电化学微传感器检测水中痕量铜离子

为改善微电极在阳极溶出伏安法检测重金属离子过程中低电流响应和低电催化能力的缺点,提出了一种在碳纤维微电极表面合成还原氧化石墨烯/纳米金材料制得还原氧化石墨烯纳米金修饰碳纤维微电极（rGO/AuNPs CFMEs）的方法.通过SEM表征,所制备的rGO/AuNPs CFMEs具有比表面积高、吸附能力强和催化活性好的特点,因此改性微电极适合作为方波阳极溶出伏安法（SWASV）测定水中铜离子（Cu²⁺）的工作电极.在构建微传感器测试水中痕量铜离子系统后,对pH值、电导率、富集时间和富集电位等检测条件进行了优化.在pH值为4,电导率为36.1S/m,富集时间为360s,富集电位为-1.2V的最佳条件下,铜的线性范围和检出限分别0~1.0μmol/L和2.4nmol/L.此外,微传感器的可重复性、长期稳定性以及选择性也得到了验证.     

人工神经网络用于铅的化学形态模拟计算

用前馈线性网络法求解水体系中Ｐｂ（２＋）与ＯＨ－之间的反应常数，不同训练算法对求解结果的精度、收敛速度及权值均有影响．结果表明，批处理算法的精度最好，权值不出现负值，但运算时间最长；在线算法的精度虽不如批处理算法，而比数据变换－在线算法好，权值有时会出现负值．运算时间较长；数据变换－在线算法的优点是运算时间短，但相对误差较大，权值出现负值的机会多。采用反馈网络模拟计算铅的各种化学形态的浓度．用物料核算的方法对反馈网络模型进行检验表明，此种模型用于平衡计算是可行的，详细分析了理论模拟和实验曲线的差异的原因，温度的影响最小，在４＜ｐＨ＜９时，ＣＯ有重要的影响．在国代检验时，ｎ值取整所引入的误差的影响亦不可忽视。从本文的结果可以看到，采用前馈网络和反馈网络相结合的方法考察水体中的化学形态是可行的．从而为解决这一类问题提供了一种可能的途径．     

重金属离子在腐殖酸表面的吸附——类颗粒表面吸附模型

本实验用伏安质子滴定法获得重金属离子(Cu~(2+)、Pb~(2+)、Cd~(2+))在腐殖酸表面吸附的实验数据,并基于这些数据提出重金属离子在腐殖酸表面的络合模型。模型中引入两个实验常数:反应系数α和竞争反应常数K_H。实验结果表明,这两个常数的实验值在一相当宽的起始溶液条件下基本稳定。基于这两个常数而获得的pH相关吸附等温线和实验数据相当符合。模型中采用了由电位滴定得到的腐殖酸表面羧基浓度作为最大表面基团浓度,并对其质子解离常数进行了表面电荷影响的修正。     

Electrochemical study of sulfide solution in the presence of surfactants

Voltammetric curve studies on aqueous Na2S solution in the presence of three types of surfactants are presented. Presence of anodic surfactant (HTAB) in creases anode current density and makes the corresponding anode peak potential shift to more negative. Potentials of the reduction of elemental sulfur to intermediates Sx2-shift to more negative with the increasing of HTAB concentrations. In the presence of HTAB, the anode current density at 77oC increases more than at 34oC. The electrolysis indicates that anodic product sulfur loosely adhered to the graphite electrode surface when HTAB is added to the anolyte. The total efficiency of producing sulfur is high after several times of cycle electrolysis.The results show that anode passivation is minimized in the presence of HTAB. The depassivation effect of HTAB is discussed.     

Electrochemical study of sulfide solution in the presence of surfactants

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Electrochemical treatment of olive mill wastewater: Treatment extent and effluent phenolic compounds monitoring using some uncommon analytical tools

