新型钛基体二氧化铅电极的制备及应用研究
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摘要
随着电化学工业的不断发展，传统的阳极材料越来越表现出其局限性。二氧化铅电极因具有化学性质稳定、耐蚀性好、导电性好等特性，而广泛应用于各类工业生产。本文主要就制备性能优良的二氧化铅电极及其直接测定水体中COD和苯酚降解进行了探索与研究，为电化学工业电极的选用提供技术基础。因此，具有一定的学术和应用价值。
在总结现有Ti/PbO_2电极制备方法的基础上，提出在钛基体上热涂覆锡锑氧化物底层的新方法；然后在碱性条件下电沉积a-PbO_2为中间层；最后在酸性条件下电沉积β-PbO_2为表面层。
采用XRD和SEM对制备的电极进行晶相分析和表面形貌分析。结果表明，表面层中主要是β-PbO_2，且电极表面均匀平整，无裂纹等缺陷，晶粒排布紧密规则。对苯酚降解结果表明电极具有良好的电催化性能。线性扫描伏安曲线表明，电极具有较高的析氧电位，实现了电极的高催化活性和宽电位窗口，适应于各种还原性有机物的降解。
探讨了Ti/PbO_2电极直接测定水体中COD的方法。确定最佳测定条件为：工作电极电压为1．4V，Na_2SO_4电解液浓度为0．02mol/L，在一定的搅拌速度下，电解1．5min，测定其电流变化值；COD测定线性范围为20-200mg/L。每次测定后，对二氧化铅电极进行再生。再生液浓度为0．5mol/L，再生电压1．8V，再生时间为2min。实验采用增大电位气泡更新法使电极得到充分再生，保证了结果的准确性和重现性。该法用于实际水样与标准方法对照测定，结果表明，二者具有较好的一致性。
通过实验确定了Ti/PbO_2电极电催化氧化降解苯酚的最佳工艺条件为：电流密度30mA/cm~2、Na_2SO_4电解质浓度0．1mol/L、pH3．0、降解时间为2．5h。在此条件下，苯酚去除率可达91．3％。苯酚降解过程中不同时间的紫外光谱表明，苯酚的降解是一个复杂的过程，反应过程经历了苯醌中间产物产生和进一步降解的步骤。通过对苯酚降解过程动力学方程的讨论可知，苯酚的电催化氧化降解符合表观一级反应动力学特征。
With the development of the electrochemistry industy, conventional anodes showed more and more limitations. Lead dioxide is characterized by stable chemical property, anticorrosion, high electric conductivity, etc, So it is applied in various industries. In this paper, preparation of the excellent performance lead dioxide electrode and it's usage for direct determination COD and phenol degradation were studied. The results provided technical basis for choosing electrodes for electrochemistry industy production and had certain theoretic significance and applied value.
In the basis of summarized current methods of Ti/PbO_2 electrode preparation, a new method that covered stannum and antimony mixed oxide compounds as bottom was provided in this paper;Thenα-PbO_2 was electrodeposited in alkaline medium as mesosphere; At last, electrodepositedβ-PbO_2 in acidity medium was used as surface layer.
The crystal phase and the micrographs of the electrode surface layer were analyzed by SEM and XRD respectively.The results showed that the Ti/PbO_2 electrode surface layer,which was uniform、even and crack-free, crystal grain distribution was closely and regular, wasβ-PbO_2 mainly. The results of phenol degradat test showed that the electrode have high catalytic activity.Curve of linear sweep voltammetric showed that the electrode had high oxygen evolution potential, which realized high catalytic activity and wider potential window, and could adapt to various organic compounds degradation.
Direct determination of COD by Ti/PbO_2 electrode was discussed. By experiment the optimum determination condition was as follows: working voltage was 1.4v, sodium sulfate electrolyte concentration was 0.02 mol/L, measuring the current value change after electrolysis 1.5min, the optimum COD determination range was 20-200mg/L.After determination, the Ti/PbO_2 electrode was regenerated. The optimum regeneration condition was as follows: regeneration solution concentration was 0.5mol/L, regeneration voltage was 1.8v and the regeneration time was 2.0min; The surface of electrode was regenerated by bubbling in order to get a good reproducibility. The results showed that the method keeps good consistency with standard method when used in actual water samples.
The optimum condition of electrocatalytic oxidation degradation of phenol waste water using Ti/PbO_2 electrode was determined as follows:current density was 30mA/cm~2, sodium sulfate electrolyte concentration was 0.1mol/L, pH was 3.0, degradation time was 2.5h. Under this condition, the phenol remove rate was 91.3%.The ultraviolet spectrum of phenol degradation at different time showed that phenol degradation was a complex process, which experienced quinone intermediate products and then advanced degraded. The kinetics study showed that phenol degradation reaction accorded apparently with the-first-order kinetics.
