CN101519233A - Method for degrading organic substances by using photoelectric catalysis of short TiO2 nano-tube array film electrode - Google Patents
Method for degrading organic substances by using photoelectric catalysis of short TiO2 nano-tube array film electrode Download PDFInfo
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Abstract
本发明涉及一种利用短TiO2纳米管阵列薄膜电极光电催化降解有机物的方法，属于环境污染治理技术领域。将清洗过的钛片作为阳极，置于含氟离子的电解质溶液中，以铂电极为对电极，进行阳极氧化反应，在整个阳极氧化反应过程中，对进行反应的电解质溶液进行超声波超声分散，阳极氧化完成后，再经烧结得到短TiO2纳米管阵列薄膜电极。以得到的短TiO2纳米管阵列薄膜电极为工作电极，以Ag－AgCl为参比电极，Pt为对电极，在有机污染物溶液中加入0.01－1M的硫酸钠溶液，即可对有机污染物进行降解。本发明采用管长较短、结实的TiO2纳米管阵列薄膜做电极，光生电荷复合低，传输快，表现出更高的光电催化降解有机物的性能。
The invention relates to a method for photocatalytically degrading organic matter by using a short TiO2 nanotube array thin film electrode, and belongs to the technical field of environmental pollution control. The cleaned titanium sheet is used as the anode, placed in the electrolyte solution containing fluorine ions, and the platinum electrode is used as the counter electrode to carry out anodic oxidation reaction. During the entire anodic oxidation reaction process, the reacting electrolyte solution is ultrasonically dispersed, After the anodic oxidation is completed, short TiO2 nanotube array film electrodes are obtained by sintering. Take the obtained short TiO2 nanotube array film electrode as the working electrode, use Ag-AgCl as the reference electrode, and Pt as the counter electrode, add 0.01-1M sodium sulfate solution to the organic pollutant solution, and the organic pollutant can be treated. for degradation. The invention adopts the short and strong TiO2 nanotube array film as the electrode, has low recombination of photogenerated charges, fast transmission, and exhibits higher photoelectric catalytic degradation performance of organic matter.
Description
技术领域 technical field
本发明涉及一种利用短TiO2纳米管阵列薄膜电极光电催化降解有机物的方法，属于环境污染治理技术领域。The invention relates to a method for photocatalytically degrading organic matter by using a short TiO2 nanotube array thin film electrode, and belongs to the technical field of environmental pollution control.
背景技术 Background technique
纳米TiO2作为一种优良的光催化剂已广泛应用于催化氧化环境中的有机污染物。近十几年来，TiO2已广泛应用于纺织品、卫生用品、建筑材料、涂料等领域，且其光化学稳定性优良，无毒、价廉。2001年，美国科学家Grimes等人利用阳极氧化的方法在氢氟酸水溶液介质中制备出TiO2纳米管阵列薄膜(Gong D W et al J.Mater.Res.(2001)16：3331-3334)。在这种材料中，光催化剂TiO2纳米管垂直、整齐有序地排列在金属钛基体上，有利于光生电荷的分离与传输，作为电极材料，能表现出优良的光电催化降解有机物的性能。通过改变阳极氧化中电解质的组成，如采用有机电解质，可以提高纳米管的长度至几微米甚至几百微米。然而，从光电催化降解有机污染物性能效果来看，随着TiO2纳米管管长的增加并没有带来催化性能的提高，反而引起了纳米管电极稳定性的下降。Grimes等(Grimes，et al(2007)J Phys Chem C 111：14770-14776)研究表明随着管长的增加，管与管之间的结合力以及纳米管薄膜层与底层基质之间的结合力也相应减弱。同时，在有机电解质中阳极氧化制备纳米管过程中产生断裂的长管及其它残渣等会很容易造成纳米管层的堵塞。这些原因均降低了长TiO2纳米管阵列电极的稳定性，影响了其光生电荷的分离效率与传递速率，进而影响了TiO2纳米管阵列电极的光电催化降解有机污染物的性能。现有技术制备的TiO2纳米管阵列，其阳极氧化过程是在磁力搅拌下进行的，在搅拌条件下制备的TiO2纳米管阵列电极，管长较长，金属钛与基底的结合力较弱，这是造成TiO2纳米管阵列电极纳米管与基底结合力弱，稳定性差主要原因。As an excellent photocatalyst, nano- TiO2 has been widely used to catalyze the oxidation of organic pollutants in the environment. In the past ten years, TiO 2 has been widely used in textiles, sanitary products, building materials, coatings and other fields, and it has excellent photochemical stability, non-toxicity and low price. In 2001, American scientists Grimes et al. prepared TiO 2 nanotube array films in hydrofluoric acid aqueous medium by anodic oxidation (Gong D W et al J. Mater. Res. (2001) 16: 3331-3334). In this material, the photocatalyst TiO2 nanotubes are arranged vertically and orderly on the metal titanium substrate, which is beneficial to the separation and transmission of photogenerated charges. As an electrode material, it can show excellent performance in photocatalytic degradation of organic matter. By changing the composition of the