钛基银电极的水热法制备与电活性

以硝酸银、聚乙二醇、水合肼、EDTA为原料,采用水热法制备了3种新型钛基银电极(Ag/Ti-N2H4,Ag/Ti-PEG,Ag/Ti-PEG-EDTA)。扫描电镜(SEM)和能谱分析(EDS)表明,银颗粒在基体钛表面形成了稳定的沉积层,3种电极的表面呈现不同的结构特征,Ag/Ti-N2H4电极上形成了直径1μm银颗粒,Ag/Ti-PEG电极上形成了直径400～600nm银球形颗粒,Ag/Ti-PEG-EDTA电极上的银金属球形颗粒粒径最小,约为200～300nm,并且分布均匀、相互连接形成空间网状结构。在1mol·L-1NaOH溶液中,利用循环伏安法研究了这3种电极对肼氧化的电催化活性。结果表明,3种电极对肼都具有催化氧化作用,与多晶银电极相比(-0.35V),肼在这3种电极上的电化学氧化起始电位更低,Ag/Ti-PEG-EDTA和Ag/Ti-N2H4电极为-0.6V,Ag/Ti-PEG电极为-0.7V。在加入的肼为20mmol·L-1,在电位为-0.36V处,多晶银、Ag/Ti-N2H4,Ag/Ti-PEG和Ag/Ti-PEG-EDTA电极对肼氧化的阳极电流密度分别为2.5,33,42和51mA.cm-2。相比而言,Ag/Ti-PEG-EDTA和Ag/Ti-PEG电极对肼氧化的电活性最为优异,有望作为水合肼燃料电池的阳极材料。     

直接甲醇燃料电池Pt／C催化剂对甲醇的电催化氧化研究

通过循环伏安法研究了Pt/C催化剂对甲醇的电催化氧化活性,详细地考察了甲醇浓度、温度、介质以及酸度等电化学体系因素对Pt/C催化剂活性的影响。结果表明,上述四个电化学体系因素对Pt/C催化剂活性存在着明显的影响。甲醇浓度和温度的增加可以显著降低工作电极内阻,增加电极反应速率,提高Pt/C催化剂活性。改善溶液介质和控制适宜的酸度有利于Pt/C催化剂活性的提高。在本实验条件下,其最佳的运行工艺参数为:溶液介质为二次去离子水,酸度为1.0 mol/L H2SO4。     

一种高效双功能电催化剂CoP/Co@NPC@rGO的制备

简单的热处理和热处理磷化ZIF-67/氧化石墨烯（GO）前驱体得到具有典型的多孔碳结构特征的CoP/Co@NPC@rGO纳米复合材料电催化剂。通过扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线衍射（XRD）、X射线光电子能谱（XPS）、拉曼光谱（Raman）和N₂等温吸脱附曲线等对其形貌、成分和结构进行分析和表征。采用线性扫描伏安法、电化学阻抗谱和计时电位法探讨了CoP/Co@NPC@rGO纳米复合电催化剂对氢气析出反应（HER）和氧气析出反应（OER）的电催化活性和稳定性。结果表明,CoP/Co@NPC@rGO?350在1.0 mol·L–1 KOH溶液中达到10 mA·cm?2电流密度的析氢过电位仅127 mV;同时,在1.0 mol·L–1 KOH溶液中显示出优于贵金属RuO₂的析氧性能,达到10 mA·cm?2电流密度的过电位为276 mV,塔菲尔斜率仅为42 mV·dec?1。这种高析氢和析氧电催化活性主要归因于高度石墨化的N掺杂多孔碳与N掺杂石墨烯之间的协同效应。CoP/Co@NPC@rGO是电催化全解水电催化剂的候选材料,且为基于金属有机骨架（MOFs）/氧化石墨烯复合材料的高效电催化剂的设计开辟了一条新的途径。      

碱性介质中钯镍合金纳米线阵列电极对乙醇的电催化氧化

本文研究了一种简单、可控的方法制备直立金属纳米线阵列。采用恒电位法在多孔阳极氧化铝(AAO)模板中电沉积了钯镍(PdNi)合金纳米线阵列。高分辨扫描电子显微镜(HRSEM)图证明模板孔洞的填充率非常高,纳米线阵列的直径和模板的孔径一致,分布较均匀,纳米线的直径平均为60 nm。运用循环伏安法和计时电流法研究了钯镍纳米线阵列电极在碱性溶液中对乙醇的电催化氧化行为。结果表明,相比裸玻碳电极及PdNi膜电极,PdNi纳米线阵列电极在碱性溶液中对乙醇氧化具有更高的电催化活性,峰电流密度可达到32 mA·cm-2。研究了PdNi纳米线阵列电极对不同乙醇浓度的电催化氧化的影响。结果表明,乙醇的浓度从0.01 mol·L-1增加到2.00 mol·L-1,峰电流密度随乙醇的浓度增加而逐渐增大,峰电流密度与乙醇浓度存在一定的线性关系。     

