有机合成型燃料电池

现在燃料电池已进入实用化开发阶段。除氢作燃料的氢-氧燃料电池外;以甲醇、天然气、石油、煤作原料制成氢或氢和一氧化碳的混合物作燃料的燃料电池以及把甲醇等有机物直接作燃料的有机物燃料电池也不断问世。燃料电池在一般情况下,其发电的同时发     

BaCe_(0.8)Y_(0.2)O_(3-α)固体电解质的离子导电性及其燃料电池性能

用高温固相反应合成了BaCe0.8Y0.2O3-α固体电解质用氢浓差电池和氧浓差电池方法研究了它的离子导电特性。以该氧化物为固体电解质多孔性Pt为电极材料组成氢空气燃料电池测定了该燃料电池的电流电压特性。研究发现BaCe0.8Y0.2O3-α在氢气中几乎是一个纯的质子导体在氧气中是一个氧离子和电子空穴的混合导体其燃料电池的开路电压OCV接近于理论值最大输出电流密度约为820mA·cm-21000℃最大输出功率密度约为200mW·cm-21000℃放电性能稳定具有良好的电池性能。     

用于质子交换膜燃料电池催化剂结构研究的原位XAFS实验方法

依托上海光源的X射线吸收精细结构(XAFS)谱学线站(BL14W1),建立并发展了用于氢-氧质子交换膜燃料电池(PEMFC)原位XAFS实验的测试装置,以Pt/C纳米催化剂作为PEMFC的阴极催化剂, Pd/C作为燃料电池的阳极催化剂,采集在工作状态下的阴极催化剂的XAFS数据,同步监测燃料电池的电流-电压(J-V)曲线和功率密度曲线,观察到Pt/C催化剂在反应过程中不同电位下氧化态的变化,在高电位下Pt/C催化剂的表面存在较强的Pt-O键,降低了Pt/C催化剂的性能.本文同时也验证了我们所建立的实验装置和研究方法的可行性和可靠性.     

低温燃料电池氧电极催化剂*

氧电极催化剂及缓慢的阴极氧还原动力学是制约低温燃料电池商业化的关键瓶颈因素之一。为此,国内外研究者近年来从提高低温燃料电池氧电极催化剂的催化活性和稳定性、降低催化剂的成本、发展非贵金属氧还原催化剂等方面开展了大量的研究工作,有力地促进了低温燃料电池的发展进程。本文在简要介绍低温燃料电池氧电极反应机理的基础上,从催化剂载体、贵金属及其合金催化剂、金属大环化合物及M-N/C类催化剂和过渡金属硫族化合物类催化剂等方面详细综述了低温燃料电池氧电极催化剂近年来的主要研究进展,并指出了各类催化剂目前尚待解决的问题和发展方向。     

Ba_(0.95)Ce_(0.9)Y_(0.1)O_(3-α)固体氧化物的离子导电性及其燃料电池性能

以Ba0 .95Ce0 .9Y0 .1O3-α氧化物陶瓷为固体电解质 ,以多孔性Pt为电极材料 ,分别组成氢、氧浓差电池和氢_空气燃料电池 ,测定了 6 0 0～ 10 0 0℃范围内的浓差电池电动势 ,燃料电池的放电性能和电极极化性能 .结果表明 ,Ba0 .95Ce0 .9Y0 .1O3-α在氢气氛中几乎是一个纯质子导体 ,在氧气氛中是氧离子与电子空穴的混合导体 ,氧离子迁移数在 0 .3～ 0 .5之间 ,在氢_空气燃料电池条件下显示出混合离子 (质子 +氧离子 )导电性 ,总离子迁移数大于 0 .9.该燃料电池性能良好 ,Pt电极极化性能很小 ,最大输出电流密度为 6 80mA·cm- 2 (10 0 0℃ ) ,最大输出功率密度为 16 0mW·cm- 2 (10 0 0℃ ) .     

BaCe0.8Y0.2O3-α固体电解质的离子导电性及其燃料电池性能

用高温固相反应合成了BaCe08Y02O3-α固体电解质,用氢浓差电池和氧浓差电池方法研究了它的离子导电特性.以该氧化物为固体电解质,多孔性Pt为电极材料,组成氢-空气燃料电池,测定了该燃料电池的电流-电压特性.研究发现,BaCe0.8Y0.2O3-α在氢气中几乎是一个纯的质子导体,在氧气中是一个氧离子和电子空穴的混合导体,其燃料电池的开路电压(OCV)接近于理论值,最大输出电流密度约为820mA@cm-2(1000℃),最大输出功率密度约为200mW@cm-2(1000℃),放电性能稳定,具有良好的电池性能.     