electrolyte in anodic oxidation, such as using an organic electrolyte, the length of the nanotubes can be increased to several microns or even hundreds of microns. However, from the perspective of photocatalytic degradation of organic pollutants, the increase in the length of TiO 2 nanotubes did not bring about an improvement in catalytic performance, but instead caused a decrease in the stability of nanotube electrodes. Grimes et al. (Grimes, et al (2007) J Phys Chem C 111: 14770-14776) have shown that as the tube length increases, the binding force between the tubes and the binding force between the nanotube film layer and the underlying matrix also increases. Correspondingly weakened. At the same time, broken long tubes and other residues generated during the preparation of nanotubes by anodic oxidation in organic electrolytes can easily cause blockage of the nanotube layer. These reasons all reduce the stability of the long TiO 2 nanotube array electrode, affect the separation efficiency and transfer rate of the photogenerated charge, and then affect the performance of the TiO 2 nanotube array electrode for photocatalytic degradation of organic pollutants. The TiO2 nanotube array prepared by the prior art, its anodic oxidation process is carried out under magnetic stirring, the TiO2 nanotube array electrode prepared under the stirring condition, the tube length is longer, and the binding force between metal titanium and the substrate is weak , which is the main reason for the weak binding force and poor stability between the TiO 2 nanotube array electrode nanotubes and the substrate.
发明内容 Contents of the invention
本发明的目的在于针对现有技术的不足，提供一种利用短TiO2纳米管阵列薄膜电极光电催化降解有机物的方法，制备管长较短、结实的TiO2纳米管阵列薄膜电极，提高光电催化降解有机污染物的活性。The object of the present invention is to aim at the deficiencies in the prior art, provide a kind of method that utilizes short TiO 2 nanotube array thin film electrodes to degrade organic matters photocatalytically, prepare tube length relatively short, strong TiO 2 nanotube array thin film electrodes, improve photocatalytic activity to degrade organic pollutants.
为实现上述目的，本发明在阳极氧化制备TiO2纳米管阵列薄膜电极的过程中，对于所用的阳极氧化反应电解质溶液进行超声波超声的方法进行分散，以制备管长较短、结实的TiO2纳米管阵列薄膜电极用于光电催化降解有机污染物。In order to achieve the above object, the present invention, in the process of preparing TiO2 nanotube array thin film electrode by anodic oxidation, disperses the used anodic oxidation reaction electrolyte solution by ultrasonic ultrasonic method, so as to prepare short and strong TiO2 nanometer tubes. Tube-array thin-film electrodes for photocatalytic degradation of organic pollutants.
本发明制备短TiO2纳米管阵列薄膜电极的具体方法是：The present invention prepares short TiO The concrete method of nanotube array film electrode is:
将清洗过的钛片作为阳极，置于含氟离子的电解质溶液中，以铂电极为对电极，进行阳极氧化，阳极氧化电压控制在10-30V。在整个阳极氧化反应过程中，对进行反应的含氟离子的电解质溶液进行超声波超声分散，反应时间控制在10-60min，超声波的频率控制在25KHz-80KHz之间；阳极氧化完成后，得到短TiO2纳米管阵列薄膜样品；将所得的短TiO2纳米管阵列薄膜样品用水冲洗后置于烘箱中干燥，冷却至室温后，再经烧结，得到短TiO2纳米管阵列薄膜电极。The cleaned titanium sheet is used as an anode, placed in an electrolyte solution containing fluorine ions, and a platinum electrode is used as a counter electrode for anodic oxidation, and the anodic oxidation voltage is controlled at 10-30V. During the whole anodic oxidation reaction process, the electrolytic solution containing fluorine ions is ultrasonically dispersed, the reaction time is controlled at 10-60min, and the frequency of the ultrasonic wave is controlled between 25KHz-80KHz; after the anodic oxidation is completed, short TiO 2 nanotube array film samples; the resulting short TiO2 nanotube array film samples were rinsed with water, dried in an oven, cooled to room temperature, and then sintered to obtain short TiO2 nanotube array film electrodes.
