铈掺杂Ti/Sn-Sb阳极制备及催化氧化苯酚研究
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摘要
本文以电沉积-热分解法制备铈掺杂钛基锡锑电极。主要以电极对苯酚的催化降解性能和电解时的槽压作为主要指标,对钛基锡锑电极进行了优化,确定了铈掺杂比例、热处理温度等工艺条件。采用SEM、EDX、EPMA及XRD等检测方法对所制备电极的微观形貌、元素组成、分布及相组成进行了分析。研究了铈的掺杂和热处理温度对电极性能的影响,结果表明铈适量掺杂能使晶粒细化,电极涂层结构致密,氧化物分布均匀,基体覆盖完全,对苯酚有较好的催化性能;过量的铈掺杂导致晶格破坏,电极性能降低。热处理温度对电极性能有较大影响。温度不同导致涂层形貌、析氧电位和电极的导电性不同,热处理温度为550℃较为适宜。
以优化的Ti/SnSbCe电极为阳极,钛板为阴极,在无隔膜电解槽中,采用恒流电解法对苯酚模拟废水进行氧化降解研究。系统地研究了电解质浓度、溶液初始pH值、苯酚初始浓度、电流、溶液温度及电极材料对降解的影响。实验结果表明:在0.1～0.5mol/L的范围内,电解质浓度越高,苯酚和COD的去除效果越好;初始pH在5到7苯酚的去除效果最好,碱性条件下最差;苯酚初始浓度增加,苯酚和COD的去除率有较大降低,但去除量却有大幅度的提高;电流增大,苯酚和COD的去除效果有很大提高,但是电流效率降低;溶液温度升高,苯酚和COD的去除率都有所增加,槽压降低;不同的电极材料对苯酚的催化性能有明显差异,SnSbCe/Ti电极降解效果最好,SnSb/Ti电极次之,RuO_2/Ti电极最差。
采用电化学测试系统,以循环伏安法和极化法对苯酚在Ti/SnSbCe阳极上的氧化降解行为进行了研究。结果表明,苯酚在Ti/SnSbCe阳极氧化为典型的不可逆反应过程,反应受扩散控制;电极对苯酚的催化活性和析氧电位密切相关,析氧电位高,催化活性好;苯酚浓度增加,析氧曲线没有发生变化,析氧电位也没有随苯酚浓度的变化发生移动,反应过程中电极表面不存在有机物的聚合现象,电极在苯酚浓度较高时保持了良好的催化活性;电极在经过40次的循环伏安后曲线不变,电极的稳定性较好。
通过对不同电解时间溶液的高效液相色谱分析,发现高浓度苯酚降解过程较复杂,倾向于电化学转化过程,首先苯酚吸附在阳极表面,随后被氧化为各种中间产物,然后中间产物继续被氧化,苯环被打开生成有机酸,最终把苯酚降解为CO_2和H_2O;低浓度苯酚的氧化降解过程倾向于电化学燃烧过程,降解更为彻底,没有中间产物生成。
In this paper,the Ce-doped Ti/SnSb electrode was prepared by electrodeposition and thermal decomposition methods.Ti/SnSb electrode was optimized with catalytic properties and cell voltage as the main assessing items and finally,the optimum doping ratio and thermal oxidation temperature was determined.The microstructure,element compositions and distributions,phase compositions of the Ce-doped Ti/Sn-Sb electrode had been studied by means of scanning electron microscopy with energy dispersive X-ray(SEM-EDX),electron probe microanalysis(EPMA),X-ray diffraction(XRD).The effects of Ce doping and thermal oxidation temperature on the properties of electrode were investigated and the results have shown that grains can be facilitated in fine size with suitable content of Ce,the anode has a compact texture,the oxide of its coat distributes equably and completely covers the Ti matrix,it has catalysis for the oxidative degradation of phenol.However,SnO_2 crystal lattice can be destroyed and the performance of electrode can be decreased with excess content of Ce. Thermal oxidation temperature has significant effect on the performance of the electrode.The micrographs of the surface layer,oxygen evolution potential,electrical conductivity differ with diffrient oxidation temperature and the suitable oxidation temperature is about 550℃.
