CN115490304A - Preparation method and application of cerium dioxide doped titanium nanotube electrode - Google Patents
Preparation method and application of cerium dioxide doped titanium nanotube electrode Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 101
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- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 83
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
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- 238000006731 degradation reaction Methods 0.000 claims abstract description 89
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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Abstract
The invention discloses a preparation method and application of a cerium dioxide doped titanium nanotube electrode, wherein the preparation process comprises etching a titanium sheet to be used as an electrode anode, and carrying out anodic oxidation; then, taking the anode oxidized electrode as an anode, reacting under constant voltage, and calcining the obtained electrode at high temperature to obtain a titanium dioxide nanotube electrode; preparing one or two mixture solution of cerium sulfate or cerium nitrate as an electrodeposition solution, performing electrochemical deposition with constant potential by using the electrode as a working electrode, and annealing and calcining the obtained electrode to obtain the cerium dioxide doped titanium nanotube electrode. The preparation process is safe, the cost is low, experiments prove that the electrode prepared by the invention has good conductivity, high oxygen evolution potential, excellent electrochemical oxidation activity and pollutant degradation capability and high stability, has good degradation and mineralization effects on simulated dye wastewater, particularly wastewater containing acid orange 7, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of electrochemical oxidation degradation of pollutants, and particularly relates to a preparation method of a cerium dioxide doped titanium nanotube electrode and application of the cerium dioxide doped titanium nanotube electrode in electrochemical oxidation.
Background
The textile and printing industry, as a major consumer of industrial water, produces large amounts of waste water on a daily basis. The dye wastewater generally has the characteristics of complex components, high organic matter concentration, large pH change, difficult biodegradation and the like, so the treatment of the dye wastewater is always a difficult problem in the environmental field. The dye wastewater contains a large amount of organic pollutants with a 'three-cause' effect, such as benzene, anthracene, amine compounds, polycyclic aromatic hydrocarbon, azo substances and the like, has a toxic effect on microorganisms in water, and is more harmful to the life health of human beings. In addition, dye wastewater has high chromaticity, and the pollution can destroy the self-purification function of a water body, interfere the growth of aquatic organisms and seriously destroy the ecological balance.
At present, the treatment of dye wastewater mainly comprises a physical adsorption method, a membrane separation method, biodegradation and advanced oxidation technology. The adsorption technology is convenient to operate, but the adsorption material is high in manufacturing cost and difficult to regenerate, and is difficult to treat a large amount of wastewater; the separation effect of the membrane separation technology depends on the performance of the semipermeable membrane, the components of the dye wastewater are complex, the pollution problem of the semipermeable membrane exists in the treatment process, and the service life is reduced; the application of advanced oxidation technology has the problems of secondary pollution, high energy consumption, high operation cost and the like, and industrial operation is difficult to realize. The electrochemical oxidation technology has the characteristics of no secondary pollution, small equipment floor area, easiness in automation, high reaction efficiency, low toxicity of reaction products and the like, and has a good development prospect in treatment of dye wastewater.
In the anode materials applied in the electrochemical oxidation at present, the boron-doped diamond electrode and the dimensionally stable electrode have better electrochemical oxidation performance. The common commercial electrode has low cost, but has poor oxidation capacity, and can not meet the requirement of wastewater degradation. However, the boron-doped diamond electrode material has high cost and complex preparation process, and cannot be produced in a large scale; the shape stable electrode active layer is easy to fall off to cause electrode deactivation, and metals which can cause heavy pollution, such as lead metal and the like, are generally required to be doped, so that the electrode has potential harm to the environment. Therefore, there is an urgent need to develop a novel electrode with high electrocatalytic activity, high chemical stability, low cost and no harm to the environment.
Disclosure of Invention
The invention aims to: aiming at the problems in the prior art, the invention provides a preparation method of a cerium dioxide doped titanium nanotube electrode which has good electrocatalytic oxidation capability, is cheap and has high efficiency.
The invention also provides application of the cerium dioxide doped titanium nanotube electrode.
The technical scheme is as follows: in order to achieve the above object, the present invention provides a method for preparing a ceria-doped titanium nanotube electrode, comprising the following steps:
(1) Polishing a titanium plate, a titanium rod or a titanium net into a titanium sheet, and etching the titanium sheet by adopting a concentrated sulfuric acid and/or concentrated nitric acid mixed solution; soaking the etched titanium sheet in ultrasonic waves and drying;
(2) Taking the electrode obtained in the step (1) as an anode, taking a platinum sheet electrode as a cathode, preparing an anodic oxidation electrolyte, carrying out anodic oxidation, taking out the anode electrode after the reaction is finished, washing and drying;
(3) Preparing a phosphoric acid-containing ethylene glycol solution as an electrolyte, taking the electrode obtained in the step (2) as an anode, taking a platinum sheet electrode as a cathode, reacting under constant voltage, and then calcining the obtained electrode at high temperature to obtain a titanium dioxide nanotube electrode, namely TiO 2 An NTA electrode;
(4) Preparing a solution containing one or two of cerium sulfate or cerium nitrate as an electrodeposition solution, performing constant-potential electrochemical deposition on the electrode obtained in the step (3) as a working electrode, a platinum sheet electrode as a reference electrode and a saturated calomel electrode as a counter electrode, and annealing and calcining the obtained electrode to obtain a cerium dioxide doped titanium nanotube electrode, namely a CeO 2 /TiO 2 NTA。
Wherein, a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a molar ratio of 1-1.
