NaBH4溶液催化制氢的阴离子效应研究

研究了Cl-和NO3-阴离子对NaBH4溶液现场制氢反应的影响,发现在制氢反应过程中存在着生成金属硼化物和生成金属氢氧化物的竞争反应.当溶液中阴离子为Cl-时,金属离子在催化NaBH4溶液制氢反应时将与硼结合,促使其活化为高活性金属硼化物,能有效促进制氢反应;当溶液中的阴离子为NO3-时,将诱导金属离子生成没有催化活性的金属氢氧化物,抑制制氢反应.     

直接甲醇燃料电池研究进展

介绍了直接甲醇燃料电池的工作原理、研究现状及最新进展,认为直接甲醇燃料电池是目前较理想的燃料电池,有广阔的发展前景。     

直接甲酸燃料电池研究进展

直接甲酸燃料电池是近年来出现的一类新型燃料电池.本文从直接甲酸燃料电池的原理、阳极和阴极催化剂、小型直接甲酸燃料电池电池堆的研究开发等几个方面,对直接甲酸燃料电池的国内外研究现状进行了较为系统的介绍,并指出了直接甲酸燃料电池目前的发展遇到的困难及挑战.     

直接尿素燃料电池研究进展

直接尿素燃料电池可同时处理含尿素废水(尿液等)并发电,且Ni基材料为阳极尿素电氧化反应的有效催化剂。然而由于尿素电氧化反应复杂且缓慢的动力学使得Ni基催化剂活性低且稳定性差,导致直接尿素燃料电池功率密度普遍较低。实现其应用的关键在于对Ni基催化剂进行改性以构建高效稳定的催化剂层及其膜电极组件。因此,详细评述了组装成直接尿素燃料电池的阳极催化剂研究进展,深入分析改性后的催化剂组成结构对系统性能的影响机制(包括载体效应和协同效应),旨在为设计高效稳定的尿素电氧化催化剂提供科学依据。此外,阐述了直接尿素燃料电池系统中膜材料的研究现状及其膜电极组件的构建。最后,总结并展望了该领域的研究重点及未来研究的发展方向,为开发高性能直接尿素燃料电池以推进其商业化进程提供借鉴。     

直接利用生物质的化学燃料电池研究进展

近些年燃料电池技术有了长足的发展,利用燃料电池处理废弃生物质并产电是一种新型途径,可以达到废物处理、能源回收的目的。然而,受限于燃料种类、电池性能、产物分离等因素,传统的燃料电池难以直接用于处理废弃生物质。本文首先针对中低温燃料电池如碱性燃料电池、质子交换膜燃料电池的研究现状进行了综述,结果表明,碱性燃料电池在以小分子有机物作为燃料时性能良好,但是容易受到产物CO₂酸化影响;液相催化燃料电池在催化剂耐受性、生物质处理、电池功率密度等方面表现出优异的性能。然后介绍了电催化剂如过渡金属氧化物、多酸等研究现状,此类催化剂具有较强的氧化性、布朗斯特酸性和路易斯酸性等,具有很强的催化分解生物质的能力,针对液相催化剂不易分离的局限,介绍了催化剂固载化、纳米复合材料等研究进展。之后介绍了电极材料和膜材料的研究进展,碳极板因其综合性能和成本成为当前的主流选择,全氟磺酸膜性能优异,成为实验探究应用的理想材料,同时对一些复合材料的研究现状进行了简要介绍。最后,对化学燃料电池应用于生物质处理的方向进行了展望,液相催化燃料电池综合性能突出,在可处理生物质种类、催化剂循环等问题进一步优化之后,有望成为一种废弃生物质处理的新途径。     

直接甲醇燃料电池用质子交换膜的研究进展

综述了质子交换膜在直接甲醇燃料电池中的作用和要求,目前质子交换膜的研究进展,重点介绍了适用于直接甲醇燃料电池用质子交换膜的各种材料的改性方法。按照物理和化学两种方法对几类质子交换膜材料进行改性。同时对比了改性前和改性后各种聚合物膜的物性特点。     

直接碳燃料电池研究进展

碳燃料电池直接采用固态碳作阳极,不存在气体燃料面临的存储与运输问题.碳燃料电池的热效率远高于氢燃料电池,产物二氧化碳不须进一步纯化就可工业应用或隔离存放.另外,碳燃料来源广泛,生产纯碳的过程往往比生产纯氢的过程有效能保持率高.近几年来,因固体碳燃料电池的已有的技术在集中或分散式供电方面展示出良好的应用前景,受到广泛关注.故对固体碳燃料电池的原理、碳材料结构对阳极放电性能的影响和其它组成部件及单电池原型化设计的相关内容进行了论述.     

