香兰素在 Cu－PTFE 复合电极上的电还原行为

以纯铜片为基材,利用复合电镀法制得具有疏水性的Cu－PTFE（聚四氟乙烯）复合电极,并用作阴极应用于香兰素电还原制备香草醇。实验中分别测定了香兰素乙醇水溶液中Cu－PTFE复合电极的循环伏安、交流阻抗和Tafel极化曲线等电化学参数。结果表明,香兰素电还原制备香草醇的转化率为87．23％,电流效率为43．62％。通过对电化学行为研究的结果进行推测,香兰素在Cu－PTFE复合电极上的电极反应可能受到电子传递控制,可用RS（CCQ（CdlRct）RC）等效电路模拟复合电极／溶液界面的电化学行为。     

3-甲基吡啶在Pb-PTFE修饰电极上的电氧化行为

采用复合电镀法制得Pb-PTFE疏水性修饰电极,并作为阳极应用于3-甲基吡啶水溶液的电氧化。结果表明,3-甲基吡啶在Pb-PTFE疏水性修饰电极上呈现明显的电氧化行为。根据电氧化产物的FT-IR谱图推测3-甲基吡啶在Pb-PTFE修饰电极上可能被电氧化为烟酸。电化学交流阻抗测试表明3-甲基吡啶在Pb-PTFE修饰电极上的电氧化动力学过程主要受电荷迁移和浓差扩散混合控制,可用R(Q(CW))等效电路进行模拟。     

环己醇与环己酮在疏水性复合电极上的电化学转化

将自制的2种疏水性复合电极(M-PTFE,M=Ni、Zn)分别应用于环己醇的电化学氧化和环己酮的电化学还原,测定了不同条件下的循环伏安曲线和电极稳定性,结果表明环己醇电化学氧化的转化率达92.5%和环己酮电化学还原的转化率达94.6%。     

Cu2O/CuO/Cu电极光电催化还原CO2

利用表面氧化法在铜基底上制备CuO纳米带(CuO NRs),通过电化学法将Cu_2O沉积到CuO NRs上,得到复合电极Cu_2O/CuO/Cu。借助X射线衍射(XRD)、透射电子显微镜(TEM)对Cu_2O/CuO/Cu复合电极的结构进行了表征。通过线性扫描伏安法(LSV)、光电流-时间测试、电化学阻抗测试对Cu_2O/CuO/Cu复合电极光电催化CO_2性能进行了考察。借助变色酸分光光度法来测定CO_2光电还原产物。结果表明:氧化铜在铜基底上呈纳米带生长;复合电极Cu_2O/CuO/Cu对CO_2有较强的光响应性,表现出优异的光电催化性能;Cu_2O/CuO/Cu复合电极光电催化还原CO_2的主要产物是甲醇,在0.1 mol/L NaHCO_3溶液中光电催化6 h后,甲醇质量浓度为32.2mg/L。     

高效液相色谱法测定工业品苯甲醇的含量

选用Hypersil ODS2色谱柱,甲醇与质量分数2％的Na2SO4水溶液体积比为48：52混合液为流动相（体积流量lmL／min）,建立了以苄苯为原料合成的工业品苯甲醇的高效液相色谱测定方法。结果表明,苯甲醇的相对标准偏差为O．12％,笨甲醇进样量在0．04—1．60μg时呈良好的线性关系（R=0．9999）。该方法操作简便、快速,符合定量分析要求,适用于工业品苯甲醇的分析。     

