乙醇电催化氧化

乙醇作为典型的可再生绿色环保型能源,具有易储存和携带、较高的能量密度、易生产等优点而备受关注。本文详细介绍了近年来国内外乙醇电催化氧化研究的重要进展,着重叙述了乙醇电催化氧化的反应机理,不同催化剂材料对乙醇电氧化的优缺点,进一步探讨了影响乙醇电氧化反应活性和选择性的因素,总结了提高乙醇电氧化活性和选择性的策略,最后,对其今后可能的研究方向进行了展望。     

乙醇催化氧化实验的改进

高中化学（人教版）中“乙醇催化氧化实验”,用闻气味的方法,来证明乙醛的生成。但实际操作过程中往往由于乙醇较多,而闻不到乙醛的刺激性气味。     

乙醇催化氧化实验的改进

在苏教版高中《化学2（必修）》中,乙醇的催化氧化实验的做法是：向试管中加入3～4mL无水乙醇,浸入50℃左右的热水中,以保持反应所需的温度。将铜丝烧热,迅速插入乙醇中,反复多次,观察并感受铜丝颜色和乙醇气味的变化。     

乙醇催化氧化实验的改进

通过分析高中化学教材中实验的不足及相关文献报道,运用注射器、洗耳球、试管、酒精灯等简单仪器,设计了一套乙醇在铜催化下与氧气反应生成乙醛的实验装置,取得了较好的实验效果。     

乙醇的催化氧化实验改进

乙醇的催化氧化是高中有机化学中的一个重要的实验,从人教版全日制高级中学教科书《化学》（必修加选修》第二册的第一版,到山东科技版《普通高课程标准实验教科书·有机化学基础》,此实验的设计一直没变,但该实验的效果不理想,因此笔者对此实验进行改进。     

生物乙醇重整制氢反应器

生物乙醇重整制氢是一种具有良好应用前景的制氢技术,是当前低碳能源领域的研究热点.发展生物乙醇重整制氢技术的关键是研发在低温下具有高活性和高选择性的新型重整催化剂,以及开发新式高效的催化反应器.本文着眼于反应器对生物乙醇重整制氢过程的影响,综述了国内外固定床反应器、微通道反应器和膜反应器等生物乙醇重整制氢反应器的研究现状...     

激光促进乙醇氧化偶联反应

用ＸＲＤ、ＩＲ和脉冲ＣＯ２激光，研究了在固体Ｃｕ２（ＰＯ４）（ＯＨ）ｔ Ｐｂ３（ＰＯ４）２表面上激光促进乙醇氧化偶联的反应性能。实验结果表明：乙醇的定位化学吸附态决定着反应产物的选择性，甲基吸附态（〉Ｐ＝０…Ｈ－ＣＨ２ＣＨ２ＯＨ）反应生成１，４－丁二醇，而羟基吸附态（〉Ｐｂ…ＯＨＣＨ２ＣＨ３）则生成乙烯；固体表面构造基元的振动结构是影响激光能量利用率的主要因素，Ｃｕ２（ＰＯ４）（ＯＨ）表面Ｐ＝Ｏ键     

乙醇氧化脱氢实验的深度研究

通过实验验证和理论分析,说明教材乙醇脱氢反应的实验设计存在不足。分析研究乙醇的2种脱氢方式,认为使用氧化铜欠妥,在此基础上提出了较为科学、合理的实验设计。     

乙醇的低温光催化氧化实验研究

利用傅里叶变换红外光谱仪(FT-IR),在间歇式反应器中研究了高浓度乙醇的低温光催化氧化特性。研究结果表明,FT-IR技术能够用来研究气态有机物的光催化降解特性;在乙醇的光催化降解过程中,有乙醛等中间产物生成,乙醇先被氧化为乙醛,再被氧化为二氧化碳;在间歇式反应器中,乙醇的循环流量对乙醇的瞬时降解速率影响不大;高浓度乙醇的低温光催化氧化过程可以用单步Langmuir-Hinshelwood 方程来描述;温度对乙醇光催化氧化的初始反应速率的影响十分显著,高浓度乙醇的初始反应速率随温度的升高而迅速提高。     

乙醇、甲醛的被氧化实验

不久以前我做了“在H_2SO_4作用下KMnO_4对乙醇、甲醛的氧化作用实验”,我取二只20毫升试管,分别装95％乙醇和40％福美林各3毫升,然后用长滴管吸取浓H_2SO_4小心插入盛乙醇的试管底部,慢慢注入3毫升浓H_2SO_4,小心提出滴管,不使H_2SO_4和C_2H_5OH相混。以     

滴醇生花——乙醇催化氧化反应的改进

针对乙醇催化氧化实验装置的不足,紧扣新课标,本着操作简单、现象明显、易推广的原则,用铜片代替铜丝,使得改进后的实验具有美、趣、省、简、易的优点.     