本发明的降解有机污染物的方法为：The method for degrading organic pollutants of the present invention is:
以烧结后的短TiO2纳米管阵列薄膜为工作电极，以Ag-AgCl为参比电极，以Pt为对电极，在有机污染物溶液中加入摩尔浓度为0.01-1M的硫酸钠溶液作为电解质，并施加偏电压0.4-1.2V，打开光源，对有机污染物进行降解。With the sintered short TiO2 nanotube array film as the working electrode, Ag-AgCl as the reference electrode, and Pt as the counter electrode, add a sodium sulfate solution with a molar concentration of 0.01-1M in the organic pollutant solution as the electrolyte, And apply a bias voltage of 0.4-1.2V, turn on the light source, and degrade the organic pollutants.
本发明制备短TiO2纳米管阵列薄膜电极时，所述的含氟离子的电解质溶液为氢氟酸水溶液，其中氟离子的质量百分数为0.2-1％，构成氟离子的化合物是氢氟酸。When preparing short TiO2 nanotube array film electrodes in the present invention, the electrolyte solution containing fluorine ions is hydrofluoric acid aqueous solution, wherein the mass percentage of fluorine ions is 0.2-1%, and the compound constituting fluorine ions is hydrofluoric acid.
本发明中，所述的短TiO2纳米管阵列薄膜样品烧结时，其烧结温度为400～700℃，烧结时间0.5-3小时，烧结气氛可以是空气气氛也可以是氧气气氛。In the present invention, when the short TiO 2 nanotube array film sample is sintered, the sintering temperature is 400-700° C., the sintering time is 0.5-3 hours, and the sintering atmosphere can be air atmosphere or oxygen atmosphere.
本发明制备得到的短TiO2纳米管阵列薄膜电极，其管长范围为70-300nm。The short TiO2 nanotube array film electrode prepared by the invention has a tube length range of 70-300nm.
本发明的光电催化降解有机污染物的方法，与已有技术相比具有显著的优点。由于在阳极氧化制备TiO2纳米管阵列电极的过程中，采用超声波超声的方法替代现有搅拌的方法对电解质溶液进行分散，所制备的TiO2纳米管阵列电极管长短，管与基底结合牢固，纳米管表面光滑，当作光电催化电极时，光生电荷复合更低，传输更快，因而能表现出更高的光电催化降解有机物的性能。超声波超声的方法替代现有搅拌的方法之所以能够制备出管长较短且结实有序的TiO2纳米管阵列薄膜，是由超声分散特有的性能所决定的。在超声过程中，超声场中液体内的微小气泡随声压变化而产生强烈振荡，瞬时产生的强压力和局部温度升高对溶液质点产生强烈的超声空化作用。这与传统的搅拌方法相比，超声作用可以提高电化学反应速度，增加体系内的传质，缩短阳极氧化时间，从而得到薄膜厚度较短、尺寸可控、高度有序并与金属钛基底直接相连，结合更为牢固的TiO2纳米管阵列薄膜。正是上述原因，使得本发明制备的电极具有更高的光电催化降解有机物的活性。本发明方法可广泛应用于各类废水的处理。Compared with the prior art, the photoelectric catalytic degradation method for organic pollutants of the present invention has significant advantages. In the process of preparing TiO2 nanotube array electrode by anodic oxidation, ultrasonic ultrasonic method is used instead of the existing stirring method to disperse the electrolyte solution. The surface of the nanotube is smooth, and when it is used as a photoelectrocatalytic electrode, the photogenerated charge recombination is lower and the transport is faster, so it can show a higher performance of photocatalytic degradation of organic matter. Ultrasonic method instead of the existing stirring method can prepare TiO 2 nanotube array film with short tube length and orderly structure, which is determined by the unique performance of ultrasonic dispersion. During the ultrasonic process, the tiny bubbles in the liquid in the ultrasonic field oscillate strongly with the change of the sound pressure, and the instantaneous strong pressure and local temperature rise produce a strong ultrasonic cavitation effect on the solution particles. Compared with the traditional stirring method, ultrasonic action can increase the electrochemical reaction speed, increase the mass transfer in the system, and shorten the anodic oxidation time, so that the film thickness is shorter, the size is controllable, highly ordered, and it can be directly bonded to the metal titanium substrate. Connected, combined with a stronger TiO 2 nanotube array film. It is for the above reasons that the electrodes prepared in the present invention have higher photoelectric catalytic activity for degrading organic matter. The method of the invention can be widely applied to the treatment of various waste water.
