利用荧光素异硫氰酸酯检测季铵盐阳离子表面活性剂的方法

使用荧光素异硫氰酸酯（FITC）实现了对季铵盐阳离子表面活性剂（QAS）在水溶液中临界胶束浓度（CMC）的准确测量及其在CMC以下的浓度定量。用该法测得十二烷基三甲基溴化铵（DTAB）和十六烷基三甲基溴化铵（CTAB）在水中的CMC分别为12～13 mmol·L^-1和0.70～096 mmol·L^-1,与电导率法、表面张力法和芘荧光法的检测值相近。对DTAB和CTAB的检测下限分别是011 mmol·L^-1和1.7 μmol·L^-1,定量范围分别为0.11～9.73 mmol·L^-1（0.034～3.0 g·L^-1）和1.7 μmol·L^-1～0.27 mmol·L^-1（6.2×10^-4～0.1 g·L^-1）。结果表明,使用FITC荧光探针检测QAS具有安全、简便、灵敏度和准确度高的优点。     

碳纳米管/纳米TiO2-聚苯胺复合膜电极的制备及电化学性能

在含有0.2 mol·L^-1苯胺的0.5 mol·L^-1 H2SO4溶液中;采用循环伏安法（CV）;以扫描速度50 mV·s^-1;扫描电位为-0.1～0.9 V;在碳纳米管/纳米TiO₂（CNT/nanoTiO₂）膜电极上实现了苯胺的电化学聚合;通过CV法和电化学阻抗谱（EIS）并结合电子扫描显微镜和红外谱图对制备的碳纳米管/纳米TiO₂-聚苯胺（CNT/nanoTiO₂-PAn）复合膜电极的电化学性质和结构进行了表征;同时研究了复合膜电极对抗坏血酸（AH₂）的电催化性能;发现该复合膜电极对抗坏血酸的氧化具有较高的电催化活性。     

硼掺杂金刚石膜电极电催化降解环己酮废水

采用循环伏安法、稳态极化法等对硼掺杂金刚石薄膜电极的电化学性能及电氧化降解含环己酮模拟废水的电极过程进行了研究,考察了电流密度、支持电解质浓度、起始环己酮浓度和pH值等因素对硼掺杂金刚石薄膜电极电氧化降解含环己酮模拟废水效果的影响。实验结果表明,硼掺杂金刚石薄膜电极能够对环己酮进行有效且稳定的降解,通过正交优化实验,得到较优工艺条件为阳极电流密度为5 mA·cm^-2,pH值为7,Na₂SO₄浓度为10 g·L^-1,起始环己酮浓度为20 mmol·L^-1,在该条件下COD去除率达92.95%,电流效率达80.81%,降解效果显著。     

铌酸光催化降解甲基橙溶液

以铌酸为光催化剂,在高压汞灯照射下,对模拟染料废水甲基橙溶液进行光催化降解,研究过氧化氢加入量、催化剂用量和甲基橙起始浓度对光催化降解的影响。结果表明,当甲基橙起始浓度为15 mg·L^-1、30%过氧化氢用量为5.0 mL·L^-1和催化剂用量为1.5 g·L^-1时,光照1 h,甲基橙溶液降解率达到97％,在较低浓度下,甲基橙溶液的光催化降解反应符合一级动力学方程。     

基于膜分离技术的生物聚合铁的制备

开展基于膜分离技术优化反复序批式工艺制备生物聚合铁（BPFS）的技术研究。考察了应用聚偏氟乙烯中空纤维微滤膜（PVDF）对微生物的分离效果,Fe^2+的生物催化氧化速率,制备周期及膜的污染与处理的情况。研究表明,PVDF膜可有效分离微生物,显著提高原液中的生物量。在优化工艺的基础上,制备了全铁含量分别为60、80、100 kg·m^-3 BPFS,Fe^2+的生物催化氧化速率分别达到1.75、1.85、1.43 g·L^-1·h^-1,制备周期分别为15.5、21、40 h,比工艺优化前分别缩短了38%、42%、18%,反应液中的生物量达到10⁸ 个·ml^-1数量级。实验中发现,随着分离次数和全铁含量的增加,膜污染加剧,膜通量下降;采用0.2 mol·L^-1的草酸钠和0.2 mol·L^-1硫酸的混合溶液对PVDF膜进行清洗,可基本清除膜表面的污染物,满足分离要求。     

W/O微乳液法制备Ni-Zr/Pani电催化剂及其性能

通过反相微乳液法(W/O)制备了金属质量分数为40%的不同原子比的Ni-Zr/Pani催化剂。采用SEM和XRD分析了催化剂的形态,循环伏安法考察了催化剂对甲醇的电催化性能。结果表明,当微乳液ω=7.52制备的Ni和Zr原子比=1∶〖KG-*2〗1时,催化剂成球形非晶态,在常温2 mol·L^-1的甲醇硫酸溶液中,Ni₁Zr₁/Pani表现出较好的电催化性能,其氧化电位为1.046 V,氧化电流密度为4.44 mA·cm^-2。     