BaxCe0.8Y0.2O3-α固体氧化物燃料电池性能

用高温固相反应法合成了BaxCe0.8Y0.2O3-α（x=1.03,1,0.98)系列固体电解 质，用粉末X射线衍射法研究了样品的晶体结构，用氢及氧浓差电池方法研究了样 品的质子及氧离子导电特性，测定了它们的氢－空气燃料电池的放电性能。结果表 明，各样品均为钙钛矿斜方晶单相结构；质子导电和燃料电池输出电流密度均随样 品中钡离子含量的增加而增大，Ba1.03Ce0.8Y0.2O3-α具有最大的质子导电性和燃 料电池输出电流密度；各样品的氧离子导电性几乎不受钡离子含量影响。     

氧化镧作为直接硼氢化物燃料电池阴极催化剂的研究

通过采用线性电势扫描(LSV)和恒电流计时电势扫描方法对氧化镧作为直接硼氢化物燃料电池阴极催化剂的电化学性能进行了研究.实验结果表明:在单室燃料电池体系中,氧化镧对氧还原具有良好的活性,同时在强碱溶液中对硼氢根离子具有很强的稳定性且对硼氢根的水解没有任何促进作用.以镍基储氢合金作为电池的阳极催化剂组装成简单的单室燃料电池,电池的开路电压达到1.052 V,在常温下(21℃),电池于0.491 V获得最高功率密度65.25 mW·cm-2,电池运行稳定.     

Pt/TiO_2催化剂上的氢—氧作用——Ⅱ. 程序升温还原和程序升温氧化研究

本文采用TPR、TPO技术分别考察了氧处理Pt/TiO_2上氧物种的还原行为和氢还原样品的氧化过程.TPR结果表明,表面含有活泼氧物种的Pt/TiO_2样品对氢很活泼,室温条件下可以吸附大量氢,并且这些吸附氢又可以在TPR过程中脱附.表面活泼氧物种与氢的反应温度在500—673K之间,当大于673K时,Pt/TiO_2继续耗氢,可能是氢与还原产生的表面Ti~(3+)离子进一步反应生成钛—氢物种,并向TiO_2体相扩散与TiO_2体相晶格氧发生反应.对于773K还原的Pt/TiO_2作品,室温吸附氧在TPD过程中可以与表面吸附氢反应;473K氧化处理可以消除表面的吸附氢,但并不能完全去除体相储氢;573K氧化处理则基本上恢复了原样品的氧化状态.不同温度氢还原处理的Pt/TiO_2样品在动态氧化过程(TPO)中,在300-600K温区,气相氧与样品上表面吸附氢和表面氧空位反应;在大于600K温区,氧主要与表面钛—氢物种发生反应,并向体相扩散,与体相氢发生反应.文中描述了气相氢、氧分别与Pt/TiO_2催化剂存在的氧或氢物种作用的形式.     

质子交换膜燃料电池阴极非贵金属M-Nx/C型氧还原催化剂研究进展

氧还原反应(ORR)是燃料电池能量转换的关键步骤,开发高性能低成本的催化剂以替代铂族贵金属是推动燃料电池商业化的重要途径。本文综述了质子交换膜燃料电池非贵金属M-N_x/C型催化剂的最新研究进展,概括了氧还原反应的基础理论,系统展示了先进表征技术对活性位点鉴定和反应机理研究的作用,总结了M-N_x/C型催化剂近年来的代表工作和活性突破,阐述了稳定性问题的根源及对应的方案策略,我们认为M-N_x/C型催化剂未来的发展方向是理性设计具高位点密度和高稳定性的催化剂。     

Electrocatalytic mechanism and kinetics of SOMs oxidation on ordered PtPb and PtBi intermetallic compounds: DEMS and FTIRS study

