直接甲醇燃料电池质子交换膜研究进展

直接甲醇燃料电池(DMFC)以其燃料来源丰富、储存方便、结构简单、安全等优点而日益受到广泛的关注。预计将在很多领域中能得到广泛的应用。过去,人们对DMFC做了很多研究,针对直接甲醇燃料电池中的质子交换膜(PEM)的阻甲醇性能方面的研究进展作如下评述。     

直接甲醇燃料电池

介绍了直接甲醇燃料电池的原理、结构,并与发展较早的氢气燃料电池进行优劣比较。针对近期商业化便携式燃料电池的技术指标,主要讨论了直接甲醇燃料电池在性能和成本上的现状和问题,并着重阐述了阳极催化剂和电解质膜（决定其性能的两个关键因素）的研发进展。     

直接甲醇燃料电池

介绍了直接甲醇燃料电池的原理、结构,并与发展较早的氢气燃料电池进行优劣比较。针对近期商业化便携式燃料电池的技术指标,主要讨论了直接甲醇燃料电池在性能和成本上的现状和问题,并着重阐述了阳极催化剂和电解质膜(决定其性能的两个关键因素)的研发进展。     

直接甲醇燃料电池质子交换膜的发展现状

直接甲醇燃料电池(DMFC)是20世纪90年代兴起的第六代燃料电池,以其诸多的优点引起人们的广泛关注和研究。其中聚合物电解质膜是DMFC的关键技术,起着隔离阴阳极、质子传输、绝缘电子的作用。它的作用决定着DMFC的输出功率、电池效率、成本及应用前景。本文介绍了已商品化的全氟磺酸膜(Nafion膜)的结构及性能、以及替代膜的国内外发展现状,指出DMFC用膜的研究是21世纪能源研究的重点。     

燃料电池碱性聚合物阴离子膜研究进展

阴离子交换膜(AEM)是碱性聚合物电解质燃料电池APEMFC内部结构中的核心部件,但是目前因离子导电率差和化学稳定性不足等问题还不能满足APEMFC商业方面的推广应用。因此,迫切需要开发出高性能的AEM以备APEMFC使用。介绍了一些比较成熟的AEM功能化方法,并综述了近年来国内外关于APEMFC的最新研究成果。     

燃料电池碱性聚合物阴离子膜研究进展

阴离子交换膜(AEM)是碱性聚合物电解质燃料电池APEMFC内部结构中的核心部件,但是目前因离子导电率差和化学稳定性不足等问题还不能满足APEMFC商业方面的推广应用。因此,迫切需要开发出高性能的AEM以备APEMFC使用。介绍了一些比较成熟的AEM功能化方法,并综述了近年来国内外关于APEMFC的最新研究成果。     

直接甲醇燃料电池膜电极制备技术进展

简述了直接甲醇燃料电池(DMFC)的核心部件———膜电极(MEA)的结构及制备技术的最新进展,包括传统厚层电极法、薄层电极法、双层电极法、电沉积法和溅射沉积法,分析了各种方法的优缺点。其中电化学沉积法和溅射沉积法制备MEA,具有催化剂利用率高、负载量低、电池性能好等优点,若能实现大规模的工业化生产,将是DMFC最理想的MEA制备技术。为了进一步推广DMFC的商业化应用,降低MEA的制备成本,建议改进MEA组分、优化MEA结构和开发重现性好,同时适合工业化生产的MEA制备技术。     

直接甲醇燃料电池甲醇电氧化催化剂研究的新动向

概述了直接甲醇燃料电池甲醇电氧化催化剂最近的一些研究情况。电化学沉积法和采用有机金属前驱体、有机溶剂中还原金属化合物制备催化剂的方法可以有效地控制催化剂组成、分布、颗粒大小；铂—金属大环化合物对甲醇的电催化氧化具有很好的催化活性，金属碳化物和钙饮矿类氧化物是可能代替责金属铂而作为直接甲醇燃料电池阳极催化剂的非责金属材料。     

氢燃料电池阴极氧还原非金属催化剂研究进展

氧还原反应是制约氢燃料电池效率的重要因素,也是一直以来的研究热点和突破难点.非金属催化剂是近年来新兴的氧还原催化剂,对其的研究对推动燃料电池商业化具有重要意义,本文综述了近年来氧还原反应中非金属催化剂的研究进展,包括氮掺杂碳材料,硼、磷或硫掺杂碳材料,二元掺杂碳材料,最后展望了相关催化剂的未来研究趋势.     