负载型金催化剂催化乙醇选择氧化反应

选择不同氧化物(Al2O3,SiO2,TiO2,MgO)和H-ZSM-5分子筛作为载体,以尿素为沉淀剂,采用沉积-沉淀法制备了一系列负载型金催化剂.采用X射线衍射、电感耦合等离子体发射光谱、程序升温还原、NH3程序升温脱附和透射电镜等技术对催化剂样品进行了表征,并测定了催化剂对乙醇选择氧化反应的催化性能.选择Au/Al2O3催化剂,考察了金负载量、反应条件(温度、压力、时间)和添加剂对乙醇选择氧化反应的影响.结果表明,所制备的Au/Al2O3催化剂的金负载率较高,金粒子较小(3～4 nm)且分布均匀.载体对金催化剂催化乙醇氧化反应有显著影响,主要产物为乙醛、乙酸乙酯和缩醛.以TiO2为载体时,乙醇转化率较高.以Al2O3为载体时,乙酸乙酯选择性较高;少量碱性添加剂可抑制缩醛的生成,并可提高乙醇转化率和乙酸乙酯选择性.在优化的条件下,乙醇转化率可达4.7%,乙酸乙酯选择性可达93.5%.     

Electrocatalytic Oxidation of Ethanol on Electrodcposited Palladium Electrode

Therearemanyinvestigationsabouttheelectrocatalyticoxldationofethanolontheelectrodeofplatinunlelectrode'-'.whicharemainlyinacidmedium.However.tothebestknowledgeoftheauthor.therearenoinvestigationsabouttheoxidatiollofethanolonpalladiumelectrode.letaloneonPd/GCelectrodepreparedbyelectrodeposition.Accordingtotheexperimentalresultsinthispaper,Pd/GCelectrodeismoreelectroactivetotheoxidationofethanolthantothatofmethanolinalkalinemedium(e.g.inI.0mol/LNaOH).basedontheiroxidationpeakpotentialswhicha…     

Electrochemical Impedance of Ethanol Oxidation in Alkaline Media

Nickel modified NiOOH electrodes were used for the electrocatalytic oxidation of ethanol in alkaline solutions. The electro-oxidation of ethanol in a 1 mol/L NaOH solution at different concentrations of ethanol was studied by ac impedance spectroscopy. Electrooxidation of ethanol on Ni shows negative resistance on impedance plots. The impedance shows different patterns at different applied anodic potential. The influence of the electrode potential on impedance was studied and a quantitative explanation for the impedance of ethanol oxidation was given by means of a proposed mathematical model. At potentials higher than 0.52 V(vs. Ag/AgCl), a pseudoinductive behavior was observed, but at those higher than 0.57 V, impedance patterns were reversed to the second and third quadrants. The conditions required for the reversing of impedance pattern were delineated with the impedance model.     

温度对乙醇电催化氧化的影响

升高温度可以提高反应速率和增加物质的输运,因此通过不同温度下反应机理的研究可以深入理解电催化过程,对催化剂的设计具有指导意义。本工作初步建立了变温原位红外测定方法。采用温控电极,用电势测温法进行温度的校准,实验得出控温仪器加热温度Th与电极表面温度TS的关系为T_S=0.57T_h+7.71 (30°C T_h≤50°C);T_S=0.62T_h+5.12 (50°C T_h≤80°C),误差分析最大温差为1°C。利用该方法我们研究了商业Pt/C催化剂在不同温度下乙醇的电氧化过程。从循环伏安图可以明显看到随着温度的升高整体氧化电流增大,起始电位、峰电位均负移,说明热活化使得氧化反应更容易进行;第一个峰电流与第二个峰电流的比值用于定性评估CO_2的选择性,对比25°C,商业Pt/C催化剂在65°C下第一峰提高30%,说明高温有利于C―C键的断裂。对比25°C的原位红外谱图,我们发现35°C及50°C下商业Pt/C催化剂上CO_2产物的起始电位负移200 m V,说明高温下,Pt/C催化剂能在更低的电位提供含氧物种;而CH_3CHO、CH_3COOH起始电位不随温度变化。用CO_2与CH_3COOH的积分面积比来评估CO_2选择性,发现高温低电位其选择性最高,说明高温低电位有利于乙醇完全氧化生成CO_2,而高温高电位下表面吸附含氧物种占据了活性位,阻碍C―C键断裂。     