Take the optimized electrode as anode,titanic plate as cathode,the simulant phenolic wastewater is degraded in a electrolytic cell without diaphragm.The effects of influencing factors of degradation of phenol such as electrolyte concentration,original pH value of electrolyte,initial concentration of phenol,electrical current,electrolyte temperature,electrode material on degradation of phenol are systematically investigated.It has been found that,the greater the Na_2SO_4 concentration,the better the removal effect of phenol and COD in the concentration range of 0.1 to 0.5 mol/L;the best removal effect of phenol is in the original pH value from 5 to 7 of electrolyte and the worst is under the condition of high pH value;phenol and COD removal rate decrease as initial phenol concentration increases,but the absolute wiping off value increases obviously;the removal effect of phenol and COD increase with increasing of electrical current,but the current efficiency decrease;An increase in electrolyte temperature is found to reduce cell voltage and have a beneficial effect on the phenol oxidation degradation;catalytic properties of different electrode vary considerably, SnSbCe/Ti anode is the best,SnSb/Ti anode is in the middle,RuO_2/Ti anode is the worst.
Using electrochemical test System,the oxidation degradation behaviors of phenol on SnSbCe/Ti electrode were studied by cyclic voltammetry and polarization curves.The results of the tests indicate that,the process of anodic oxidation of phenol on SnSbCe/Ti electrode is irreversible,and it is controlled by diffusion process;catalytic activity of the electrode is closely bound up with oxygen evolution potential,high oxygen evolution potential can improve catalytic activity for phenol;there is no variation of oxygen evolution curve with the increase of phenol concentration,there was no phenomena of organic matter polymerization during the reaction and the electrode keeps good catalytic activity for oxidation of high concentration phenol;cyclic voltammetry curve remains the same after 40 times scans,the electrode shows the merit of good stability.
The results of high performance liquid chromatographic analysis of electrolyte with different degradation time show that degradation of phenol with high concentration is complex and the degradation process inclines to electrochemical conversion;first,phenol is adsorbed on the surface of electrode and is oxidized to intermediate products,and then intermediate products are converted to organic acids along with the break of benzene ring, finally the organic intermediate products are oxided to CO_2 and H_2O;the degradation process of low concentration inclines to electrochemical combustion,the degradation is more thorough and there is no organic intermediate product in the process of the degradation.
以优化的Ti/SnSbCe电极为阳极,钛板为阴极,在无隔膜电解槽中,采用恒流电解法对苯酚模拟废水进行氧化降解研究。系统地研究了电解质浓度、溶液初始pH值、苯酚初始浓度、电流、溶液温度及电极材料对降解的影响。实验结果表明:在0.1～0.5mol/L的范围内,电解质浓度越高,苯酚和COD的去除效果越好;初始pH在5到7苯酚的去除效果最好,碱性条件下最差;苯酚初始浓度增加,苯酚和COD的去除率有较大降低,但去除量却有大幅度的提高;电流增大,苯酚和COD的去除效果有很大提高,但是电流效率降低;溶液温度升高,苯酚和COD的去除率都有所增加,槽压降低;不同的电极材料对苯酚的催化性能有明显差异,SnSbCe/Ti电极降解效果最好,SnSb/Ti电极次之,RuO_2/Ti电极最差。
采用电化学测试系统,以循环伏安法和极化法对苯酚在Ti/SnSbCe阳极上的氧化降解行为进行了研究。结果表明,苯酚在Ti/SnSbCe阳极氧化为典型的不可逆反应过程,反应受扩散控制;电极对苯酚的催化活性和析氧电位密切相关,析氧电位高,催化活性好;苯酚浓度增加,析氧曲线没有发生变化,析氧电位也没有随苯酚浓度的变化发生移动,反应过程中电极表面不存在有机物的聚合现象,电极在苯酚浓度较高时保持了良好的催化活性;电极在经过40次的循环伏安后曲线不变,电极的稳定性较好。
通过对不同电解时间溶液的高效液相色谱分析,发现高浓度苯酚降解过程较复杂,倾向于电化学转化过程,首先苯酚吸附在阳极表面,随后被氧化为各种中间产物,然后中间产物继续被氧化,苯环被打开生成有机酸,最终把苯酚降解为CO_2和H_2O;低浓度苯酚的氧化降解过程倾向于电化学燃烧过程,降解更为彻底,没有中间产物生成。