Problems related with industrials effluents can be divided in two parts: (1) their toxicity associated to their chemical content which should be removed before discharging the wastewater into the receptor media; (2) and the second part is linked to the difficulties of pollution characterisation and monitoring caused by the complexity of these matrixes. This investigation deals with these two aspects, an electrochemical treatment method of an olive mill wastewater (OMW) under platinized expanded titanium electrodes using a modified Grignard reactor for toxicity removal as well as the exploration of the use of some specific analytical tools to monitor effluent phenolic compounds elimination. The results showed that electrochemical oxidation is able to remove/mitigate the OMW pollution. Indeed, 87% of OMW color was removed and all aromatic compounds were disappeared from the solution by anodic oxidation. Moreover, 55% of the chemical oxygen demand (COD) and the total organic carbon (TOC) were reduced. On the other hand, UV- Visible spectrophotometry, Gaz chromatography/mass spectrometry, cyclic voltammetry and 13 C Nuclear Magnetic Resonance (NMR) showed that the used treatment seems efficaciously to eliminate phenolic compounds from OMW. It was concluded that electrochemical oxidation in a modified Grignard reactor is a promising process for the destruction of all phenolic compounds present in OMW. Among the monitoring analytical tools applied, cyclic voltammetry and 13 C NMR are among the techniques that are introduced for the first time to control the advancement of the OMW treatment and gave a close insight on polyphenols disappearance.     

二氧化铅电极的制备、表征及其电催化性能研究

以电沉积法制备了Ti/PbO2和Ti/MnO2/PbO22种电极.采用SEM、XRD和XPS等分析方法表征了电极的形貌、元素组成及元素化学态,并以罗丹明B为目标有机物,考察了所制备电极的析氧极化曲线和电催化活性以及Ti/MnO2/PbO2电极的循环伏安曲线.研究结果表明,Ti/MnO2/PbO2电极的稳定性、使用寿命、析氧电位和电催化活性较Ti/PbO2电极都有所提高,并且罗丹明B在Ti/MnO2/PbO2电极上的反应主要发生在析氧反应区,且反应不可逆.     

Concentrations of cadmium and lead heavy metals in Dardanelles seawater

Cadmium and lead were determined simultaneously in seawater by differential pulse stripping voltammetry (DPSV) preceded by adsoptive collection of complexes with 8-hydroxyquinoline (oxine) on to a hanging mercury drop electrode (HMDE). In preliminary experiments the optimal analytical condition for oxine concentration was found to be 2.10⁻⁵ M, at pH 7.7, the accumulation potential was −1.1 V, and the initial scannig potential was −0.8 V. The peak potentials were found −0.652 V for Cd and −0.463 V for Pb At the 60 s accumalation time. The limit of detection (LOD) and limit of quantitatification (LOQ) were found to be by voltammetry as 0.588 and 1.959 μg l⁻¹ (RSD, 5.50%) for Cd and 0.931 and 3.104 μg l⁻¹ (RSD, 4.10%) for Pb at 60 s stirred accumulation time respectively. In these conditions the most of the seawater samples are amenable for direct voltammetric determination of cadmium and lead using a HMDE. An adsorptive stripping mechanism of the electrode reaction was proposed. For the comparison, seawater samples were also analysed by ICP-atomic emission spectrometry method (ICP-AES). The applied voltammetric technique was validated and good recoveries were obtained.     

Determination of Nitrobenzene in Wastewater Using a Hanging Mercury Drop Electrode

The determination of trace amount nitrobenzene in wastewater on a hanging mercury drop electrode was studied. The determination conditions of pH, supporting electrolyte, accumulation potential, accumulation time, and voltammetric response were optimized. The sharp peak of the nitrobenzene was appeared at 0.05 V. The peak electric current was proportional to the concentration of nitrobenzene in the range of 1.47 × 10⁻⁵ ∼ 1.0 × 10⁻³ mol/l with relative standard deviations of 3.99 ∼ 8.94%. The detection limit of the nitrobenzene in water was 5 × 10⁻⁶ mol/l. The proposed method offered low limit of determination, easy operation, the use of simple instrumentation, high sensitivity and good reproducibility. It was applied to the determination of nitrobenzene in wastewater with an average recovery of 94.0% ∼ 105%. The proposed method provided fast, sensitive and sometimes real time detection of nitrobenzene.     

基于方波溶出伏安法的电化学传感器检测水体中痕量铅

基于方波溶出伏安法运用丝网印刷电极探索了一种利用电化学传感器检测水样中痕量铅的方法.得到了该检测方法的最佳参数:方波频率30 Hz,振幅80 mV,电位增量5 mV;0.5 mol/L的支持电解质(KCl);沉积电位-1.1 V,沉积时间400 s.在该优化条件下,在浓度为25 ～ 500μg/L范围内溶出峰电流与铅离子浓度呈良好的线性关系(R2=0.9945).对于几种其他金属离子的干扰实验结果表明,Mn2的存在严重抑制铅离子的峰电流.