在总结现有Ti/PbO_2电极制备方法的基础上，提出在钛基体上热涂覆锡锑氧化物底层的新方法；然后在碱性条件下电沉积a-PbO_2为中间层；最后在酸性条件下电沉积β-PbO_2为表面层。
采用XRD和SEM对制备的电极进行晶相分析和表面形貌分析。结果表明，表面层中主要是β-PbO_2，且电极表面均匀平整，无裂纹等缺陷，晶粒排布紧密规则。对苯酚降解结果表明电极具有良好的电催化性能。线性扫描伏安曲线表明，电极具有较高的析氧电位，实现了电极的高催化活性和宽电位窗口，适应于各种还原性有机物的降解。
探讨了Ti/PbO_2电极直接测定水体中COD的方法。确定最佳测定条件为：工作电极电压为1．4V，Na_2SO_4电解液浓度为0．02mol/L，在一定的搅拌速度下，电解1．5min，测定其电流变化值；COD测定线性范围为20-200mg/L。每次测定后，对二氧化铅电极进行再生。再生液浓度为0．5mol/L，再生电压1．8V，再生时间为2min。实验采用增大电位气泡更新法使电极得到充分再生，保证了结果的准确性和重现性。该法用于实际水样与标准方法对照测定，结果表明，二者具有较好的一致性。
通过实验确定了Ti/PbO_2电极电催化氧化降解苯酚的最佳工艺条件为：电流密度30mA/cm~2、Na_2SO_4电解质浓度0．1mol/L、pH3．0、降解时间为2．5h。在此条件下，苯酚去除率可达91．3％。苯酚降解过程中不同时间的紫外光谱表明，苯酚的降解是一个复杂的过程，反应过程经历了苯醌中间产物产生和进一步降解的步骤。通过对苯酚降解过程动力学方程的讨论可知，苯酚的电催化氧化降解符合表观一级反应动力学特征。
With the development of the electrochemistry industy, conventional anodes showed more and more limitations. Lead dioxide is characterized by stable chemical property, anticorrosion, high electric conductivity, etc, So it is applied in various industries. In this paper, preparation of the excellent performance lead dioxide electrode and it's usage for direct determination COD and phenol degradation were studied. The results provided technical basis for choosing electrodes for electrochemistry industy production and had certain theoretic significance and applied value.
In the basis of summarized current methods of Ti/PbO_2 electrode preparation, a new method that covered stannum and antimony mixed oxide compounds as bottom was provided in this paper;Thenα-PbO_2 was electrodeposited in alkaline medium as mesosphere; At last, electrodepositedβ-PbO_2 in acidity medium was used as surface layer.
The crystal phase and the micrographs of the electrode surface layer were analyzed by SEM and XRD respectively.The results showed that the Ti/PbO_2 electrode surface layer,which was uniform、even and crack-free, crystal grain distribution was closely and regular, wasβ-PbO_2 mainly. The results of phenol degradat test showed that the electrode have high catalytic activity.Curve of linear sweep voltammetric showed that the electrode had high oxygen evolution potential, which realized high catalytic activity and wider potential window, and could adapt to various organic compounds degradation.
Direct determination of COD by Ti/PbO_2 electrode was discussed. By experiment the optimum determination condition was as follows: working voltage was 1.4v, sodium sulfate electrolyte concentration was 0.02 mol/L, measuring the current value change after electrolysis 1.5min, the optimum COD determination range was 20-200mg/L.After determination, the Ti/PbO_2 electrode was regenerated. The optimum regeneration condition was as follows: regeneration solution concentration was 0.5mol/L, regeneration voltage was 1.8v and the regeneration time was 2.0min; The surface of electrode was regenerated by bubbling in order to get a good reproducibility. The results showed that the method keeps good consistency with standard method when used in actual water samples.
The optimum condition of electrocatalytic oxidation degradation of phenol waste water using Ti/PbO_2 electrode was determined as follows:current density was 30mA/cm~2, sodium sulfate electrolyte concentration was 0.1mol/L, pH was 3.0, degradation time was 2.5h. Under this condition, the phenol remove rate was 91.3%.The ultraviolet spectrum of phenol degradation at different time showed that phenol degradation was a complex process, which experienced quinone intermediate products and then advanced degraded. The kinetics study showed that phenol degradation reaction accorded apparently with the-first-order kinetics.
引文
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