本发明的光电催化降解有机物方法，采用管长较短、结实的TiO2纳米管阵列薄膜做电极，光生电荷复合低，传输快，能表现出更高的光电催化降解有机物的性能，可广泛应用于各类废水的处理。The method for photocatalytic degradation of organic matter of the present invention adopts a short and strong TiO2 nanotube array film as an electrode, has low recombination of photogenerated charges and fast transmission, can show higher performance of photocatalytic degradation of organic matter, and can be widely used for the treatment of various types of wastewater.
附图说明 Description of drawings
图1是本发明实施例1在制备短TiO2纳米管阵列薄膜过程中电流-时间曲线，对照为在相同条件磁力搅拌下制备过程中电流-时间曲线。Fig. 1 is the current-time curve during the preparation of the short TiO2 nanotube array film in Example 1 of the present invention, and the comparison is the current-time curve during the preparation process under the same magnetic stirring conditions.
图2是本发明实施例1制备的短TiO2纳米管阵列的扫描电镜照片，(a)为正视图，(b)为侧视图，(c)为对照例中利用传统磁力搅拌方法制备得到TiO2纳米管阵列的侧视图。Fig. 2 is the scanning electron micrograph of the short TiO2nanotube array prepared in Example 1 of the present invention, (a) is a front view, (b) is a side view, (c) utilizes traditional magnetic stirring method to prepare TiO in the comparative example 2 Side view of the nanotube array.
图3是本发明实施例1制备的短TiO2纳米管阵列薄膜(曲线a)与用传统磁力搅拌方法制备得到的TiO2纳米管阵列薄膜(曲线b)在1M氢氧化钾溶液中的光电流曲线比较。Fig. 3 is the short TiO2 nanotube array film (curve a) prepared by the embodiment of the present invention 1 and the TiO2 nanotube array film (curve b) prepared by traditional magnetic stirring method in the photocurrent of 1M potassium hydroxide solution Curve comparison.
图4是本发明实施例1制备的短TiO2纳米管阵列薄膜(曲线a)与用传统磁力搅拌方法制备得到的纳米管阵列薄膜(曲线b)在不同有机物溶液中的光电流响应曲线。其中，(I)为10mM葡萄糖溶液；(II)为1mM邻苯二甲酸氢钾溶液；(III)为0.1mM甲基橙溶液。Figure 4 is the photocurrent response curves of the short TiO2 nanotube array film (curve a) prepared in Example 1 of the present invention and the nanotube array film (curve b) prepared by traditional magnetic stirring method in different organic solutions. Wherein, (I) is 10mM glucose solution; (II) is 1mM potassium hydrogen phthalate solution; (III) is 0.1mM methyl orange solution.
具体实施方式 Detailed ways
以下结合附图和实施例对本发明的技术方案作进一步描述。以下实施例不构成对本发明的限定。The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and embodiments. The following examples are not intended to limit the present invention.