NaBH4水解制氢技术

介绍了一种方便、实用且能有效制备高纯度氢气的新型制氢技术———NaBH4水解制备氢气。NaBH4(水溶液)与催化剂作用,水解产生氢气和一种水溶性盐———NaBO2。该反应中,氢的生成速度容易控制;制得的氢气纯度高,不需要纯化过程,可直接作为燃料电池的原料;催化剂可以循环使用;甚至在0℃下也可以生产氢气,无污染。另外,还介绍了本文发明的催化剂和相应的反应器体系,具有催化剂便宜,反应器安全、易于控制等特点。     

Span-80/NiCl2∙6H2O/甲醇/NaBH4体系高效选择性催化还原α-蒎烯

以斯盘类表面活性剂为稳定剂,以NiCl₂?6H₂O 为催化剂前体,以NaBH₄替代外源易燃易爆的氢气,在室温条件下于“一锅”中实现了α-蒎烯的催化还原。考察了斯盘类型、反应介质、NaBH₄用量及反应时间对于反应的影响,得到适宜的反应条件为：Span-80为稳定剂,甲醇为反应介质,NaBH₄∶α-蒎烯摩尔比为0.5,5%NiCl₂·6H₂O,室温反应5h,α-蒎烯的转化率可高达98%,顺式蒎烷的选择性达99%,催化剂能循环使用3次。使用ICP-AES及TEM研究了循环过程中催化剂的流失及形貌,结果表明：在循环过程中Ni的流失率仅为0.2％;催化剂运行1次后的粒径约为4.2nm且分散均匀,循环3次后部分Ni纳米粒子的粒径因聚集而变大,这也许是造成催化剂活性降低的主要原因。XPS和一系列中毒实验结果表明,催化反应的活性物种在性质上很可能是均相的,而原位生成的纳米镍粒子也许仅作为催化物种的“储库”。与传统α-蒎烯加氢工艺相比,该工艺的特点是安全、温和、操作性强、选择性高。     

吡啶改性Pd/SiO2催化剂用于H2和O2直接合成H2O2

引言过氧化氢(H2O2)是一种理想的绿色氧化剂,广泛应用于化学品合成、纺织、造纸、环保、食品、医药、冶金和农业等领域[1]。目前,蒽醌法[2-5]是工业上生产H2O2的主要方法。20世纪40年代,德国I.G.Farbenindustrie首先采用蒽醌法(又称Riedl-Pfleiderer法)工业化生产过氧化氢。该方法首先将2-烷基蒽醌(通常是2-乙基蒽醌)溶解于合适的有机溶剂中,溶液中的2-烷基蒽醌经催化剂催化加氢,被还原成蒽氢醌或5,6,7,8-四氢蒽氢醌,再经空气氧化得到蒽醌或四氢蒽醌和     

微波/过氧化氢系统催化降解苯酚水溶液

研究了在微波/过氧化氢（MW/H₂O₂）系统下苯酚的降解效果，并且详细探讨了影响MW/H₂O₂系统催化氧化降解苯酚的各种因素。实验结果表明：在单独的微波辐照或者过氧化氢氧化下苯酚去除率很小，而在MW/H₂O₂组合氧化系统中有显著的提高，苯酚降解的拟一级动力学速率常数增强因子可达到5.98，表明存在明显的协同效应。另外，在实验中加入Fe²⁺能加速苯酚的降解。     

动态UV-vis/H2O2/草酸铁络合物法光解苯胺

UV -vis/H₂ O₂ /草酸铁络合物法是一种高级氧化工艺 ,这个工艺产生的羟自由基·OH是一种很强的氧化剂 ,能很快和水中有机物发生反应 .以苯胺为处理对象对该法的氧化能力和效果进行了研究 ,并确定了降解苯胺的最佳工艺条件 :pH =3 .5 ,Fe^{2 +} ∶H₂ O₂ ∶C₂ O^{2 -}₄ ≈ 1∶4∶6 (mole) .UV -vis/H₂ O₂ /草酸铁络合物法处理高浓度苯胺水样非常有效 ,12min内苯胺去除率均在 99%以上 .流动法处理苯胺模拟废水的效果明显好于静态法     

氢氧质子交换膜燃料电池阴极流道设计模型

为了优化氢氧质子交换膜燃料电池阴极的气体流道,建立了沿流道长度和深度方向的气体流道设计模型.模型考虑了阴极气体在流道中的动量传递、质量传递和电极反应等物理过程.将二维问题经积分均化后转化为较简单的一维问题,偏微分方程组转变为常微分方程组,使计算过程得以简化.以50 cm长的流道为例,计算了沿流道方向的浓度、流速以及电流密度的分布.还利用此模型分析了各操作与设计参数如入口流速、流道深度、交换电流密度等对浓度、流速和电流密度分布的影响.     

Electro-reduction of hydrogen peroxide on iron tetramethoxy phenyl porphyrin and lead sulfate electrodes with application in direct borohydride fuel cells

Electroreduction of hydrogen peroxide in acidic medium is reported onto carbon-supported iron tetramethoxy phenyl porphyrin (FeTMPP/C) as well as carbon-supported lead sulphate (PbSO₄/C) electrodes. Both the catalytic electrodes can sustain electroreduction of hydrogen peroxide in direct borohydride fuel cells using hydrogen peroxide as oxidant but PbSO₄/C electrode shows catalytic activity.     