用聚苏木精/TiO2-石墨烯复合膜修饰玻碳电极差分脉冲伏安法测定水样中对苯二酚

采用滴涂法和电聚合法制备了聚苏木精/TiO2-石墨烯复合膜修饰玻碳电极。用循环伏安法研究了对苯二酚（HQ)在修饰电极上的电化学行为。实验结果表明,该修饰电极对于HQ的氧化还原具有良好的电催化性能。相对于裸电极和TiO2-石墨烯修饰电极,HQ在聚苏木精/TiO2-石墨烯修饰玻碳电极上的氧化峰电流显著提高。利用差分脉冲伏安法测定,HQ在3.0×10-6~1.0×10-3 mol/L浓度范围内与氧化峰电流呈良好的线性关系,相关系数分别为0.993。信噪比为3时,HQ检出限为1.0×10-7 mol/L。将该方法用于环境水样分析,回收率为96.2% ~ 105.6%。     

高硫高砷金精矿电化学氧化机理研究

通过对黄铁矿、毒砂、金精矿的电化学氧化极化曲线、由平衡状态下的电化学反应速度计算的电化学反应参数和电化学氧化产物的Ｘ射线衍射（ＸＲＤ）分析结果的分析、推理,得到金精矿的电化学氧化机理。     

1—（—2—吡啶偶氮）—2—萘酚修饰碳糊电极测定铜的研究

本文报告１－（２－吡啶偶氮）－２－萘酚（ＰＡＮ）修饰碳糊电极在乙酸盐缓冲液（ｐＨ５．０）中，与铜离子生成电活性螯合物，并吸收在电极表面，经介质交换到０．１ｍｏ１／ＬＫＣ１中，用微分脉冲伏安法测定，用－０．１５Ｖ出现一灵敏的还原峰。用正交试验优化法研究了测定铜的最佳条件。其相对标准偏差３．２７％。这一方法用于阳极泥中铜的测定，回收率为９４．３％。还用双电位阶跃计时仑法，循环伏安法研究了ＰＡＮ修饰碳糊     

钨酸根离子在银、金电极上的电化学行为研究

在电化学工作站中以三电极体系研究WO₄2-在金、银电极上的电化学行为. 结果表明:298 K时,在0.05 mol/L Na₂WO₄的水溶液体系,研究分析知钨酸根离子在银、金电极上的电化学还原过程不可逆,计算得出钨酸根离子在银、金电极上的转移电子数分别为3、4. 以银作阴电极,溶液中钨酸根离子发生WO₄2-+2e→WO₃2-+O和WO₃2-+e→WO₂-+O电化学反应;以金作阴电极,溶液中钨酸根离子发生WO₄2-+2e→WO₃2-+O和WO₃2-+2e→WO₂2-+O电化学反应.      

电催化氧化处理高盐废水

针对电催化氧化技术处理含盐废水具有氧化能力强、设备简单、无二次污染等特点,本文采用不同材料的电催化阳极对湿法冶金产生的含有机物高盐废水处理情况进行了对比分析,结果表明:不同材料的阳极析氧过电位次序为Ti/Ta2O5-IrO2电极＞石墨电极＞Ti/RuO2-IrO2电极;三种电极处理高盐废水的COD去除效率分别为62.0...     

水热电化学法制备LiNiO2薄膜

采用水热电化学法在Ni基体上一步合成结晶完好、具有网状结构的LiNiO2薄膜。由于薄膜多孔，具有很大的内表面积，组装成电池后电解质溶液能浸入薄膜内部的毛细管中，增大电极与电解质的接触面积，使电极材料的活性得到充分发挥。循环伏安电性能测试结果表明，薄膜电极在4．3V左右出现强氧化峰（脱锂），在3．5V左右出现还原峰（嵌锂），说明薄膜电极具有较好的电化学性能，因为LiNiO2氧化物层具有空穴导电性，是一种P型半导体。通过循环伏安法模拟水热电化学反应过程可知，在Ni基体上生成LiNiO2薄膜的反应历程为：Ni→Ni（OH）2→NiOOH→LiNiO2。     