The electrocatalytic activities and mechanisms of PtPb and PtBi ordered intermetallic phases towards formic acid, formaldehyde and methanol oxidation have been studied by DEMS and FTIRS, and the results compared to those for a pure polycrystalline platinum electrode. While PtPb exhibits an enhanced electrocatalytic activity for the oxidation of all three organic molecules when compared to a Pt electrode, PtBi exhibits an enhanced catalytic activity towards formic acid and formaldehyde oxidation, but not methanol. FTIRS data indicate that adsorbed CO does not form on PtPb or PtBi intermetallic compounds during the oxidation of formic acid, formaldehyde and methanol, and therefore their oxidation on both PtPb and PtBi intermetallic compounds proceeds via a non-CO(ads) pathway. Quantitative DEMS measurements indicate that only CO(2) was detected as a final product during formic acid oxidation on Pt, PtPb and PtBi electrodes. At a smooth polycrystalline platinum electrode, the oxidation of formaldehyde and methanol produces mainly intermediates (formaldehyde and formic acid), while CO(2) is a minor product. In contrast, CO(2) is the major product for formaldehyde and methanol oxidation at a PtPb electrode. The high current efficiency of CO(2) formation for methanol and formaldehyde oxidation at a PtPb electrode can be ascribed to the complete dehydrogenation of formaldehyde and formic acid due to electronic effects. The low onset potential, high current density and high CO(2) yield make PtPb one of the most promising electrocatalysts for fuel cell applications using small organic molecules as fuels.     

Influence of bi modification of pt anode catalyst in direct formic acid fuel cells

The influence of Bi modification of Pt anode catalyst on the performance of direct formic acid fuel cells was investigated. Compared with the unmodified Pt anode, the Bi modified Pt (PtBi(m)) electrode prepared by under-potential deposition (UPD) caused faster electrocatalytic oxidation of formic acid at the same value of the overpotential, and thus, PtBi(m) resulted in an increase in the power performance of direct formic acid fuel cells. Electrochemical impedance spectra helped to explain the difference of performance between the unmodified Pt and Bi modified Pt electrodes. Solution conductivity and dehydration phenomena occurring in highly concentrated formic acid solutions can also explain the higher power performance of PtBi(m).     

铂铋金属间化合物催化剂的氧还原与抗甲醇氧化性能

采用氩弧熔炼后热处理方法制备了PtBi金属间化合物材料.采用循环伏安法和旋转圆盘电极进行电化学性能测试.通过在0.5 mol•L^－1 H₂SO₄＋0.25 mol•L^－1 CH₃OH溶液中对氧还原的起始电位和电流密度大小比较发现,与光滑铂电极相比,PtBi金属间化合物具有良好的氧还原催化性能和抗甲醇中毒性能.从结构方面分析了PtBi具有抗甲醇中毒性能的原因,认为是PtBi中Pt-Pt的间距大，不利于甲醇的吸附解离. X射线光电子能谱(XPS)结果表明,PtBi材料中Pt的d电子空穴增加,可能是导致PtBi电极表面氧还原电流增大的原因.     

甲酸在Pt-Ru/GC电极上氧化的SERS研究

采用循环伏安(CV)法、计时电流法和电化学原位表面增强拉曼散射光谱(SERS)技术研究了甲酸在Pt-Ru/GC电极上的氧化行为, 发现甲酸在Pt-Ru/GC电极上与在粗糙Pt电极上一样, 也能自发解离出强吸附中间体CO和活性中间体—COO－. 从分子水平证实钌的加入有利于提高电极对甲酸的电催化氧化活性, 当镀液中Pt：Ru的摩尔比从10∶1变化到1∶1, CO的氧化峰电位从0.41 V负移至0.35 V, 约负移了60 mV. Pt-Ru/GC(1∶1)电极与粗糙Pt电极相比, CO在电极表面氧化完毕的电位亦负移了约200 mV. 该研究结果表明, 电化学原位表面增强拉曼散射光谱技术可望成为研究电催化反应机理的普适谱学工具.     

Modification of a Pt surface by spontaneous Sn deposition for electrocatalytic applications. 2. Oxidation of CO,formaldehyde, formic acid,and methanol

The electrocatalytic activity of a spontaneously tin-modified Pt catalyst, fabricated through a simple dip-coating method under open-circuit conditions and characterized using surface analysis methods, was studied in electrooxidation reactions of a preadsorbed CO monolayer and continuous oxidation of methanol, formic acid, and formaldehyde in the potentiodynamic and potentiostatic modes. The catalytic activity of the tin-modified Pt surface is compared with that of a polycrystalline Pt electrode. Spontaneously Sn-modified Pt catalyst shows a superior activity toward adsorbed CO oxidation and thus can be promising for PEFC applications. The methanol oxidation rate is not enhanced on the Sn-modified Pt surface, compared to the Pt electrode. Formic acid oxidation is enhanced in the low potential region on the Sn-modified surface, compared to the Pt electrode. The formaldehyde oxidation rate is dramatically increased by modifying tin species at the most negative potentials, where anodic formaldehyde oxidation is completely suppressed on the pure Pt electrode. The results are discussed in terms of poisoning CO intermediate formation resulting from dehydrogenation of organic molecules on Pt sites, and oxidation of poisoning adsorbed CO species via the surface reaction with OH adsorbed on neighboring Sn sites.     