“三明治”型PTFE/Cu/炭黑/石墨气体扩散电极的制备及其电催化二氧化碳还原的性能研究

采用聚四氟乙烯(PTEF)为基底,制备具有"三明治"结构的PTFE/Cu/炭黑/石墨气体扩散电极,并探究其在流动电解池中电催化二氧化碳还原性能。结果表明:相比传统的Cu/碳纸气体扩散电极,PTFE/Cu/炭黑/石墨气体扩散电极在相同电压下具有更大的二氧化碳还原电流密度和电化学活性面积,更小的电化学阻抗。在100～500 mA/cm2下,PTFE/Cu/炭黑/石墨气体扩散电极生成多碳产物(乙醇、乙烯、乙酸和正丙醇)的法拉第效率,均明显高于Cu/碳纸气体扩散电极。在300 mA/cm2下,PTFE/Cu/炭黑/石墨气体扩散电极最大法拉第效率可达74.4%。在3 mol/LKOH中,PTFE/Cu/炭黑/石墨气体扩散电极可保持70%以上的法拉第效率,并稳定运行50 h,远高于Cu/气体扩散碳纸电极。     

磁控溅射制备Cu_(1-x)Co_xO复合氧化物的催化析氧

采用直流反应磁控溅射法制备了Cu1-xCoxO(0.02≤x≤0.14)复合氧化物电极。利用XRD、EDS和SEM分析技术对沉积氧化物的晶体结构、化学组成及表面形貌进行了表征,并利用循环伏安、线性扫描及电化学交流阻抗对沉积氧化物电极的电化学性能进行了测试。XRD分析结果显示复合氧化物Cu1-xCoxO具有CuO单斜晶体结构,不存在氧化钴独立相。电化学测试结果表明Cu1-xCoxO复合氧化物电极对水氧化反应的催化活性远高于CuO和Co3O4电极,更好的催化活性、较低的电阻和高的表面粗糙度是Cu1-xCoxO复合氧化物电极催化活性提高的主要原因。生成最优Cu1-xCoxO(0.02≤x≤0.14)复合氧化物的溅射功率为45W(Co)、100W(Cu)。     

苯甲醇在铂和钯电极上的电化学反应活性研究

为研究电极性能对苯甲醇（BA）反应活性的影响,用差示电化学质谱分析（DEMS）和循环优安法对0．1mol/L HCIO4中的2mmol/L苯甲醇在铂和钯电极上的电化学反应进行了研究。挥发性产物的在线质谱分析显示,苯甲醇和这些金属相互作用,部分离解成苯。CO2是检测出来的唯一一种氧化产物。相应的质谱信号显示出3种不同的组成。用伏安扫描时发现,每种组成的范围强烈依赖于电极性质,但以钯为电极时,每种组成的范围也随着伏安扫描时的电极电势范围的变化而变化。在电解还原过程中,铂和钯表现出不同的催化活性,在铂电极上发生分子的氢解和芳环的氢化作用,而在钯电极上芳环的氢化作用很少发生。     

Ni-Cu合金电极上苯甲醇的选择性电氧化

通过恒电流电沉积法在不同条件下制备了一系列Ni-Cu合金电极,采用扫描电镜(SEM)表征了其表面形态,用循环伏安法(CV)研究了在碱性溶液中苯甲醇在不同工艺条件下制备的Ni-Cu合金电极上的电氧化行为.并进一步用电化学原位红外光谱(in situ FTIP)从分子水平研究了苯甲醇在Ni-Cu合金电极上的电氧化过程.结果...     

甲醇在Pt电极上电催化氧化的CV研究

运用电化学循环伏安法研究0．5mol·L-1H2SO4溶液中甲醇在Pt电极上吸附和氧化的情况,利用扫描速度与峰电流的关系,研究甲醇电氧化的动力学过程。     

Electrocatalytic activity of surface adsorbed ruthenium-alizarin complexone toward the oxidation of benzyl alcohol

The surface electrochemical behavior of an adsorbed alizarin complexone (abbreviated as AC) and its surface coordination with Ru(II) were studied in aqueous solution at a pH range of 0-6. The surface complex of ruthenium with AC displays strong electrocatalytic activities toward benzyl alcohol. Based on the rotating disk electrode measurement, it is believed that the electrocatalytic oxidation of benzyl alcohol is a two-electron and two-proton process with benzaldehyde as a major product. On the other hand, ruthenium-AC surface complex has also shown catalytic activities toward electro-oxidation of several small organic molecules such as methanol, formic acid, formaldehyde, ethanol, and acetaldehyde.     

