Bi掺杂的直接甲醇燃料电池阳极催化剂研究进展

发展可替代能源对缓解全球能源问题具有重要意义。直接甲醇燃料电池(direct methanol fuel cell,DMFC) 因其工作温度低、能量密度高以及污染物排放少等特性,正逐渐成为最有发展前景的便携式能源技术之一。目前,其商业化进程主要取决于甲醇氧化反应(methanol oxidation reaction,MOR) 的动力学快慢、催化剂的成本和寿命。Bi元素的掺杂可以极大地提高甲醇电催化氧化的性能,并且可以提高阳极催化剂抵抗CO中毒的能力。介绍了掺杂Bi的贵金属和非贵金属阳极电催化剂,以及贵金属掺杂Bi₂O₃、Bi₂WO₆ 等光辅助电催化剂;综述了它们提高甲醇电催化氧化性能的机制,并展望了阳极Bi电催化剂在DMFC中所面临的机遇和挑战。     

The preparation and performance of high activity Ni-Cr binary catalysts for direct borohydride fuel cells

Ni-Cr binary anode catalysts used in direct borohydride fuel cells (DBFCs) were prepared using a constant potential electrodepo- sition method. Compared with pure metal Ni catalysts, the electro-oxidation currents of borohydride ions (BH-4) more than doubled when using Ni-Cr binary catalysts under the same conditions. The enhanced activity of the Ni-Cr binary catalysts could be attributed to the change in distribution of BH-4ions on the surface of the Ni electrode. This is due to Cr electrodeposits, which allows a greater number of hydrogen atoms to catalyze from each tetrahedron BH-4 ion. The performance of Ni-Cr binary catalysts could also be improved by optimizing the electrodeposition conditions. The results show that Ni-Cr binary catalysts are optimally prepared using an electrodeposition method of 1s with a Cr3+ concentration of 0.2 mol L-1 and a potential of -0.100 V.     

金属支撑固体氧化物燃料电池阻抗谱动态分析

采用悬浮等离子喷涂工艺制造金属支撑固体氧化物燃料电池(SOFC),阴极为SSCo-SDC(质量分数比为75%:25%),电解质为SDC,阳极为NiO-SDC(质量分数比为70%:30%),支撑体为多孔Hastelloy X合金.在450～600℃下,对极化电阻、欧姆电阻、本体电阻与界面接触电阻分别进行了静态分析,分析结果显示接触电阻对欧姆极化损失的影响较大.电池经受3次慢速热循环(3℃/min)和12次快速热循环(60℃/min),并记录600℃时动态阻抗谱和开路电压.基于对欧姆电阻和极化电阻的动态分析,给出了金属支撑SOFC可能的降解机理.动态分析结果也显示,金属支撑体的抗氧化性在金属支撑SOFC稳定性中发挥重要作用.     

Cu改性直接甲醇燃料电池Pd/C阴极催化剂的电催化性能

用铜做掺杂元素,采用浸渍法以活性炭为载体制备了贵金属载量为20%的Pd-Cu/C系列直接甲醇燃料电池阴极催化剂,比较了4种不同Cu含量催化剂的电催化性能。采用ICP和X射线衍射分析了催化剂中金属元素的比例以及Cu掺杂对Pd/C催化剂晶体结构的影响。结果表明:催化剂中Pd与Cu的物质的量之比与预设值相近,Pd和Cu基本被全部还原;Pd-Cu/C催化剂为面心立方结构,元素铜的加入使催化剂的Pd-Pd间距缩小,从而HO2 ads和OO键能更好地吸附在催化剂金属表面;当采用NaBH4为还原剂,Pd与Cu物质的量比为3∶1时,催化剂(Pd3Cu/C)的平均粒径为3.4 nm,催化剂的催化性能最好,电化学活性表面积EAS达到38.9m2/gPd,电化学性能较Pd/C催化剂有很大提高,接近Pt/C商用催化剂。     

质子交换膜燃料电池金属双极板表面改性涂层研究进展

用于质子交换膜燃料电池(PEMFC)的金属双极板,因其可加工性强、导热导电性优而受到广泛关注．作为燃料电池的重要组成部分,双极板的生产成本和性能是电堆投入实际应用、扩大应用范围的关键．金属双极板在PEMFC酸性且润湿的环境中,受到的侵蚀及其表面氧化带来的接触电阻的降低对其实际应用产生了挑战．本文简述了制备双极板表面改性涂层的方法,对比了用于极板改性的多类型涂层(金属基涂层、非晶碳涂层和氮化物涂层)在膜基结合力、界面导电性、耐腐蚀性能和疏水性等方面的差别,分析了改性涂层的腐蚀机制和影响涂层性能表现的因素,探讨了涂层在结构设计、失效机制、元素选择等方面存在的问题,讨论了降低极板成本、提高耐久性这一极板改性研究的主要趋势．      

