFC performance measurably. Even though thick electrodes were prepared in this work, the R_p values of the stenciled anodes were found to be comparable to results reported in the literature for much thinner electrodes made using high metal catalyst loadings on carbon. This observation is most probably due to the higher Nafion content used in this work.     

Effect of Porosity in Catalyst Layers on Direct Methanol Fuel Cell Performances

Effects of porosity of catalyst layers (CLs) on direct methanol fuel cell (DMFC) performances are investigated using silicon dioxide (SiO₂) particles as a pore former. The pore size and volume of CLs are controlled by changing the size and content of SiO₂. As the size of pore formed by removal of SiO₂ increases, DMFC performances are enhanced. The augmentation in performances can be explained by facilitation of fuel transport to catalyst particles, increase of utilization efficiency of catalysts, diminishment in methanol crossover, reduction in activation loss and facilitation of water discharging out of CLs of cathode due to the controlled porosity in CLs. The enhanced fuel transport, accessibility of fuels to Pt catalyst surface, is proved by the active areas of Pt catalyst. In addition to the active area of Pt catalyst, porous CLs exhibit a decline in methanol crossover, leading to increase of open circuit voltage (OCV). The porous CLs also show improvements in activation loss due to high porosity, causing enhancement in DMFC performances. In aspect of pore volume contribution to cathode performance, the SiO₂ content is optimized. Based on the DMFC performances, it can be suggested that the optimum conditions of SiO₂ are 500 nm in size and 20 wt.% in content. The porosity effect on both electrodes appears as follows: the pores in cathode are more effective on DMFC performances (55.5%) than those of anodes (44.5%) based on the maximum power of DMFC, indicating that the pores in CLs facilitate removal of water from electrodes.     

DMFC多孔Pt-Ru阳极甲醇氧化宏观动力学模型化

本文旨在建立和求解DMFC多孔阳极甲醇氧化宏观动力学理论数模。根据Pt-Ru催化剂上双位机理,得到包含CO和OH覆盖率的甲醇水解本征动力学表达式;通过对该多孔阳极微元体积中的物料和电（荷）量衡算,导出了描述电极中浓度和超电势分布的两个耦联的模型方程。经量纲1化后,获得以量纲1变量和准数表示的普遍化宏观动力学数模。该模型包括催化层厚度l、比表面积a、有效扩散系数D_e和有效液相电导率κ_e等工程参数,特别是包括了与动力学参数相关且作为厚度变量函数的CO和OH覆盖率。进而,文中还给出了DMFC多孔阳极效率因子和极化曲线的计算公式。该数模为一非线性二阶微分方程组边值问题,经解耦,可得到两个同解的微分方程。用Newman的BAND（J）程序对方程进行数值求解,并在每一节点计算中嵌入一个计算CO和OH覆盖率的子程序。将模型预测值与甲醇氧化多孔阳极的极化实验数据进行对比发现：当宏观电流密度较低时二者能很好相符;当宏观电流密度较高、CO₂形成气泡的影响变大时,实验值有规律地偏低于预测值。详细的宏观动力学分析表明：提高催化剂Pt位甲醇电分解活性以减少功率损失、优化多孔电极微观和宏观结构以削弱两相流影响,应是改善该阳极性能的重要课题。本工作也可为直接乙醇燃料电池（DEFC）、直接硼氢化物燃料电池（DBFC）阳极的理论分析提供参考。     

Functionalized carbon support with sulfonated polymer for direct methanol fuel cells

Recently electrodes for direct methanol fuel cell (DMFC) have been developed for getting high fuel cell performances by controlling composition of catalysts and sulfonated polymers, developing catalyst particles, modifying carbon supports, etc. The electrodes in DMFCs are porous layers, which are composed of catalyst, which is black or carbon supported, and sulfonated polymers in a blended form. In the present study, carbon support for catalysts was functionalized to play dual roles of a mass transport and a catalyst support. The functionalized carbon support was characterized and compared with pristine one by thermal and spectroscopic analysis, and loading of platinum (Pt) catalysts on modified support was performed by gas reduction. The electrodes with Pt on functionalized carbon support were fabricated, though the conventional electrodes were prepared with sulfonated polymer and Pt catalysts. Membrane electrode assembly with Pt catalyst on functionalized support showed a higher DMFC performance of 30 mW cm⁻² at 50 °C without using additional sulfonated polymer. Integration of electrode components in one body has another advantage of easier and simpler process in preparing electrodes for DMFCs. Improved DMFC performance of the electrode containing functionalized carbon was be attributed to a better mass transport which maximize the catalytic activities.     

Tubular Cathode Prepared by a Dip‐Coating Method for Low Temperature DMFC

A novel tubular cathode for the direct methanol fuel cell (DMFC) is proposed, based on a tubular titanium mesh. A dip‐coating method has been developed for its fabrication. The tubular cathode is composed of titanium mesh, a cathode diffusion layer, a catalyst layer, and a recast Nafion® film. The titanium mesh is present at the inner circumference of the diffusion layer, while the recast Nafion® film is at the outer circumference of the catalyst layer. A DMFC single cell with a 3.5 mgPt cm^–2 tubular cathode was able to perform as well, in terms of power density, as a conventional planar DMFC. A peak power density of 9 mW cm^–2 was reached under atmospheric air at 25 °C.     

Effect of Ionomer Content in Anode and Cathode Catalyst Layers on Direct Methanol Fuel Cell Performance

The influence of ionomer content on the performance of direct methanol fuel cells (DMFC) is studied. The performance is studied as a function of the (nafion/carbon, N/C) ratio on the anode and cathode. The performance of the DMFC has been found to increase as a function of the N/C ratio. The ionomer content seems to influence the catalyst layer resistance in the anode and cathode and also the methanol oxidation potential on the anode. On the cathode, catalyst utilisation is seen to be affected by the ionomer content. Cyclic voltammetry (CV) is used to study the effect of ionomer content on Platinum (Pt) utilisation on the cathode. Theoretical calculations are used to study the catalyst layer resistance on the anode and cathode as a function of ionomer content. Findings indicate that ionomer content plays only a partial role in characterising the performance of a DMFC.     

CO_2气泡脱离扩散层孔口过程的数值模拟

在直接甲醇燃料电池(DMFC)中,阳极催化层表面反应生成的CO2气体通过扩散层,及时排出阳极通道,对提高DMFC电流密度具有重要意义,因此研究气泡脱离孔口的过程很有益。今采用Fluent6.2.16对CO2气泡脱离扩散层孔口过程、两孔时气泡形成及聚并过程进行了数值模拟,考察了阳极通道内液体流速、扩散层孔道直径等因素对气泡脱离的影响。结果表明,阳极通道内液体流速越大,气泡脱离扩散层孔口所需的时间越短;扩散层孔道直径越大,气泡脱离扩散层孔口所需的时间越长,且生成的气泡越大;由于从相邻两扩散层孔道出来的气泡的阻挡和挤压作用,使得两气泡周围的压力分布与单气泡不同,气泡脱离过程与从单个扩散层孔口的脱离过程有所不同,脱离时间更早。