Mass-transport-limited oxidation of formic acid on a PdMLPt(100) electrode in perchloric acid

In this communication, we study the electrocatalytic formic acid oxidation process on an epitaxially grown Pd monolayer on a Pt(100) single crystal in perchloric acid. The formic acid oxidation activity on this Pd_MLPt(100) electrode in perchloric acid is significantly enhanced compared to the same electrode in sulfuric acid and compared to unmodified Pt(100), with a low onset potential of around 0.14 V_RHE. The absence of hysteresis between the positive and negative scan during formic acid oxidation indicates the remarkable resistance to CO poisoning of the Pd monolayer surface. Most importantly, we report, for the first time, a mass-transport-limited formic acid oxidation rate on the Pd_MLPt(100) rotating electrode in perchlorate acid, setting a catalytic benchmark for future electrocatalysts for formic acid oxidation.     

Pt电极上甲酸电催化氧化机理研究进展

本文综述了甲酸在铂电极上电催化氧化机理的实验和理论研究进展. 铂电极甲酸的电化学氧化主要有两种途径：1）间接途径,甲酸经由CO中间物氧化为最终产物CO₂,室温下该途径对总电流贡献不超过1%;2）直接途径,甲酸直接氧化生成CO₂. 作者课题组对文献中桥式吸附甲酸根是否是甲酸氧化反应直接途径的反应中间物的争论进行了详细的分析和探讨,认为桥式吸附的甲酸根不是间接途径中生成CO的前驱体,也不是甲酸直接氧化途径的中间物. 作者课题组还指出了支持甲酸根是甲酸直接氧化途径的反应中间物的推论的问题所在.     

金属间化合物PtSb对乙醇的电催化氧化性能

采用氩弧熔炼和热处理方法获得PtSb有序金属间化合物材料. 用循环伏安和计时电流技术进行电化学性能测试. 在含有0. 25 mol•L^-1 CH₃CH₂OH的硫酸溶液中, 通过对乙醇电氧化的起始电位和电流密度大小的比较发现, PtSb金属间化合物具有良好的催化乙醇氧化性能. 利用XRD和XPS技术分析了晶体结构和电子结构. 采用不同扫描速率下的循环伏安技术得到乙醇氧化的电子交换系数(α), 发现C₂H_{5OH在PtSb催化剂表面上反应时的α远远大于在Pt电极表面的.}     

Mechanistic study of electrocatalytic oxidation of formic acid at platinum in acidic solution by time-resolved surface-enhanced infrared absorption spectroscopy

Surface-enhanced infrared absorption spectroscopy (SEIRAS) combined with cyclic voltammetry or chronoamperometry has been utilized to examine kinetic and mechanistic aspects of the electrocatalytic oxidation of formic acid on a polycrystalline Pt surface at the molecular scale. Formate is adsorbed on the electrode in a bridge configuration in parallel to the adsorption of linear and bridge CO produced by dehydration of formic acid. A solution-exchange experiment using isotope-labeled formic acids (H(12)COOH and H(13)COOH) reveals that formic acid is oxidized to CO(2) via adsorbed formate and the decomposition (oxidation) of formate to CO(2) is the rate-determining step of the reaction. The adsorption/oxidation of CO and the oxidation/reduction of the electrode surface strongly affect the formic acid oxidation by blocking active sites for formate adsorption and also by retarding the decomposition of adsorbed formate. The interplay of the involved processes also affects the kinetics and complicates the cyclic voltammograms of formic acid oxidation. The complex voltammetric behavior is comprehensively explained at the molecular scale by taking all these effects into account.     

甲酸解离吸附的动力学和时间分辨FTIR特征

 运用电化学暂态（电位阶跃）方法和时间分辨FTIR反射光谱研究甲酸在Pt电极上的解离吸附过程，揭示了这一表面分子过程的反应速率在－0．25至0．25VvsSCE区间呈火山形变化的规律，还测得在含10－3mol•L－1HCOOH的溶液中最大的初始解离速率（－0．06V时）为9.33×10－11mol•cm－2•s－1.