实施例1：Example 1:
将清洗过的钛片作为阳极，取铂片作为对电极组装成双电极体系，并在反应容器内加入氢氟酸水溶液做电解质，使得溶液中氟离子的质量百分数达到0.5％，调节电压为20V。整个阳极氧化反应过程中对电解质溶液进行超声波超声分散，超声频率40KHz，反应30min后，停止超声，即可得到短TiO2纳米管阵列薄膜样品。取下样品，用水冲洗后置于烘箱中干燥，待冷却至室温后，经SEM观察，制备的钛基TiO2纳米管阵列，管长为280nm(见图1)。将样品在400℃空气气氛中烧结3小时后，即得到短TiO2纳米管阵列薄膜电极，可用作光电催化电极用于有机污染物的降解。The cleaned titanium sheet is used as the anode, and the platinum sheet is used as the counter electrode to assemble a two-electrode system, and hydrofluoric acid aqueous solution is added to the reaction vessel as the electrolyte, so that the mass percentage of fluorine ions in the solution reaches 0.5%, and the voltage is adjusted to 20V . During the entire anodic oxidation reaction process, the electrolyte solution was ultrasonically dispersed, and the ultrasonic frequency was 40KHz. After 30 minutes of reaction, the ultrasonic wave was stopped, and the short TiO 2 nanotube array thin film sample was obtained. The sample was removed, rinsed with water and dried in an oven. After cooling to room temperature, observed by SEM, the prepared titanium-based TiO2 nanotube array had a tube length of 280nm (see Figure 1). After the samples were sintered in an air atmosphere at 400 °C for 3 hours, short TiO2 nanotube array thin-film electrodes were obtained, which can be used as photoelectrocatalytic electrodes for the degradation of organic pollutants.
将烧结后的短TiO2纳米管阵列薄膜电极放入初始浓度为20mg/L的甲基橙溶液中作为工作电极，以Ag-AgCl为参比电极，Pt为对电极，在甲基橙溶液中加入0.01M硫酸钠溶液，在室温下施加0.5V偏电压，同时采用紫外灯照射TiO2纳米管电极。反应3h后，甲基橙降解90％以上。Put the sintered short TiO2 nanotube array thin film electrode into the methyl orange solution with an initial concentration of 20 mg/L as the working electrode, with Ag-AgCl as the reference electrode and Pt as the counter electrode, in the methyl orange solution Add 0.01M sodium sulfate solution and apply a 0.5V bias voltage at room temperature while irradiating the TiO2 nanotube electrode with a UV lamp. After 3 hours of reaction, more than 90% of the methyl orange was degraded.
作为对照，将清洗过的钛片作为阳极，铂片作为对电极组装成双电极体系，并在反应容器内加入氢氟酸水溶液做电解质，使得溶液中氟离子的质量百分数达到0.5％，调节电压为20V。整个阳极氧化过程采用磁力搅拌，反应30min后，取下样品，用水冲洗后置于烘箱中干燥，待冷却至室温后，即可得到钛基TiO2纳米管阵列薄膜，管长为500nm(见图1c)。将电极薄膜在400℃空气气氛中烧结3h后，即可用作光电催化电极用于有机污染物的降解。As a comparison, the cleaned titanium sheet was used as the anode, and the platinum sheet was used as the counter electrode to assemble a double-electrode system, and hydrofluoric acid aqueous solution was added as the electrolyte in the reaction vessel, so that the mass percentage of fluorine ions in the solution reached 0.5%, and the voltage was adjusted 20V. The entire anodic oxidation process adopts magnetic stirring. After 30 minutes of reaction, the sample is removed, rinsed with water, and dried in an oven. After cooling to room temperature, a titanium-based TiO2 nanotube array film can be obtained, and the tube length is 500nm (see Fig. 1c). After the electrode film was sintered in an air atmosphere at 400°C for 3 hours, it could be used as a photoelectrocatalytic electrode for the degradation of organic pollutants.
图1给出了两种不同溶液分散条件下制备TiO2纳米管阵列薄膜过程中其电流-时间曲线，由图1可见，在超声分散过程得到的电流-时间曲线，其电流密度要远高于磁力搅拌过程得到的电流密度値，说明在超声作用下，TiO2纳米管层的溶解速率增加明显，这使得TiO2纳米管薄膜管层厚度较短。Figure 1 shows the current-time curves during the preparation of TiO2 nanotube array films under two different solution dispersion conditions. The current density value obtained during the magnetic stirring process shows that under the action of ultrasound, the dissolution rate of the TiO 2 nanotube layer increases significantly, which makes the thickness of the TiO 2 nanotube thin film tube layer shorter.
