钛基体中离子注入镍和钼的电催化活性

Grenness等发现,铂离子注入钨基体中,对H~+还原产生的电催化性能与纯铂相近,此后,Wolf等用离子注入和离子束混合技术制作了多种电极,其中Pt/RuO_2、Pt/C、Pt/WC电极用于H~+和O_2的电还原以及甲醇和甲酸的电氧化,其催化活性和稳定性均优于光滑的纯铂电极,目前,在其它方法制作的析氢电极材料中,最可能用于工业电解槽的为NiMo合金电极和复合Raney镍合金电极,本工作将镍和钼离子注入到钛基体中,研究了此电极在30 wt％KOH溶液中析氢电催化行为,并通过电子探针显微分析(EPMA)和X射线光电子能谱(XPS)分析,检测了离子注入电极的表面成分、注入元素的浓度分布及价态。     

新型聚邻苯二酚/铂复合膜修饰电极对甲醛电化学氧化

研究了聚邻苯二酚／铂复合膜（Pt／polymer／GC）修饰电极对甲醛的催化氧化作用。结果表明,甲醛在Pt／polymer／GC电极上的氧化过程是一表面控制过程。电解质体系对甲醛的催化氧化有明显影响：在0．5mol／L硫酸中,甲醛主要发生第一步氧化生成甲酸的反应。甲醛的第一氧化峰电流随浓度的增加而增大,并且呈线性关系,可用于甲醛的检测。     

低碳钢基体中离子注入镍和钼的电催化活性

离子注入不受相律和化学平衡的限制,也不受离子源和基体种类的约束,注入离子的能量和剂量精确可控,因而它是实现材料表面改性最有效的方法之一.自Grenness等发现注铂的钨电极,对H~+还原的电催化性能与纯铂接近之后,Wolf等将注入的Pt/RuO_2、Pt/C、Pt/WC电极用于H~+、O_2的电化学还原及甲酸的电化学氧化,其催化活性和稳定性均优于光滑的纯铂电极、Thompson等在钛基上注铂,用于催化析氢也得到类似的效果。近期文献报导,用热处理或电沉积方法制备的Ni-Mo、Ni-Mo-V 合金电极有很低的析氢超     

不同介质对Pt/GC电极制备及其性能的影响

应用循环伏安法(CV),扫描电子显微镜(SEM)和电化学原位红外反射光谱(in situFTIRS)研究了不同介质对碳载铂纳米薄膜电极(Pt/GC)的表面结构以及该薄膜电极对甲酸电催化氧化性能的影响.结果表明,使用不同介质的镀铂溶液,均可电沉积出分布较为均匀的Pt粒子,但其尺寸与形貌却相差很大.当以H2SO4作介质,由循环伏安法于玻碳电极上电沉积Pt得到的(Pt/GC1)电极,其Pt粒子粒径约100~200 nm;而在HClO4介质得到的(Pt/GC2)电极,则含有两种Pt微晶:其一是立方体形,粒径约200 nm,其二为菜花状,粒径约400 nm.电化学循环伏安和原位红外反射光谱测试指明,不同介质制备的Pt/GC电极对甲酸的电催化氧化均表现出与本体铂电极(Pt)相类似的特性,即可通过活性中间体或毒性中间体将甲酸氧化至CO2,但不同结构的Pt/GC电极具有不同的电催化活性.进一步以Sb或Pb修饰Pt/GC电极,不仅可以有效地抑制毒性中间体CO的生成,而且还能显著提高其电催化活性.比较本文研究的7种电极,其电催化活性顺序依次为:Sb-Pt/GC2>Pb-Pt/GC2>Pb-Pt/GC1>Sb-Pt/GC1>Pt/GC2>Pt/GC1>Pt.     