新型烯烃聚合催化剂研究进展

由于过渡金属催化剂在烯烃聚合方面具有高活性和良好的分子剪裁性，通过调节催化荆的微结构或温度、压力等聚合环境的变化，可以在分子层次上实现烯烃聚合物的分子设计与组装，实现聚合物物理性质的调控，最近引起了人们的广泛关注。本文介绍了过渡金属催化荆的合成及其负载化，水相烯烃聚合及活性聚合等方面的研究进展。     

A high-performance cathode for the next generation of solid-oxide fuel cells

Fuel cells directly and efficiently convert chemical energy to electrical energy. Of the various fuel cell types, solid-oxide fuel cells (SOFCs) combine the benefits of environmentally benign power generation with fuel flexibility. However, the necessity for high operating temperatures (800-1,000 degrees C) has resulted in high costs and materials compatibility challenges. As a consequence, significant effort has been devoted to the development of intermediate-temperature (500-700 degrees C) SOFCs. A key obstacle to reduced-temperature operation of SOFCs is the poor activity of traditional cathode materials for electrochemical reduction of oxygen in this temperature regime. Here we present Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-delta)(BSCF) as a new cathode material for reduced-temperature SOFC operation. BSCF, incorporated into a thin-film doped ceria fuel cell, exhibits high power densities (1,010 mW cm(-2) and 402 mW cm(-2) at 600 degrees C and 500 degrees C, respectively) when operated with humidified hydrogen as the fuel and air as the cathode gas. We further demonstrate that BSCF is ideally suited to 'single-chamber' fuel-cell operation, where anode and cathode reactions take place within the same physical chamber. The high power output of BSCF cathodes results from the high rate of oxygen diffusion through the material. By enabling operation at reduced temperatures, BSCF cathodes may result in widespread practical implementation of SOFCs.     

原位制备表面增强复合材料的一种新方法

提出了一种利用工频电流制备表面增强复合材料的新方法，其特点是：对合金熔体施加一个交流电，利用交流电及其感生磁场产生的电磁力，迫使电导率较低的第二相向边缘迁移，凝固后得到表面增强的复合材料．利用该方法原位制备了表面硅增强的铝硅合金，表层硬度比单纯的铝基提高10-20倍．该方法工艺简单，不受铸件形状和尺寸的限制，可用于表面增强金属材料的规模化制备．     

电催化析氧反应过渡金属硫化物催化剂研究进展

析氧反应（oxygen evolution reaction, OER）、析氢反应（hydrogen evolution reaction, HER）和氧还原反应（oxygen reduction reaction, ORR）为电解水、金属-空气电池等能源器件的半反应。其中,OER由于涉及4e^-转移和O-O键的形成而导致反应动力学迟缓和过电势高,因此,开发优异的OER电催化剂能够有效提高能量转换效率。到目前为止,过渡金属硫化物催化剂（transition metal sulfide catalysts, TMSs）被研究人员大量研究和报道,并且取得飞跃发展。介绍在不同电解质中的OER机制,并通过对近几年相关文献的综合归纳,探究TMSs催化剂的组成、导电性、质子传输、缺陷程度、界面化学等多种因素对OER的影响。综述目前过渡金属硫化物电催化剂在OER领域所面临的挑战和研究进展,希望为TMSs的研究者提供借鉴。     

非贵金属基催化剂用于催化降解有机污染物的研究进展

碳达峰、碳中和是一场极其广泛的绿色革命,可以推动经济社会高质量发展,对实现全球绿色转型具有重大意义。当前,随着环境问题的日益加剧,工业废水产生了大量有毒的有机化合物,将这些物质释放到水生环境中会对人类健康造成极大的威胁,因此,对有机污染物的合理处理变得尤为重要,制备具有高催化效率、高循环稳定性、低成本和绿色环保的非贵金属催化剂可以促进绿色可持续发展。阐述了非贵金属基催化剂的研究进展,包括最常用的单/双金属、单/双金属氧化物、层状双金属氢氧化物以及金属基复合催化剂,可以将有机污染物通过绿色环保的方法降解为无毒、无害的物质,符合可持续发展理念。对提高催化降解效果的关键影响因素进行了分析和总结,并对未来研发更加多样化的降解污染物的催化剂指出了方向。     

A bulk metal/ceramic composite material with a cellular structure

Metal/ceramic composite materials can be divided into two groups: one is ceramic reinforced metal matrix composite, and the other is metal toughened ceramic matrix composite. The research on these materials mainly focuses on the mechanical properties due …     

一种制备MPc/金属氧化物纳米复合材料的新方法

以超临界流体干燥(SCFD)制备的氧化铁气凝胶纳米粒子的表面活性Fe离子为模板,邻苯二腈为酞菁起始物,在氧化铁纳米颗粒表面原位组装生成酞菁/氧化铁纳米复合材料.研究表明,与普通浸渍法相比,该方法制得的酞菁铁与氧化铁颗粒之间存在化学键合作用.     