图2给出了两种不同分散条件下制备的TiO2纳米管阵列的扫描电镜照片，(a)为实施例1正视图，(b)为实施例1侧视图，(c)为对照例中利用传统磁力搅拌方法制备得到TiO2纳米管阵列的侧视图。扫描电镜是PHILIPS，Netherlands，Sirion200镜，加速电压5kV。由2图可见，通过超声方法制备的纳米管阵列薄膜在基体表面上排列高度有序，管
图3给出了实施例1超声分散条件下制备的短TiO2纳米管阵列薄膜(曲线a)与传统磁力搅拌方法制备得到的TiO2纳米管阵列薄膜(曲线b)在1M氢氧化钾溶液中的光电流曲线比较(曲线c为暗电流)。由图3可见，通过超声方法制备得到的短TiO2纳米管阵列薄膜显示出了比用传统磁力搅拌方法制备得到的TiO2纳米管阵列薄膜更高的催化活性。Fig. 3 has provided the short TiO2 nanotube array film (curve a) prepared under the ultrasonic dispersion condition of embodiment 1 and the TiO2 nanotube array film (curve b) that traditional magnetic stirring method prepares in 1M potassium hydroxide solution Comparison of photocurrent curves (curve c is dark current). It can be seen from Figure 3 that the short TiO 2 nanotube array film prepared by ultrasonic method shows higher catalytic activity than the TiO 2 nanotube array film prepared by traditional magnetic stirring method.
图4给出了实施例1超声分散条件下制备的短TiO2纳米管阵列薄膜(曲线a)与传统磁力搅拌方法制备得到的TiO2纳米管阵列薄膜(曲线b)在不同有机物溶液中的光电流响应曲线。其中，(I)为10mM葡萄糖溶液；(II)为1mM邻苯二甲酸氢钾溶液；(III)为0.1mM甲基橙溶液。由图4可见，不论在何种有机物溶液中，通过本发明方法制备得到的短TiO2纳米管阵列薄膜均比用传统磁力搅拌方法制备得到的电极表现出高的光电流响应，因而表现出高的光电催化降解有机污染物活性。Figure 4 shows the short TiO2 nanotube array film (curve a) prepared under the condition of ultrasonic dispersion in Example 1 and the TiO2 nanotube array film (curve b) prepared by traditional magnetic stirring method in different organic solutions Current response curve. Wherein, (I) is 10mM glucose solution; (II) is 1mM potassium hydrogen phthalate solution; (III) is 0.1mM methyl orange solution. As can be seen from Fig. 4, no matter in what kind of organic solution, the short TiO prepared by the method of the present invention The nanotube array thin film shows a high photocurrent response than the electrode prepared by the traditional magnetic stirring method, thus showing high photocatalytic degradation of organic pollutants.
实施例2：Example 2:
将清洗过的钛片作为阳极，取铂片作为对电极组装成双电极体系，并在反应容器内加入氢氟酸水溶液做电解质，使得溶液中氟离子的质量百分数达到0.2％，调节电压为30V。整个阳极氧化过程中对电解质溶液进行超声波超声分散，超声频率25KHz，反应1小时后，即可得到短TiO2纳米管阵列薄膜样品。取下样品，用水冲洗后置于烘箱中干燥，待冷却至室温后，经SEM观察，制备的钛基TiO2纳米管阵列，管长为300nm。将样品在500℃空气气氛中烧结0.5小时后，即得到短TiO2纳米管阵列薄膜电极，可用作光电催化电极用于有机污染物的降解。The cleaned titanium sheet is used as the anode, and the platinum sheet is used as the counter electrode to assemble a two-electrode system, and hydrofluoric acid aqueous solution is added in the reaction vessel as the electrolyte, so that the mass percentage of fluorine ions in the solution reaches 0.2%, and the voltage is adjusted to 30V . During the whole anodic oxidation process, the electrolytic solution is ultrasonically dispersed, and the ultrasonic frequency is 25KHz. After 1 hour of reaction, the short TiO 2 nanotube array thin film sample can be obtained. The sample was removed, rinsed with water, and dried in an oven. After cooling to room temperature, it was observed by SEM that the prepared titanium-based TiO 2 nanotube array had a tube length of 300nm. After the samples were sintered at 500 °C in an air atmosphere for 0.5 hours, short TiO2 nanotube array thin film electrodes were obtained, which can be used as photoelectrocatalytic electrodes for the degradation of organic pollutants.