The use of hydrated nickel–cobalt mixed oxide electrodes for oxidation of aliphatic and aromatic alcohols

Voltammetric studies and galvanostatic oxidation results for the electrochemical oxidation of octyl. hexyl, butyl, isobutyl and benzyl alcohols on hydrated nickel-cobalt oxide electrode in alkaline media are reported. These compounds are oxidised to their corresponding acids with high efficiency. The electrodes are not contaminated and hence their repeated use for the oxidation of same or different compounds is possible. Oxidation of benzyl chloride leads to formation of benzyl alcohol, benzaldehyde along with benzoic acid.     

Electrochemical reduction of benzaldehyde using Pt-Pb/Nafion® as electrode

The electrochemical reduction of benzaldehyde using Pt-Pb/Nafion® as electrode without supporting electrolyte in the liquid organic phase was investigated. A novel Pt-Pb/Nafion® electrode was prepared for the electrolysis of the organic compound in this solid polymer electrolyte (SPEO) system. A reaction mechanism is proposed. No benzyl alcohol was produced using fresh Nafion® as electrode. The selectivity of benzyl alcohol using Pt-Pb/Nafion® as an electrode was almost 100% and only a trace of hydrobenzoin byproduct was found in the catholyte. The optimum faradic yield of benzyl alcohol was 18.70 g F^–1. The primary factors affecting the current efficiency or faradic yield of the cathodic reduction of benzaldehyde to benzyl alcohol were cell voltage, solvent and temperature. The use of a Pt-Pb/Nafion® electrode in a SPE® system for the electrochemical reduction of benzaldehyde was found to be a feasible technique.     

Novel Nanoscale Ceria–Platinum Composite Electrodes for Direct Alcohol Electro-Oxidation

A nanocrystalline Pt/CeO₂ composite electrode is fabricated to study the electrochemical oxidation of methanol and ethanol. Three different methods have been developed for the preparation of the composite electrode and are compared in terms of their oxidation efficiencies. In general, all the electrode preparation methodologies show a great enhancement of the oxidation current for the alcohol. However, methods based on the electrodeposition of a ceria rich Pt matrix show the greatest effectiveness of alcohol oxidation. The enhancement of the anodic current is dependent on the particle loading and size distribution in the composite matrix. In general, ceria appears to be an effective alternative to ruthenium in direct alcohol fuel cells.     

Bi2O3电极的制备及其选择性氧化苯甲醇性能研究

采用滴凃法和电沉积法制备了Bi2O3薄膜电极,运用场发射扫描电子显微镜和X射线衍射仪对其进行了表征。在水相中以苯甲醇选择性氧化合成苯甲醛为模型反应,研究Bi2O3薄膜的催化性能。其中电沉积法制备的Bi2O3薄膜电极在水相溶液中表现出优异的电催化选择性氧化性能,苯甲醇的转化率最高,并且在外加偏压为2 V时达到了最高的苯甲醛选择性和苯甲醛收率。     

Electro-oxidation of N-hydroxy imides for redox mediator in acetonitrile containing lutidine as a base

The electrochemical properties of two N-hydroxy imides, N-hydroxymaleimide and N-hydroxysuccinimide, at a glassy carbon electrode in acetonitrile were examined by cyclic voltammetry. N-hydroxysuccinimide, which contains no olefinic linkage, indicated a chemically reversible redox response, and its ability as a mediator for the oxidation of benzyl alcohol was confirmed by rotating disk electrode voltammetry.     