Preparation of Ti-based Yb-doped SnO2–RuO2 electrode and electrochemical oxidation treatment of coking wastewater

In this study, the Ti/SnO₂–RuO₂ electrodes with different Yb contents were prepared by sol–gel method and thermal decomposition method, and the surface morphology and crystal structure of the electrodes were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD), the electrochemical properties of the electrodes were tested by linear sweep voltammetry (LSV) and cyclic voltammetry (CV). The electrochemical oxidation device was constructed with Yb-doped Ti/SnO₂–RuO₂ electrode as the anode and titanium plate as the cathode, and the electrochemical oxidation effect and product changes of the anode on coking wastewater were investigated. The results show that the surface of the electrode is flat with high crystallinity of SnO₂ and RuO₂ crystals at 1.5% Yb doping, and the LSV and CV curves indicate that the Yb doping of 1.5% increases the oxygen precipitation potential and electrocatalytic oxidation activity of the electrode. When the electrode with Yb doping of 1.5% is the anode with current density of 10 mA/cm² electrochemical oxidation time of 30 min, the electrode can remove chemical oxygen demand (COD) up to 85.06%, total organic carbon (TOC) up to 60.59% and UV₂₅₄ from 1.594 to 0.507 for coking wastewater. Gas chromatography (GC–MS), UV–vis and three-dimensional fluorescence results of coking wastewater before and after treatment show that large toxic substances in coking wastewater are degraded to low toxic organic substances, and most soluble organic substances are degraded and transformed. This study provides the possibility of basic research for the engineering practice of electrochemical oxidation for the treatment of coking wastewater.     

Electrochemical study of some 2-mercapto-5-R-ammino-1,3,4-thiadiazole derivatives using carbon paste electrodes

The electrochemical study of some 2-mercapto-5-R-ammino-1,3,4-thiadiazole derivatives was made by cyclic and linear sweep voltammetry using a carbon paste electrode (CPE, graphite/solid paraffin ratio 2:1) as working electrode and an Ag/AgCl reference electrode. The current-potential curves were recorded in anodic polarisation in -0.1 and +1.3 V range using aqueous solutions and different buffers (between pH 1.2 and 10.0), with 20 or 50 mV s(-1) sweep rate. The oxidation peak appears between +0.65 and +0.70 V due to disulphides formation. The 5-phenyl derivative has two oxidation peaks, the first at +0.45 +/- 0.03 V and the second at +0.65 +/- 0.03 V. The oxidation potentials are pH dependent, decreasing from 0.9 +/- 0.1 V at pH 1.2 to 0.6 +/- 0.1 V at a pH between 8.0 and 10.0. In some potential ranges depending on pKa of molecules the oxidation potential and oxidation current are pH independent. Simple, precise and accurate voltammetric methods for the determination of these compounds were developed and validated in 2.5 x 10(-6)-7.5 x 10(-4) mol l(-1) concentration ranges. The detection limits were 2.3 micromol l(-1) for 5-ammino-, 12.3 micromol l(-1) for 5-acetylammino-, 11.6 micromol l(-1) for 5-allylammino-, and 1.2 micromol l(-1) for 5-phenylammino-2-mercapto-1,3,4 thiadiazole derivatives.     

Electrooxidation of thiocyanate on the copper-modified gold electrode and its amperometric determination by ion chromatography

Cyclic voltammetry was used to investigate the electrochemical behavior of an Au/Cu electrode towards the electrooxidation of thiocyanate ion in alkaline medium. The effects of pH, copper loading, scan rate and applied potential on the electrocatalytic oxidation of thiocyanate have been investigated. Flow injection experiments and ion-chromatography (IC) were performed to characterise the electrode as an amperometric sensor for the thiocyanate determination. The effects of carbonate concentration and common interferents on the retention time were also estimated. The electrode stability, precision, limit of detection and linear range were evaluated at a constant applied potential of 0.7 V vs. Ag/AgCl. Calibration plots, obtained in IC, were linear from 1.0 to 195 microM (correlation coefficient of 0.9984). The detection limit (LOD) was 0.5 microM (29 ppb) in a 50 microlitres injection. An example of analytical application, which includes the IC separation and detection of thiocyanate ion present in human urine, is given.     