将烧结后的短TiO2纳米管阵列薄膜电极放入初始浓度为50mg/L的四环素溶液中作为工作电极，以Ag-AgCl为参比电极，Pt为对电极，在四环素溶液中加入1M硫酸钠溶液，在室温下施加1.2V偏电压，同时采用紫外灯照射TiO2纳米管电极。反应3h后，四环素降解85％以上。Put the sintered short TiO2 nanotube array thin film electrode into the tetracycline solution with an initial concentration of 50mg/L as the working electrode, use Ag-AgCl as the reference electrode, and Pt as the counter electrode, add 1M sodium sulfate to the tetracycline solution solution, apply a bias voltage of 1.2 V at room temperature, while using a UV lamp to irradiate the TiO 2 nanotube electrode. After 3 hours of reaction, more than 85% of the tetracycline was degraded.
实施例3：Example 3:
将清洗过的钛片作为阳极，取铂片作为对电极组装成双电极体系，并在反应容器内加入氢氟酸水溶液做电解质，使得溶液中氟离子的质量百分数达到0.7％，调节电压为10V。整个阳极氧化过程中对电解质溶液进行超声波超声分散，超声频率80KHz，反应60min后，即可得到短TiO2纳米管阵列薄膜样品。取下样品，用水冲洗后置于烘箱中干燥，待冷却至室温后，经SEM观察，制备的钛基TiO2纳米管阵列，管长为70nm。将样品在600℃氧气气氛中烧结3小时后，即得到短TiO2纳米管阵列薄膜电极，可用作光电催化电极用于有机污染物的降解。The cleaned titanium sheet is used as the anode, and the platinum sheet is used as the counter electrode to assemble a double-electrode system, and hydrofluoric acid aqueous solution is added to the reaction vessel as the electrolyte, so that the mass percentage of fluorine ions in the solution reaches 0.7%, and the voltage is adjusted to 10V . During the whole anodic oxidation process, the electrolytic solution is ultrasonically dispersed, the ultrasonic frequency is 80KHz, and the short TiO 2 nanotube array thin film sample can be obtained after the reaction for 60min. The sample was removed, rinsed with water, and dried in an oven. After cooling to room temperature, it was observed by SEM that the prepared titanium-based TiO 2 nanotube array had a tube length of 70nm. After the samples were sintered in an oxygen atmosphere at 600 °C for 3 hours, short TiO2 nanotube array thin-film electrodes were obtained, which can be used as photoelectrocatalytic electrodes for the degradation of organic pollutants.
将烧结后的短TiO2纳米管阵列薄膜电极放入初始浓度为15mg/L的双酚A溶液中作为工作电极，以Ag-AgCl为参比电极，Pt为对电极，在双酚A溶液中加入0.05M硫酸钠溶液，在室温下施加0.8V偏电压，同时采用紫外灯照射TiO2纳米管电极。反应2.5h后，双酚A降解85％以上。Put the sintered short TiO2 nanotube array film electrode into the bisphenol A solution with an initial concentration of 15mg/L as the working electrode, with Ag-AgCl as the reference electrode and Pt as the counter electrode, in the bisphenol A solution Add 0.05M sodium sulfate solution, apply a 0.8V bias voltage at room temperature, and at the same time irradiate the TiO2 nanotube electrode with a UV lamp. After 2.5 hours of reaction, more than 85% of bisphenol A was degraded.
实施例4：Example 4:
将清洗过的钛片作为阳极，取铂片作为对电极组装成双电极体系，并在反应容器内加入氢氟酸水溶液做电解质，使得溶液中氟离子的质量百分数达到1％，调节电压为25V。整个阳极氧化过程中对电解质溶液进行超声波超声分散，超声频率80KHz，反应10min后，即可得到TiO2纳米管阵列薄膜和金属钛基体一体化的样品。取下样品，用水冲洗后置于烘箱中干燥，待冷却至室温后，经观察，合成的纳米管薄膜排列高度有序，管长为200nm。将样品在700℃空气气氛中烧结1小时后，即得到短TiO2纳米管阵列薄膜电极，可用作光电催化电极用于有机污染物的降解。The cleaned titanium sheet is used as the anode, and the platinum sheet is used as the counter electrode to assemble a double-electrode system, and hydrofluoric acid aqueous solution is added to the reaction vessel as the electrolyte, so that the mass percentage of fluorine ions in the solution reaches 1%, and the voltage is adjusted to 25V . During the entire anodic oxidation process, the electrolyte solution is ultrasonically dispersed, and the ultrasonic frequency is 80KHz. After 10 minutes of reaction, a sample integrated with the TiO 2 nanotube array film and the metal titanium matrix can be obtained. The sample was removed, rinsed with water, and dried in an oven. After cooling to room temperature, it was observed that the synthesized nanotube film was highly ordered, and the tube length was 200nm. After the samples were sintered in an air atmosphere at 700 °C for 1 hour, short TiO2 nanotube array thin-film electrodes were obtained, which can be used as photoelectrocatalytic electrodes for the degradation of organic pollutants.