聚合物微球固载的N-羟基邻苯二甲酰亚胺在分子氧氧化苯甲醇反应过程中的催化特性

以甲基丙烯酸缩水甘油酯(GMA)和甲基丙烯酸甲酯(MMA)的交联共聚微球GMA/MMA为基质,经过几步大分子反应在微球表面合成与固载了N-羟基邻苯二甲酰亚胺(NHPI),形成固载有NHPI的聚合物微球GMA/MMA-NHPI。将GMA/MMA-NHPI与Co(OAc)₂组成共催化体系,用于分子氧氧化苯甲醇的反应过程。研究结果表明,GMA/MMA-NHPI与Co(OAc)₂所构成的共催化体系在温和条件(65℃和常压氧气)下可有效地实现苯甲醇的分子氧氧化过程,将其深度氧化为苯甲酸,显示出较好的催化活性和高的选择性(苯甲酸的选择性为96%)。主催化剂GMA/MMA-NHPI固载的NHPI与助催化剂Co(OAc)₂适宜的摩尔比为20:1;主催化剂所含NHPI的摩尔分数为底物的10%时催化剂的用量比较适宜。固体催化剂GMA/MMA-NHPI还具有良好的再循环使用性能。     

Electrocatalytic oxidation of benzyl alcohol in alkaline medium on RuO2-coated titanium electrode

The heterogeneous electrocatalytic redox behaviour of RuO₂ electrodes fabricated by thermal decomposition is investigated with and without benzyl alcohol using cyclic voltammetric and potentiodynamic techniques. The cyclic voltammetric results show that benzyl alcohol oxidation is mediated by perruthenate ion electrogenerated at the electrode surface. Evaluation of kinetic parameters in relation to Tafel lines allows the postulation of a plausible reaction scheme in which benzyl alcohol adsorbs on the RuO₂ electrode surface and the rate determining step is chemical reaction between perruthenate and adsorbed species. The reaction orders with respect to benzyl alcohol and OH^– concentrations are 0.85 and 1, respectively. The results in galvanostatic electrolysis show that the major product for benzyl alcohol oxidation in an aqueous solution is benzaldehyde, and the organic yield is affected by such electrolysis conditions as t-butanol concentration, electrolysis current density, KOH concentration and electrolysis temperature.     

基于原位红外光谱的水相苯酚电氧化机理研究

采用电化学原位红外光谱技术,研究了苯酚在Pt电极表面的电化学氧化机理。在0.1 mol/L Na₂SO₄溶液中,Pt电极上电化学氧化苯酚的反应电位为+0.9~1.0 V（vs SCE）、析氧电位为+1.3 V;电化学原位红外光谱结果表明,当电位<0.9 V时,苯酚氧化产物主要为苯二酚、醌及少量醇类物质;电位0.9~1.1 V时,苯环结构被破坏,氧化产物主要为酮、酸、醇和CO₂;根据官能团吸收峰的变化,苯酚在Pt电极表面氧化经历如下途径：苯酚→苯二酚→苯醌→酮、醇、酸→CO₂。同时研究了NH₄⁺对苯酚在Pt电极表面的电氧化的影响,结果表明在低电位区（<0.9 V）对苯酚氧化构成竞争。     

A novel hydrazine electrochemical sensor based on a zirconium hexacyanoferrate film-bimetallic Au–Pt inorganic–organic hybrid nanocomposite onto glassy carbon-modified electrode

This work describes the electrochemical behavior of zirconium hexacyanoferrate (ZrHCF) film immobilized on the surface of bimetallic Au–Pt inorganic–organic hybrid nanocomposite glassy carbon electrode and its electrocatalytic activity toward the oxidation of hydrazine. The electrode possesses a three-dimensional (3D) porous network nano architecture (NFs). The surface structure and composition of the sensor was characterized by scanning electron microscopy (SEM). Electrocatalytic oxidation of hydrazine on the surface of modified electrode was investigated with cyclic voltammetry and chronoamperometry methods and the results showed that the ZrHCF film displays excellent electrochemical catalytic activities toward hydrazine oxidation. The modified electrode indicated reproducible behavior and high level of stability during the electrochemical experiments.