汽油电化学催化氧化脱硫

采用一种新型的电化学催化氧化方法,研究了在碱性电解体系中汽油脱硫的规律.结果表明：在碱性电解体系中汽油电解催化氧化脱硫的理论分解电压范围为0.5～1.5 V;适宜的电解条件为：分解电压1.90 V,碱液浓度1.0 mol·L^-1,油/电解液进料体积比1/3,搅拌速度300 r·min^-1,适宜温度50℃,电流密度155 mA·cm^-2,进料流速200 ml·min^-1.在此条件下油品硫含量从310 μg·g^-1下降到120 μg·g^-1左右,且对油品的主要性质没有影响.     

介质阻挡放电等离子体对茜素红溶液的降解

利用介质阻挡放电等离子体法对染料茜素红溶液进行降解。考察了放电间距、输入电压及溶液pH值对茜素红降解效果的影响,并通过测定放电过程溶液中活性粒子O₃的浓度,探讨了促使茜素红降解的主要因素。结果表明,高压电极与液面间距为8 mm、输入电压为8 kV时,降解效果较好。其中弱碱性环境下（pH=8.4）降解效果最好,40 min后茜素红浓度降为0.26 mg·L^-1,在弱酸性环境（pH=5.8）中处理45 min后,茜素红浓度为1.61 mg·L^-1,而在中性环境（pH=7.0）中降解效果较差,处理45 min后茜素红残留浓度为5.70 mg·L^-1。溶液中的O₃是推动氧化反应进行的主要因素。     

1，4-二乙氧基苯与3，4-亚乙基二氧噻吩的电化学共聚

利用恒电位聚合法合成了1,4-二乙氧基苯（DEB）与3,4-亚乙基二氧噻吩（EDOT）的共聚物。单体浓度为DEB 0.1 mol·L^-1,EDOT 0.01 mol·L^-1,溶液为乙腈,四丁基高氯酸铵（TBAP）为支持电解质。研究不同电位下聚合的共聚物的电化学性能。并用扫描电子显微镜观察了共聚物在ITO玻璃上的成膜情况。结果表明EDOT的加入可提高DEB的电化学活性以及在ITO玻璃电极上的成膜性能。荧光光谱显示出共聚物在402 nm和530 nm有较强的发射峰,说明EDOT的加入成功调节了聚1,4-二乙氧基苯（PDEB）的发光波长（399 nm）。     

臭氧强化电絮凝处理直接耐晒大红4BS模拟染料废水

采用臭氧强化电絮凝法处理直接耐晒大红4BS模拟染料废水,研究了染料脱色的影响因素及其COD_Cr去除动力学。考察了电流密度、溶液初始pH 值、染料初始浓度、支持电解质浓度、反应温度和臭氧流量对臭氧强化电絮凝法处理4BS染料脱色效率的影响。结果表明,电流密度15 mA·cm^-2,pH值10.0,4BS染料初始浓度100 mg·L^-1,支持电解质浓度3000 mg·L^-1,臭氧流量06 L·h^-1,20 ℃下反应50 min后4BS脱色率达94％以上。COD_Cr去除符合拟二级动力学。     

Electro-oxidation of methanol and ethylene glycol on platinum in alkaline solution: Poisoning effects and product analysis

The electrochemical oxidation of ethylene glycol on platinum was investigated and compared with that of methanol in alkaline solution by using various electrochemical and analytical measurements. Ethylene glycol showed much less significant electrode poisoning than methanol at low potential (400 mV). This phenomenon was clarified by analyzing the products of ethylene glycol oxidation. In ethylene glycol oxidation, partial oxidation to glycolate was much faster than complete oxidation to CO₂. In addition, there were two paths for ethylene glycol oxidation: poisoning and non-poisoning paths. The poisoning path led to the production of C1 compounds and the non-poisoning path gave oxalate. The non-poisoning path prevented the formation of poisonous species on platinum.     

A comparison of the change from inhibiting to enhancing anions in the electrochemical oxidations of ethylene glycol and formaldehyde

Techniques dealing with inhibiting anions have previously been employed to measure their properties. The present approach is to change the behavior of inhibiting anions. Anions, which have long been considered to inhibit reactions, are shown to enhance some electrochemical reaction rates. Fluoroborate, nitrate, and (hydrogen) sulfate are separately shown to increase the current response of the electrochemical oxidation of formaldehyde. The reaction rate of the oxidation of ethylene glycol is increased but for a restrictive set of conditions. Experimental data, as well as theoretical considerations lead to the conclusion that adsorption of the added anions is the slow step of the process that increases the reaction rate. The differences in the response of ethylene glycol and formaldehyde follow well-documented changes of surface CO. These observations are consistent with general properties of the step in the part of the mechanism on the electrode surface that enhances the reaction rate.     