将烧结后的短TiO2纳米管阵列薄膜电极放入初始浓度为10mg/L酸性橙溶液中，以Ag-AgCl为参比电极，Pt为对电极，在酸性橙溶液中加入0.1M硫酸钠溶液，在室温下施加0.4V偏电压，同时采用紫外灯照射TiO2纳米管电极。反应2小时后，酸性橙降解75％以上。Put the sintered short TiO2 nanotube array film electrode into the acid orange solution with an initial concentration of 10mg/L, with Ag-AgCl as the reference electrode and Pt as the counter electrode, add 0.1M sodium sulfate solution to the acid orange solution , a bias voltage of 0.4 V was applied at room temperature while the TiO2 nanotube electrode was irradiated with a UV lamp. After 2 hours of reaction, more than 75% of the acid orange was degraded.
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| CN101798126A (en) * | 2010-04-23 | 2010-08-11 | 四川大学 | Method for treating industrial waste water by means of photoelectrocatalysis |
| CN102942277A (en) * | 2012-11-14 | 2013-02-27 | 东南大学 | Method for enhancing photoelectric catalytic degradation effect of tetracycline drugs |
| CN103285843A (en) * | 2013-06-06 | 2013-09-11 | 重庆三峡学院 | A TiO2 nanoparticle/TiO2 nanotube array and its application |
| CN104909437A (en) * | 2015-06-25 | 2015-09-16 | 清华大学 | Method for efficiently removing nitrate from water by Ti nano-electrode |
| CN108911056A (en) * | 2018-03-23 | 2018-11-30 | 同济大学 | { 001 } preparation and application for the titanium dioxide photoelectrode that crystal face controllably exposes |
| CN111359677A (en) * | 2020-03-13 | 2020-07-03 | 湖北文理学院 | Preparation method of photoelectric catalyst for selectively degrading dibutyl phthalate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101798126A (en) * | 2010-04-23 | 2010-08-11 | 四川大学 | Method for treating industrial waste water by means of photoelectrocatalysis |
| CN102942277A (en) * | 2012-11-14 | 2013-02-27 | 东南大学 | Method for enhancing photoelectric catalytic degradation effect of tetracycline drugs |
| CN103285843A (en) * | 2013-06-06 | 2013-09-11 | 重庆三峡学院 | A TiO2 nanoparticle/TiO2 nanotube array and its application |
| CN103285843B (en) * | 2013-06-06 | 2015-04-22 | 重庆三峡学院 | A TiO2 nanoparticle/TiO2 nanotube array and its application |
| CN104909437A (en) * | 2015-06-25 | 2015-09-16 | 清华大学 | Method for efficiently removing nitrate from water by Ti nano-electrode |
| CN104909437B (en) * | 2015-06-25 | 2017-04-12 | 清华大学 | Method for efficiently removing nitrate from water by Ti nano-electrode |
| CN108911056A (en) * | 2018-03-23 | 2018-11-30 | 同济大学 | { 001 } preparation and application for the titanium dioxide photoelectrode that crystal face controllably exposes |
| CN111359677A (en) * | 2020-03-13 | 2020-07-03 | 湖北文理学院 | Preparation method of photoelectric catalyst for selectively degrading dibutyl phthalate |
| CN111359677B (en) * | 2020-03-13 | 2023-03-28 | 湖北文理学院 | Preparation method of photoelectric catalyst for selectively degrading dibutyl phthalate |
| CN113189174A (en) * | 2021-02-09 | 2021-07-30 | 同济大学 | Titanium dioxide photoelectrode with three-dimensional crystal face junction property and preparation and application thereof |
| CN113189174B (en) * | 2021-02-09 | 2023-08-04 | 同济大学 | Titanium dioxide photoelectrode with three-dimensional crystal plane crystallization property and preparation and application thereof |
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