过氧化氢法制备二氧化氯的反应机理及动力学

To develop a cleaner production process of H2O2-based chlorine dioxide, this paper presents a study on reaction mechanism and dynamics of the process. It is shown that a complex H2ClO2-ClO3 exists as an intermediate in the process. A rational reaction process is proposed, which unifies several reaction mechanisms reported by different researchers in a wider range of reaction temperature. A theoretical model of the dynamics is presented, and parameters of the model are experimentally estimated and verified.     

硼氢化钠制氢技术在质子交换膜燃料电池中的研究进展

硼氢化钠储氢量高达10.6%,安全、无爆炸危险,携带和运输方便;供氢系统设备简单,启动速度快,产氢速度可调,因此是一个非常良好的氢载体,是为质子交换膜燃料电池供氢的理想储氢介质。硼氢化钠供氢系统也已逐步应用于质子交换膜燃料电池电源中。介绍了这种制氢方式的几项关键技术：硼氢化钠水解制氢催化剂、硼氢化钠制氢反应器、氢气净化系统等在质子交换膜燃料电池中的研究进展,并指出了今后的研究发展方向。     

Electrooxidation of borohydride on platinum and gold electrodes: implications for direct borohydride fuel cells

The electrochemical oxidation of BH₄⁻ in 2 M NaOH on Pt and Au (i.e. catalytic and non-catalytic electrodes, respectively, for BH₄⁻ hydrolysis accompanied by H₂ evolution) has been studied by cyclic voltammetry, chrono-techniques (i.e., potentiometry, amperometry, coulometry) and electrochemical impedance spectroscopy. In the case of Pt the cyclic voltammetry behaviour of BH₄⁻ is influenced by both, the catalytic hydrolysis of BH₄⁻ yielding H₂ (followed by electrooxidation of the latter at peak potentials between −0.7 and −0.9 V versus Ag/AgCl, KCl_std) and direct oxidation of BH₄⁻ at more positive potentials, i.e., between −0.15 and −0.05 V. Thiourea (TU, 1.5×10⁻³ M) was an effective inhibitor of the catalytic hydrolysis associated with BH₄⁻ electrooxidation on Pt. Therefore, in the presence of TU, only the direct oxidation of BH₄⁻ has been detected, with peak potentials between −0.2 and 0 V. It is proposed that TU could improve the BH₄⁻ utilization efficiency and the coulombic efficiency of direct borohydride fuel cells using catalytic anodes. The electrooxidation of BH₄⁻ on Pt/TU is an overall four-electron process, instead of the maximum eight electrons reported for Au, and it is affected by adsorbed species such as BH₄⁻ (fractional surface coverage ∼0.3), TU and possibly reaction intermediates.     

CH4-CaSO4和H2S-Fe2O3反应体系的热力学和动力学研究

The destruction of hydrocarbon in deep carbonate diagenetic environment is one of problems on the formation of oil and gas. Organic-inorganic reactions in the process of TSR(Thermochemical Sulfate Reduction) are the main reason to make disappearance of the hydrocarbons. The work in this field has often been the subject of much research work in recent years. In this paper, the thermodynamics of CH4-CaSO4 and H2S-Fe2O3 systems is discussed to investigate the possibility of reactions. It is found that these two reactions can proceed spontaneously.Increasing temperature is favorite for CH4-CaSO4 system but disfavorite for H2S-Fe2O3 system. Thermal simulation experiments were carried out using autoclave at high temperature and high pressure. The properties of the products were characterized by microcoulometry, FT-IR and XRD methods. On the basis of the experimental data, a reaction kinetic model is developed and kinetic parameters are determined.     

Investigation of Ti mesh-supported anodes for direct borohydride fuel cells

The use of titanium mesh-supported gold and silver anodes in direct borohydride fuel cells (DBFCs) is reported. The anodes were prepared by either thermal decomposition or electrochemical deposition and were characterised by scanning electron microscopy and X-ray diffraction analyses. The performance of the mesh electrodes was compared with that for carbon-supported electrodes. The mesh anodes gave current densities, for borohydride oxidation, up to 50% greater and cell power densities up to 20% greater than those obtained with carbon-supported anodes. The effects of catalyst loading and fuel cell operating conditions are also reported. Electrode stability was examined over a prolonged period.     

LaNi0.9Ru0.1O3 as a cathode catalyst for a direct borohydride fuel cell

LaNi_0.9Ru_0.1O₃ as cathode catalyst for a direct borohydride fuel cell (DBFC) was synthesized and investigated for the first time. The electrochemical experiments indicated that perovskite-type oxide LaNi_0.9Ru_0.1O₃ exhibited higher electrochemical performance compared with LaNiO₃, which suggested incorporation of element Ru into LaNiO₃ could further improve the catalytic ability for oxygen reduction reaction (ORR) in alkaline solution. LaNi_0.9Ru_0.1O₃ catalyst was found to have good tolerance of BH₄⁻. Meanwhile the maximum power density of 171 mW cm⁻² was obtained at 65 °C without using any precious ion exchange membrane. A life test indicated that the DBFC displayed no significant degradation for about 70 h testing. The electrochemical data suggested that LaNi_0.9Ru_0.1O₃, which provided a simple way to construct DBFCs without using any ion exchange membrane, might be promising cathode catalyst with high performance and low cost for DBFCs.