氧化还原液流电池卤化钒电解液的性能研究

采用循环伏安法、线性扫描伏安法和交流阻抗技术分别研究了石墨电极在不同浓度的卤化钒电解液中的电化学性能,并研究了不同浓度电解液的黏度性质。结果表明:卤化钒电解液中当溴的浓度在1.0~1.5 mol/L时黏度为1.0×10-3Pa.s左右,溶液的粘滞阻力较小;在石墨电极上的得到的循环伏安曲线氧化峰电流与还原峰电流之比约为1,且峰电位差较小,电极反应的可逆性较强;交流阻抗分析可知溶液电阻在此浓度范围内也较小,约为1Ω;交换电流密度和反应速率常数的计算结果表明,该电解液中溴浓度在1.0~1.5 mol/L时达到了最好的动力学性质。上述分析认为此浓度范围的电解液适合作为溴化钒氧化还原电池的正极电解液。     

High-Temperature Oxidation Behavior of Vanadium, Titanium-Bearing Magnetite Pellet

 By means of isothermal oxidation and chemical analysis, great importance was attached to the parameters that made effects on the oxidation degree of vanadium, titanium-bearing magnetite pellet in high-temperature processing (1073-1323 K). Based on the experimental data, oxidation kinetics of pellet was analyzed according to shrinking unreacted-core model subsequently. Experiment results display that the oxidation degree of pellet increases with increasing of oxidation time, oxidation temperature and oxygen content, as well as shrinking of pellet diameter. Under the condition of oxidation time 20 min, oxidation temperature 1223 K, oxygen content 15%, and pellet diameter 12 mm, oxidation degree of pellet reaches 92.92%. The analysis of oxidation kinetics indicates that oxidation process of pellet is controlled by chemical reaction with activation energy 68.64 kJ/mol at a relatively lower temperature (1073-1173 K). Oxidation process of pellet is mixed-controlled by chemistry reaction and diffusion with activation energy 39.66 kJ/mol in the temperature range of 1173-1273 K. When oxidation temperature is higher than 1273 K, the limited link of oxidation reaction is the diffusion control with the activation energy 20.85 kJ/mol. These results can serve as a reference to the production of vanadium, titanium-bearing magnetite pellet.     

液氯化法浸金过程热力学

针对氯化物体系中金的浸出反应进行热力学计算,分别绘制出Au-Cl-H2O体系电位-pH图、lg[Au(Ⅲ)]-pH图、lg[Cl-]-pH图,并分析了金氯化浸出过程的热力学影响因素。电位-pH图中存在着金氯络合物的稳定区域,在pH为中性或弱酸性并保持氧化电位高于0.9 V的条件下,金将以AuCl4-的形态浸出。AuCl4-的稳定性很差,易受氯化物浓度、AuCl4-浓度等热力学因素的影响。加大氯化物浓度或降低AuCl4-浓度,在热力学上有利于金的浸出。在保证金尽可能浸出的角度来说,热力学上最佳条件为pH 3.5～7.8、氧化电位高于0.9 V、氯化物浓度高于1 mol.L-1,AuCl4-浓度1×10-5～1×10-4mol.L-1。     

铅阳极泥氧化预处理工艺研究

铅阳极泥是粗铅电解精炼的中间产物,含有大量可进一步提取的有价伴生元素,如金、银、铅等元素.本文从生产实际出发,对铅阳极泥湿法预处理工艺进行研究,采用双氧水对铅阳极泥进行氧化预浸处理,并确定了最佳氧化预浸条件.试验表明,在双氧水用量为40 g、溶液盐酸浓度为4.5 mol/、液固比为6:1、浸出时间为3 h、浸出温度为8...     

六氰合铁酸铁/全氟磺酸 聚四氟乙烯共聚物复合膜修饰玻碳电极差分脉冲伏安法测定铅和镉

利用电聚合的方法将普鲁士蓝修饰到玻碳电极表面,然后修饰上全氟磺酸 聚四氟乙烯共聚物(Nafion)膜制成修饰电极。利用差分脉冲伏安法（DPV）对Pb2+和Cd2+在该修饰电极上的电化学行为进行了研究,建立了差分脉冲伏安法灵敏测定Cd2+和Pb2+的新方法。对富集电位、富集时间以及Nafion用量等实验条件进行了优化。在01 mol/L pH 45的NaAc HAc缓冲液中,在-11 V处搅拌富集450 s,用DPV分别测定-048 V和-073 V处的氧化峰电流。溶出峰电流与Pb2+和Cd2+的浓度分别在5×10-8~5×10-5 mol/L和2×10-8~2×10-5 mol/L范围内呈良好的线性关系,相关系数分别为0995和0992。检出限分别为5×10-9 mol/L (Pb2+)和2×10-9 mol/L(Cd2+) (S/N=3)。方法用于水样中Cd2+和Pb2+的测定,测定值与原子吸收光谱法的结果相一致,相对标准偏差为21%~38%。