镀Pd的GC电极上HCOOH的电催化氧化

在玻璃碳 (GC)基底上电沉积Pd ,应用SEM观测Pd沉积层的表面形貌 ,用循环伏安法研究了Pd/GC电极上HCOOH在HClO4溶液中的电氧化行为 .结果表明 ,Pd的电沉积条件影响电极的催化性能 .在高电流密度下制得的Pd/GC电极对HCOOH的电氧化具有比纯Pd电极更高的催化活性 .当电极表面生成PdO时 ,HCOOH被电氧化的活性很低 ,而在PdO还原后生成的Pd表面 ,HCOOH的电氧化显示极高的活性 .本文还讨论了Pd(Ⅱ )离子对HCOOH电氧化过程的影响 .     

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.     

Pt-Se纳米空球修饰玻碳电极上甲酸的电催化氧化

以无定形硒溶胶为模板制备了不同硒覆盖度(θSe)(θSe=0.49,0.39,0.06,0)的Pt-Se和Pt纳米空球(分别记为(Pt-Se)HN和PtHN),发展了利用亚硫酸盐彻底除去核壳纳米粒子上Se的方法.对获得的纳米空球进行了形貌和结构的表征,结果表明所制备的(Pt-Se)HN粒径均匀,分散性好,球壳呈多孔结构.以其作为电催化剂制备了(Pt-Se)HN修饰的玻碳(GC)电极((Pt-Se)HN/GC),利用常规电化学方法比较该电极与PtHN/GC和商用碳载铂(Pt/C)修饰GC(Pt/C/GC)电极对甲酸的催化氧化作用,发现对甲酸氧化的活性顺序为(Pt-Se)HN/GCPtHN/GCPt/C/GC.三种电极催化甲酸氧化的机理有所不同:前者更倾向于通过弱吸附中间体直接氧化成CO2的单途径机理进行,后两者则通过强吸附和弱吸附中间体的双途径机理进行.在一定Se覆盖度条件下,(Pt-Se)HN/GC对甲酸的氧化有助催化作用.     

自组装纳米金膜上铂微/纳结构电催化剂的制备及性能

基于纳米金(AuNP)表面基团的静电自组装作用制备了多层有序的纳米金超薄膜. 研究了自组装纳米金超薄膜上铂微/纳结构催化剂(Pt/AuNP)的制备过程. 考察了沉积电位和沉积时间对甲酸电氧化活性的影响, 确定了最佳沉积电位为0 V, 最佳沉积时间为600 s. 同时对比考察了Pt/AuNP/PE/GCE, AuNP/PE/GCE和纯Pt电极在0.1 mol/L H2SO4介质中对甲酸电氧化活性以及载体对沉积物形态和甲酸氧化活性的影响. 研究结果表明, 纳米金组装体对铂的电沉积有明显的促进作用; Pt/AuNP/PE/GCE对甲酸的电氧化有很好的电催化性能.     

羟基新戊醛在PbO2-SPE组合电极上的电氧化研究

采用热压-电镀法制得PbO₂-固体高聚物电解质(SPE)组合电极. 通过伏安曲线和槽压与过电位曲线的测量, 研究羟基新戊醛在该组合电极上电氧化行为. 通过PbO₂-SPE组合电极在阳极液中有、 无液相支持电解质及不同阴极液情况下的循环伏安曲线和线性伏安曲线比较, 证明该组合电极对羟基新戊醛氧化有较好的电催化作用.     

Pt-Mo2C/GC催化甲醇氧化的现场电化学-红外光谱研究

应用离子交换法制备了40%Pt在Mo2C/GC上的电催化剂.X射线衍射(XRD)显示,Pt在Mo2C载体上有较好的分散度,平均粒径为3 nm.循环伏安、计时电位测试表明,酸性溶液中,Pt-Mo2C/GC具有良好的甲醇氧化性能.其催化甲醇氧化的起始电位比Pt/C的负移了90 mV.这一优异性能与Pt和载体Mo2C之间的协同作用有关.现场红外光谱电化学测量显示,甲醇在Pt/C电极氧化的中间产物是桥式吸附COB和线性吸附COL,而在Pt-Mo2C/GC电极则未检测到有害中间产物CO,其氧化终产物均为CO2.     