Electrolyte materials for intermediate-temperature solid oxide fuel cells

Solid oxide fuel cells (SOFCs) directly convert chemical energy that is stored in a wide range of fuels into direct current electricity, with high efficiency and low emissions, via a series of electrochemical reactions at elevated operating temperatures (generally 400–1000 °C). During such an energy conversion process, the properties of electrolyte materials determine the working principle and operating temperature of the SOFC. When considering the cost and stability, lowering the operating temperature is critical, and this has become one of the developing trends in SOFC research. The key point for realizing a reduction in operating temperature is to maintain low ohmic resistance of the electrolyte and low polarization resistance of the electrodes. In practice, the mechanical and chemical stability of the electrolyte is also a big concern. According to their differences in ion conduction mechanisms, there are three main types of electrolyte material available, namely, oxygen ion-conducting, proton-conducting, and dual ion-conducting electrolytes. In this review, we give a comprehensive summary of the recent advances in the development of these three types of electrolyte material for intermediate-temperature SOFCs. Both conductivity and stability are emphasized. In conclusion, the current challenges and future development prospects are discussed.     

Electrocatalyst approaches and challenges for automotive fuel cells

Fuel cells powered by hydrogen from secure and renewable sources are the ideal solution for non-polluting vehicles, and extensive research and development on all aspects of this technology over the past fifteen years has delivered prototype cars with impressive performances. But taking the step towards successful commercialization requires oxygen reduction electrocatalysts--crucial components at the heart of fuel cells--that meet exacting performance targets. In addition, these catalyst systems will need to be highly durable, fault-tolerant and amenable to high-volume production with high yields and exceptional quality. Not all the catalyst approaches currently being pursued will meet those demands.     

The use of metal hydrides in fuel cell applications

This paper reviews state-of-the-art developments in hydrogen energy systems which integrate fuel cells with metal hydride-based hydrogen storage. The 187 reference papers included in this review provide an overview of all major publications in the field, as well as recent work by several of the authors of the review. The review contains four parts. The first part gives an overview of the existing types of fuel cells and outlines the potential of using metal hydride stores as a source of hydrogen fuel. The second part of the review considers the suitability and optimisation of different metal hydrides based on their energy efficient thermal integration with fuel cells.The performances of metal hydrides are considered from the viewpoint of the reversible heat driven interaction of the metal hydrides with gaseous H_2. Efficiencies of hydrogen and heat exchange in hydrogen stores to control H_2 charge/discharge flow rates are the focus of the third section of the review and are considered together with metal hydride – fuel cell system integration issues and the corresponding engineering solutions. Finally, the last section of the review describes specific hydrogen-fuelled systems presented in the available reference data.     

甲烷部分氧化制合成气负载型过渡金属催化剂性能的研究

考察了负载在不同载体上的过渡金属催化剂用于甲烷部分氧化(POM)制合成气反应的催化性能.结果发现,负载型贵金属催化剂一般表现出比过渡金属催化剂更好的POM反应性能,活性金属组分在载体上的分散度可以影响其催化性能,但金属的电子组态对催化剂性能的影响更为明显,适中的未成对d电子对POM反应是有益的.在各种载体材料中,SiO2等低酸性且无明显氧化还原性能的材料是制备POM反应催化剂的良好载体,在所研究的各种催化剂中,SiO2负载的Rh催化剂具有最佳的POM反应性能.反应条件可以明显地影响POM反应的性能,升高温度有利于提高甲烷转化率和CO选择性,原料气中过高的VCH4/Vo2不利于POM反应的进行.     

火电厂SCR脱硝催化剂在线活化试验装置

提出了一种SCR催化剂在线活化试验装置及其工艺流程,并对该装置的设计方法、活性测试方法及其操作步骤进行了详细说明．该装置同时具有催化剂活性测试和失活催化剂活化功能,是其他现有催化剂检测装置和活化装置功能的组合,其目的在于提供一种新的烟气脱硝催化剂活化工艺,同时也为实际工程催化剂的活性检测、活化液的配制提供一种方法．