In this paper,the Ce-doped Ti/SnSb electrode was prepared by electrodeposition and thermal decomposition methods.Ti/SnSb electrode was optimized with catalytic properties and cell voltage as the main assessing items and finally,the optimum doping ratio and thermal oxidation temperature was determined.The microstructure,element compositions and distributions,phase compositions of the Ce-doped Ti/Sn-Sb electrode had been studied by means of scanning electron microscopy with energy dispersive X-ray(SEM-EDX),electron probe microanalysis(EPMA),X-ray diffraction(XRD).The effects of Ce doping and thermal oxidation temperature on the properties of electrode were investigated and the results have shown that grains can be facilitated in fine size with suitable content of Ce,the anode has a compact texture,the oxide of its coat distributes equably and completely covers the Ti matrix,it has catalysis for the oxidative degradation of phenol.However,SnO_2 crystal lattice can be destroyed and the performance of electrode can be decreased with excess content of Ce. Thermal oxidation temperature has significant effect on the performance of the electrode.The micrographs of the surface layer,oxygen evolution potential,electrical conductivity differ with diffrient oxidation temperature and the suitable oxidation temperature is about 550℃.
Take the optimized electrode as anode,titanic plate as cathode,the simulant phenolic wastewater is degraded in a electrolytic cell without diaphragm.The effects of influencing factors of degradation of phenol such as electrolyte concentration,original pH value of electrolyte,initial concentration of phenol,electrical current,electrolyte temperature,electrode material on degradation of phenol are systematically investigated.It has been found that,the greater the Na_2SO_4 concentration,the better the removal effect of phenol and COD in the concentration range of 0.1 to 0.5 mol/L;the best removal effect of phenol is in the original pH value from 5 to 7 of electrolyte and the worst is under the condition of high pH value;phenol and COD removal rate decrease as initial phenol concentration increases,but the absolute wiping off value increases obviously;the removal effect of phenol and COD increase with increasing of electrical current,but the current efficiency decrease;An increase in electrolyte temperature is found to reduce cell voltage and have a beneficial effect on the phenol oxidation degradation;catalytic properties of different electrode vary considerably, SnSbCe/Ti anode is the best,SnSb/Ti anode is in the middle,RuO_2/Ti anode is the worst.
Using electrochemical test System,the oxidation degradation behaviors of phenol on SnSbCe/Ti electrode were studied by cyclic voltammetry and polarization curves.The results of the tests indicate that,the process of anodic oxidation of phenol on SnSbCe/Ti electrode is irreversible,and it is controlled by diffusion process;catalytic activity of the electrode is closely bound up with oxygen evolution potential,high oxygen evolution potential can improve catalytic activity for phenol;there is no variation of oxygen evolution curve with the increase of phenol concentration,there was no phenomena of organic matter polymerization during the reaction and the electrode keeps good catalytic activity for oxidation of high concentration phenol;cyclic voltammetry curve remains the same after 40 times scans,the electrode shows the merit of good stability.
The results of high performance liquid chromatographic analysis of electrolyte with different degradation time show that degradation of phenol with high concentration is complex and the degradation process inclines to electrochemical conversion;first,phenol is adsorbed on the surface of electrode and is oxidized to intermediate products,and then intermediate products are converted to organic acids along with the break of benzene ring, finally the organic intermediate products are oxided to CO_2 and H_2O;the degradation process of low concentration inclines to electrochemical combustion,the degradation is more thorough and there is no organic intermediate product in the process of the degradation.
引文
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