一种无膜直接甲醇燃料电池

通过热解法将含有间硝基苯胺、碳黑、聚乙烯吡咯烷酮(PVP)、多壁碳纳米管(CNT)与醋酸钴的前驱体在CO_2气氛下于800℃下加热,得到不同间硝基苯胺含量的钴掺杂C-N催化剂;通过化学还原法制备了多壁碳纳米管(MWCNT)以及β-环糊精(β-CD)修饰的MWCNT(β-CD-MWCNT)负载的金属钯/锡纳米颗粒。碱性溶液中,Co-C-N系列催化剂表现出对氧还原具有较好的催化活性,对醇也具有较好的耐受力;PdSn/β-CD-MWCNT也对醇也表现出较强且稳定的催化活性。以PdSn/β-CD-MWCNT为阳极,同时将Co-C-N催化剂制备成气体扩散电极,组装成无膜直接燃料电池,以0.5 mol·L~(-1)甲醇为燃料进行了放电测试,电池具有较高的放电功率,而且放电稳定。     

Co-Fe-Pd纳米粒子的可控制备及其氧还原催化性能

以Co(COOH)₂、FeCl₃和PdCl₂为原料,柠檬酸为稳定剂,乙醇为加速剂,采用超声辅助制备Co-Fe-Pd金属纳米粒子,并评估其氧还原反应(ORR)电催化性能。研究结果表明,Co-Fe-Pd金属纳米粒子平均粒径约3～5 nm,由于Co、Fe固溶于Pd晶格,使Co-Pd、Fe-Pd和Co-Fe-Pd纳米粒子仅显示Pd衍射峰,且伴有不同程度的宽化;相比于Co-Fe、Fe-Pd或Co-Pd纳米粒子,三元Co-Fe-Pd晶格压缩更为明显,晶格缺陷诱使的活性位点增加,氧还原催化能力增强;其氧还原起峰电位为1.03 V(vs RHE),Tafel斜率为?87 mV/dec,可与商用Pt/C催化剂相媲美;氧还原过程中电子转移数为3.80±0.04,说明其主导四电子转移路径;此外,RRDE结果显示氧还原过程中的中间产物H₂O₂含量约10%。     

Selective catalytic reduction of NO by propane in excess oxygen over IrCu-ZSM-5 catalyst

The selective reduction of NO by propane over bimetallic IrCu-ZSM-5 was investigated in this study. IrCu-ZSM-5, together with Cu-ZSM-5 and Ir-ZSM-5, was characterized by FTIR of pyridine adsorption, UV–vis spectroscopy and H₂-TPR. The results indicated that the nature of Cu species changed with iridium as a modifier. The reaction mechanism over IrCu-ZSM-5 was investigated using in situ DRIFT spectra and nitrate species were observed as the main reaction intermediate for NO reduction by propane. The addition of trace iridium into Cu-ZSM-5 favored the formation of nitrate species, and thus better catalytic activity could be obtained on IrCu-ZSM-5.     

NOX removal in excess oxygen by plasma-enhanced selective catalytic reduction

In the off-gases of internal combustion engines running with oxygen excess, non-thermal plasmas (NTPs) have an oxidative potential, which results in an effective conversion of NO to NO₂. In combination with appropriate catalysts and ammonia (NH₃-SCR) or hydrocarbons (HC-SCR) as a reducing agent, this can be utilized to reduce nitric oxides (NO and NO₂) synergistically to molecular nitrogen.

The combination of SCR and cold plasma enhanced the overall reaction rate and allowed an effective removal of NO_X at low temperatures. Using NH₃ as a reducing agent, NO_X was converted to N₂ on zeolites or NH₃-SCR catalysts like V₂O₅–WO₃/TiO₂ at temperatures as low as 100–200 °C. Significant synergetic effects of plasma and catalyst treatment were observed both for NH₃ stored by ion exchange on the zeolite and for continuous NH₃ supply.

Certain modifications of Al₂O₃ and ZrO₂ have been found to be effective as catalysts in the plasma-assisted HC-SCR in oxygen excess. With an energy supply of about 30 eV/NO-molecule, 500 ppm NO was reduced by more than half at a temperature of 300 °C and a space velocity of 20 000 h⁻¹ at the catalyst. The synergistic combinations of NTP and both NH₃- and HC-SCR have been verified under real diesel engine exhaust conditions.     