乙醇在Ni-Mo合金电极上氧化的动力学模型

利用循环伏安以及稳态极化曲线等方法研究了在１ｍｏｌ．Ｌ＾－１ＫＯＨ溶液中,乙醇在电沉积Ｎｉ－Ｍｏ合金电极上氧化的电化学特性,提出了一个数学模型来预计乙醇在电沉积Ｎｉ－Ｍｏ合金电极上的电化学行为,在碱性溶液中,Ｎｉ（ＯＨ）２／ＮｉＯＯＨ电对的氧化还原过程是乙醇氧化的前期步骤,Ｎｉ（ＯＨ）２／ＮｉＯＯＨ）电对相应的速度常数（即ｋ１和ｋ－１）是电极电位的函数,乙醇氧化是通过一个速度常数为ｋｃ１的化学反应来完成,推导出了各个动力学方程并将实验数据与方程进行比较而获得各个动力学参数,电化学速度常数ｋ１（Ｅ）＝１．４１＊１０＾７ｅｘｐ（０．５ＦＥ／ＲＴ）ｍｍｏｌ．ｃｍ＾－２．ｓ＾－１以及ｋ－１（Ｅ）＝０．７１１ｅｘｐ（０．５ＦＥ／ＲＴ）ｍｍｏｌ．ｃｍ＾－２．ｓ＾－１,Ｅ是相对饱和甘汞电极（ＳＣＥ）的电极电位,而化学反应的速     

High Temperature Electrochemical Oxidation of Ethanol Over Perovskite-Type Oxides

Ethanol oxidation was investigated in a solid electrolyte electrochemical reactor using a perovskite-type oxide La_0.6Sr_0.2Co_0.8Fe_0.2O₃ as anode. Experiments were conducted between 300–750°C at atmospheric pressure in an ytrria-stabilized-zirconia continuous stirred tank reactor using fuel-rich reactant mixtures.     

Oxidation of Ethanol in Cu-Faujasites Studied by IR Spectroscopy

In this study, IR studies of the coadsorption of ethanol and CO on Cu⁺ cations evidenced the transfer of electrons from ethanol to Cu⁺, which caused the lowering of the frequency of the band attributed to CO bonded to the same Cu⁺ cation due to the more effective π back donation of d electrons of Cu to antibonding π* orbitals of CO. The reaction of ethanol with acid sites in zeolite HFAU above 370 K produced water and ethane, polymerizing to polyethylene. Ethanol adsorbed on zeolite Cu(2)HFAU containing acid sites and Cu⁺_exch also produced ethene, but in this case, the ethene was bonded to Cu⁺ and did not polymerize. C=C stretching, which is IR non-active in the free ethene molecule, became IR active, and a weak IR band at 1538 cm⁻¹ was present. The reaction of ethanol above 370 K in Cu(5)NaFAU zeolite (containing small amounts of Cu⁺_exch and bigger amounts of Cu⁺_ox, Cu²⁺_exch and CuO) produced acetaldehyde, which was further oxidized to the acetate species (CH₃COO⁻). As oxygen was not supplied, the donors of oxygen were the Cu species present in our zeolite. The CO and NO adsorption experiments performed in Cu-zeolite before and after ethanol reaction evidenced that both Cu⁺_ox and Cu²⁺ (Cu²⁺_exch and CuO) were consumed by the ethanol oxidation reaction. The studies of the considered reaction of bulk CuO and Cu₂O as well as zeolites, in which the contribution of Cu⁺_ox species was reduced by various treatments, suggest that ethanol was oxidized to acetaldehyde by Cu²⁺_ox (the role of Cu⁺_ox could not be elucidated), but Cu⁺_ox was the oxygen donor in the acetate formation.