Preparation of Platinum Implanted Glassy Carbon Electrode and Electro-oxidation of Formic Acid and Formaldehyde

Electrocatalytic oxidation of small organic molecules has attracted considerable at-tentionin system of fuel celll-4. In this research field, Parsons4 pointed out that the electrodeswhich were prepared from non-noble substrates modified by excellent dispersal noblemetal particles and which still exhibited better catalytic activity should be studied. Ionimplantation is a technique with unique advantage and has been used in manyelectrochemical research fieldss'6. The present study is an at-tempt…     

Carbon‐Supported Pt Particles as a Catalyst for Electrooxidation of Methanol and Cyclic Voltammetry Studies Under Acidic Conditions

Electrooxidation of methanol on glassy carbon (GC) electrode modified by optimum carbon supported Pt electrocatalyst (Pt‐C/GC) in acid media is investigated. The catalyst is prepared by ultrasonicating Pt/C powders in aqueous media. The activity of prepared Pt‐C/GC electrode is studied in potential range of 0–1000 mV (versus SCE) by cyclic voltammetry. The results showed that the Pt/C dispersed layer at the surface of glassy carbon electrode, behaves as an electrocatalyst for the oxidation of methanol in acid medium by optimum loading of Pt (0.2 mg cm^?2). The electrochemical properties of prepared electrode are studied under various conditions. However the effect of various parameters in the catalytic enhancement of Pt/C, such as platinum loading, sulfuric acid concentration, different scan rates, different final potentials, and medium temperature are considered and examined.     

碱性介质中甘氨酸在Pt电极上解离吸附和氧化反应的原位红外反射光谱研究

运用原位红外反射光谱研究了碱性介质中甘氨酸在Pt电极上的解离吸附和氧化反应行为,并利用纳米Pt膜电极的异常红外效应鉴定反应过程中生成的表面吸附物种.结果表明:甘氨酸在Pt电极上极易发生解离,生成强吸附于电极表面上的氰基负离子,该吸附物种在低于0V电位下能稳定存在,并抑制甘氨酸的进一步反应.当电位高于0.2V时,氰基负离子被氧化为氰酸根离子进入溶液,使甘氨酸发生氧化反应,生成氰酸盐和碳酸盐等产物.     

The effect of electrochemically treated glassy carbon on the activity of supported Pt catalyst in methanol oxidation

Effect of electrochemical oxidation of glassy carbon on deposition of platinum particles and electrocatalytic activity of platinum supported on oxidized glassy carbon (Pt/GC_OX) were studied for methanol oxidation in H₂SO₄ solution. Platinum was potentiostatically deposited from H₂SO₄ + H₂PtCl₆ solution. Glassy carbon was anodically polarised in 0.5 M H₂SO₄ at 2.25 V vs. saturated calomel electrode (SCE) during 35 s. Electrochemical treatment of GC support, affecting not significantly the real Pt surface area, leads to a better distribution of platinum on the substrate and has remarkable effect on the activity. The activity of the Pt/GC_OX electrode for methanol oxidation is larger than polycrystalline Pt and for more than one order of magnitude larger than Pt/GC electrode. This increase in activity indicates the pronounced role of organic residues of GC support on the properties of Pt particles deposited on glassy carbon.     

团聚铂纳米粒子电极在甲醇氧化中的电催化特性

用H2还原法并以Nafion作为稳定剂合成团聚的Pt纳米粒子，附载于玻碳表面制备电催化剂.透射电子显微镜（TEM）和扫描电子显微镜（SEM）表征结果指出,团聚Pt纳米粒子的平均尺寸约为400 nm.运用电化学循环伏安法(CV)和原位傅立叶变换红外反射光谱（in situ FTIRS）研究甲醇的氧化过程，发现团聚Pt纳米粒子电极具有较高的电催化活性.原位FTIRS研究结果检测到甲醇在所制备的电催化剂上氧化的中间体为线型吸附态CO物种，其红外吸收给出异常红外效应的光谱特征.     