A Facile Diethylene Glycol Reduction Method for the Synthesis of Ultrafine Pd/C Electrocatalyst with High Electrocatalytic Activity for Methanol Oxidation

The high‐quality carbon supported Pd nanoparticles (Pd/C) composites have wide applications in catalysis. In this work, we demonstrate an efficient diethylene glycol (DEG) reduction method for the synthesis of a Pd/C catalyst with high dispersion and small particle size. During the synthesis, no surfactants and halogen ions are introduced in the reaction system, and DEG efficiently acts as solvent and reducing agent, which results in a “clean” Pd surface. Meanwhile, compared to the classic ethylene glycol (EG) reduction method, the present DEG reduction method can produce the high‐quality Pd/C composites. As a result, the as‐prepared Pd/C electrocatalyst exhibits a large electrochemical active surface area and good electrocatalytic performance for the methanol oxidation reaction in an alkaline media, due to the high dispersion and small particle size. This result indicates the as‐prepared Pd/C electrocatalyst has potential applications in alkaline direct methanol fuel cells.     

二甘醇的综合利用技术新进展

二甘醇（DEG）是环氧乙烷用水合法生产乙二酵（EG）的副产物,随着我国乙二醇工业的迅速发展二甘醇产量不断增加,充分利用二甘醇资源开发下游产品、拓展二甘醇的用途越来越受到重视。综述了国内二甘醇的综合利用进展,介绍了二甘醇的直接利用途径和二甘醇合成吗啉、二甘醇醚、二甘醇酯、1,4-二氧六环、二甘酸和二甘醇胺等精细化学品的利用情况。     

Synergistic effect of CeO2 modified Pt/C catalysts on the alcohols oxidation

The effect of the addition of CeO₂ to Pt/C catalysts on electrochemical oxidation of alcohols (methanol, ethanol, glycerol, ethylene glycol) was studied in alkaline solution. The ratios of Pt to CeO₂ in the catalysts were optimised to give the better performance. The electrochemical measurements revealed that the addition of CeO₂ into Pt-CeO₂/C catalysts could significantly improve the electrode performance for alcohols oxidation, in terms of the reaction activity and the poisoning resistance, due to the synergistic effect. The electrode with the weight ratio of Pt to CeO₂ equals 1.3:1 with platinum loading of 0.30 mg/cm² showed the highest catalytic activity for oxidation of ethanol, glycerol and ethylene glycol.     

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.     

Electrochemical oxidation of propylene utilising a thallium redox system

The oxidation of propylene in the presence of electrochemically regenerated thallium(III) was investigated over a range of electrode potentials. Polarisation curves made with the aid of a rotating platinum disc electrode, as well as current efficiencies for the formation of propylene glycol and acetone, are presented. At electrode potentials <2.2 V(E_H), product formation can be satisfactorily explained in terms of thallium(I) reoxidation. At higher electrode potentials, direct oxidation of the thallium-propylene complex as well as further electrochemical oxidation of the products so obtained must be postulated.     

Relationship among the physicochemical properties, electrocatalytic performance and kinetics of carbon supported Pt catalyst for ethanol oxidation

A new carbon supported Pt (Pt/C(b)) catalyst was prepared by reducing H₂PtCl₆ in glycol solution using formic acid as a reducing agent, and has been found in this work to be highly active and stable for the electrochemical oxidation of ethanol. The preparation produces highly dispersed Pt particles, of 2.6 nm average size, and with high electrochemical surface area, 98 m²/g. The apparent activation energy of ethanol oxidation over the Pt/C(b) catalyst electrode is low, 10–14 kJ/mol, over the range of potentials from 0.3 to 0.6 V.     

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。     

Conductivities enhancement of poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) transparent electrodes with diol additives

High conductivity, good stability, and high transmittance in the visible region are the three essential requirements for the polymer electrodes used in the optoelectronic devices. It was found that with addition of diols, such as ethylene glycol, diethylene glycol, or poly(ethylene glycol) (PEG), to the poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS) emulsion before spin-coating could increase dramatically the conductivities of the resultant PEDOT:PSS thin films from 1 to 90 S cm^?1 while maintain the optical transparency of the modified thin films. With up to ?2.4 V potential applied, the PEDOT:PSS with PEG 200 additive does not show obvious color change, indicating its good electrochemical stability as polymer electrode. Detailed studies on the structures and morphologies of these modified PEDOT:PSS thin films, in comparison to that of PEDOT:PSS without additives were carried out using AFM, Raman, and FTIR to investigate the underlying mechanisms.