超薄钯铜纳米片组装纳米花的构建及其氧还原性能

在原子水平上精确调控电催化剂的组成是增强其氧还原（ORR）性能的有效途径。本文采用简单的一步溶剂热还原法制备了由不同PdCu组成的超薄双金属纳米片自组装而成的三维（3D）合金纳米花（Pd₁Cu_x NCFs）。利用透射电子显微镜（TEM）、扫描透射电子显微镜-能谱仪（STEM-EDS）、X射线粉末衍射（XRD）和X射线光电子能谱（XPS）等手段系统表征了Pd₁Cu_x NCFs的形貌、晶体结构及成分。相比于传统二维（2D）纳米材料,Pd₁Cu_x NCFs丰富的快速传质路径、较高的Pd原子利用效率和更强的PdCu双金属间协同作用使得其在碱性介质中表现出增强的ORR性能。另外,本文还研究了Pd、Cu前体用量对ORR性能的影响。结果显示,Pd、Cu前体摩尔比为1∶0.5时,催化剂（Pd₁Cu_0.5NCFs）在碱性介质中ORR活性和电化学稳定性最佳。其半波电位E_1/2（0.937V）远高于商业Pt/C（0.851V）;在加速循环1000次扫描后,E_1/2几乎没有变化,说明其稳定性优异;0.90V电势下,Pd₁Cu_0.5 NCFs的质量比活性为1.09A/mg,是商业Pt/C的14.5倍。     

Electroreduction of oxygen over iron macrocyclic catalysts for DMFC applications

The performance of macrocyclic catalysts in oxygen reduction was investigated for a direct methanol fuel cell. The dependence of catalytic activity on different factors was determined for two classes of precursors; namely, iron porphyrin (Fe-PC) and iron phthalocyanine (Fe-TPP). It was found that there was an optimal heat-treating temperature for each precursor. Heat-treated Fe-TPP shows maximum activity at 750 °C, while the highest performance in the case of Fe-PC is observed at 500 °C. It was shown that oxygen reduction activity is affected by the number of nitrogen bonds formed with iron, particle size, and formation of carbon layers.     

富氧条件下金属催化CO还原NO的研究进展

CO广泛存在于燃煤烟气及汽车尾气中,利用未完全燃烧的CO催化还原NO可同时脱除NO和CO,过程中催化剂起着决定性作用。本文对近年来含氧条件下CO催化还原NO的研究成果进行了系统梳理,重点关注了Pd系、Ir系、Cu系、其他贵金属及金属氧化物催化剂的研究进展,分析了催化剂制备方法、掺杂改性及反应条件对催化性能的影响,同时考察了O₂浓度、H₂O以及SO₂对催化反应的影响,总结并对比了不同体系催化剂的活性位点及其催化机理,指明了O₂在催化还原过程中的抑制机理,得出了几种体系催化剂催化CO还原NO的活性顺序。最后,针对富氧条件下CO催化还原NO所存在的问题和难点,提出深入研究O₂抑制机理、降低贵金属用量、添加活性助剂是今后的研究方向。     

富氧条件下氢气选择性催化还原NOx催化剂研究进展

着重介绍了NOx脱除技术中的选择性催化还原技术,分析了以不同还原剂(NH3、H2、CO、HC)选择性催化还原NOx技术的优缺点,认为H2-SCR脱硝技术具有较高的研究价值和实际的应用前景。从催化剂的活性组分、助剂及载体的角度分析了不同催化剂在氢气选择性催化还原脱硝技术中的应用及其所达到的效果,得出负载贵金属Pt与Pd、添加酸性助剂以及采用复合载体的催化剂性能更佳,并对今后氢气选择性催化还原脱硝技术的研究方向进行展望。     

Surface coverage of Pt atoms on PtCo nanoparticles and catalytic kinetics for oxygen reduction

The surface coverage of Pt atoms on PtCo nanoparticles and its effect on catalytic kinetics for oxygen reduction were investigated. The PtCo nanoparticles with different surface coverage of Pt atoms were synthesized with various methods, including normal chemical method, microemulsion synthesis, and ultrasound-assisted microemulsion. A model of Pt atoms filling into a spherical nanoparticle was proposed to explain the relationship of surface metal atoms and nanoparticle size. The catalytic activity of the PtCo nano-particles is highly dependent on the synthetic methods, even if they have the same chemical composition. The PtCo nano-particles synthesized with ultrasound-assisted microemulsion showed the highest activity, which is attributed to an increase of active surface coverage of Pt atoms on the metal nanoparticles. The rate of oxygen reduction at 0.5 V (vs. SCE) catalyzed by the PtCo synthesized with ultrasound-assisted micro-emulsion was about four times higher than that of the PtCo synthesized with normal chemical method. As demonstrated with rotating-ring disk electrode measurement, the PtCo nano-particles can catalyze oxygen 4-electron reduction to water without intermediate H₂O₂ detected.