Size-controlled synthesis of colloidal platinum nanoparticles and their activity for the electrocatalytic oxidation of carbon monoxide

Using polyvinylpyrrolidone (PVP) as a stabilizing agent, stable colloidal solutions of platinum nanoparticles of different size distributions have been prepared by reducing H2PtCl6 with hydrogen. The UV-vis adsorption peaks at 258 nm due to the adsorption of Pt(IV) species disappear completely, indicating that the Pt(IV) species has been used up and colloidal Pt has been formed. The electrodes have been prepared from aqueous Pt colloids and glassy carbon (GC). The effect of platinum particle size of Pt/GC catalyst electrode on the electrocatalytic oxidation of carbon monoxide has been investigated. The voltammetry shows that a higher potential is needed for the oxidation of absorbed carbon monoxide with a decrease of the platinum particle size for particle sizes larger than 1 nm. But for particle sizes smaller than 1 nm, the potential remains constant while the activity decreases with decreasing the size. The snowlike, well-dispersed, and highly ordered platinum nanoparticles demonstrate high activity in the oxidation reaction of carbon monoxide. The reason may be due to the geometric structure of platinum nanoparticles.     

Electrocatalytic reduction of dioxygen at platinum particles deposited on Nafion- and clay-coated electrodes

Nafion- and clay-coated electrodes are prepared by casting a known amount of Nafion and clay solutions on the glassy carbon electrode (GC) surface. Subsequently platinum (Pt) particles are deposited on the GC electrodes and on the Nafion- and clay-coated GC electrodes. The formation of Pt particles on the modified electrode surface is analysed by scanning electron microscope, while cyclic voltammetry provides information on the anodisation of Pt particles deposited on the GC electrodes at >0.5 V(SCE) leading to the formation of platinum oxide (PtO). The involvement of PtO on the catalysed dioxygen reduction to hydrogen peroxide is reported. Macrocyclic cobalt(III) complex is also used as the electrocatalyst. The effect of pH on the reduction of PtO and dioxygen in deaerated and oxygenated solutions is studied to understand the dioxygen reduction processes. Received: 24 January 1997 / Accepted: 14 April 1997     

酸性和碱性介质中甘氨酸解离吸附和氧化的EQCM研究

用电化学石英晶体微天平(EQCM)研究酸性和碱性介质中甘氨酸在Pt电极上的吸附和氧化过程.结果表明,甘氨酸的解离吸附和氧化行为与溶液的酸碱性密切相关.酸性溶液中甘氨酸吸附较弱,碱性溶液中则产生强吸附物,且当电位低于0V(vs.SCE)时可吸附于Pt电极表面.此外,碱性溶液中甘氨酸还表现出较高的电氧化活性.通过EQCM定量检测上述过程中Pt电极表面的质量变化,测定了不同电位区间(氢区、双电层区和氧区)每传递一个电子所对应的电极表面吸附物种的平均摩尔质量.     

Pt/DNA-MWCNTs/GC电极制备及其H2O2还原的电催化活性

将DNA功能化多壁碳纳米管（MWCNTs）复合材料修饰于玻碳基底（GC）表面制得DNA-MWCNTs/GC电极,并在此基础上电沉积负载Pt纳米颗粒构建了一种新型无酶H₂O₂传感电极. 利用扫描电子显微镜（SEM）表征制得的修饰电极,同时通过循环伏安法和计时电流法研究了该传感电极的H2O2响应性能. 结果表明,该传感电极的H₂O₂检测在0.04 ~ 18.07 mmol·L^-1浓度范围内成线性相关,检出限3.85 μmol·L^-1（S/N = 3）,且有良好的重现性、稳定性与选择性.