Wherein the anodic oxidation electrolyte in step (2) contains 0.1-0.75wt% of ammonium fluoride and 1-3wt% of H 2 A glycol solution of O.
Preferably, the mass fraction of ammonium fluoride in the anodizing electrolyte is 0.25wt%, and the mass fraction of water is 2wt%.
Wherein, the anodic oxidation in the step (2) adopts a constant voltage method, and the anodic oxidation is carried out for 2-6h under 50-70V.
Preferably, the voltage is 50V, and the optimal reaction time is 5h.
Preferably, the mass fraction of phosphoric acid in the solution prepared in step (3) is 0.1 to 0.5wt%.
Wherein the reaction under the constant voltage in the step (3) is reaction for 1-2h under the constant voltage of 50-70V.
Wherein the high-temperature calcination in the step (3) is carried out at 450-800 ℃ for 2-3h.
Wherein the concentration of cerium ions in the electrodeposition solution in the step (4) is 1-10mmol/L.
Preferably, the potential of the electrochemical deposition in the step (4) is 0.4-1.2V Vs.SCE, the reaction time is 5-30min, and the annealing calcination is carried out at 450-800 ℃ for 1-2h.
The cerium dioxide doped titanium nanotube electrode prepared by the preparation method disclosed by the invention is applied to electrochemical oxidation degradation of acid orange 7 dye (AO 7) wastewater.
Further, the specific steps of the application are as follows: taking the waste water solution containing acid orange 7 as electrolyte, taking a ceric oxide-doped titanium nanotube electrode as an anode and a platinum sheet electrode as a cathode, and carrying out degradation treatment under constant current density of 1-20 mA/cm 2 The electrolyte is 0.01-0.1 mol/L sodium sulfate, the stirring speed is 500-1000r/min, and the reaction time is 1-2h.
The invention provides a cerium dioxide doped titanium nanotube electrode, which is prepared by taking a titanium plate as a substrate and sequentially performing processes of polishing, acidizing etching, anodic oxidation, anodic reoxidation, high-temperature calcination, electrodeposition and annealing on the substrate. Specifically, the titanium plate is used as a substrate, and oxides and irregular particles on the surface of titanium are removed from the substrate through the processes of sand paper polishing, concentrated sulfuric acid/concentrated nitric acid acidification and etching in sequence, so that the subsequent titanium nano tube is generated more uniformly; then, carrying out anodic oxidation on the electrode slice in an electrolyte solution containing glycol and fluoride ions to generate a titanium nanotube structure; oxidizing again in the solution containing phosphoric acid and glycol to make the surface structure of the electrode more stable; preparing and changing the crystalline phase of the titanium nanotube through a high-temperature calcination process; then taking the electrode as an anode, and carrying out electrodeposition in electrolyte containing trivalent cerium at constant potential to realize doping of cerium metal; the doped cerium metal is converted into a cerium oxide nanoparticle morphology by a high temperature annealing process. The specific surface area of the electrode material can be remarkably increased by the titanium nano-tube, the doping of the cerium dioxide nano-particles can form a special electronic action mechanism with the titanium nano-tube, and meanwhile, oxygen vacancies and defects are introduced on the surface of the electrode by the introduction of the cerium dioxide nano-particles, so that OH is generated more easily, and the electrochemical oxidation reaction process is facilitated. Further experiments prove that the electrocatalytic oxidation process of the electrode prepared by the invention mainly realizes the degradation of pollutants through the efficient oxidation of hydroxyl radicals, and in addition, electrochemical analysis finds that the electrode prepared by the invention has an oxygen evolution potential higher than that of a BDD electrode and has stronger electrocatalytic oxidation potential. The invention aims at degrading dye pollutants through electrochemical oxidation, provides the electrocatalytic anode electrode which is cheap and efficient and has good electrocatalytic activity, and the electrode has good application prospect in electrochemical oxidation.
The cerium dioxide doped titanium nanotube electrode prepared by the invention can quickly oxidize and degrade typical dye AO7 wastewater in a solution in a conventional electrocatalysis reactor, the solution decoloration effect is obvious after a period of treatment, and the cerium dioxide doped titanium nanotube electrode has a good effect on removing COD. Compared with the commercialized electrode which is widely applied at present, the electrode provided by the invention has optimal electrochemical oxidation activity on typical dye AO7 wastewater, and has the advantages of low cost, wide source of raw materials, no need of large-scale equipment in the preparation process, and is expected to be widely applied in the field of electrochemical treatment of dye wastewater.
According to the invention, a titanium plate is taken as a substrate, and oxides and irregular particles on the surface of titanium are removed from the substrate through sand paper grinding, concentrated sulfuric acid/concentrated nitric acid acidification and etching processes in sequence, so that the subsequent titanium nano tube is generated more uniformly; then, carrying out anodic oxidation on the electrode plate in an electrolyte solution containing glycol and fluoride ions to generate a titanium nanotube structure; oxidizing again in the solution containing phosphoric acid and glycol to make the surface structure of the electrode more stable; preparing and changing the crystalline phase of the titanium nanotube through a high-temperature calcination process; then taking the electrode as an anode, and carrying out electrodeposition in electrolyte containing trivalent cerium at constant potential to realize doping of cerium metal; the doped cerium metal is converted into a cerium oxide nanoparticle morphology by a high temperature annealing process. The specific surface area of the electrode material can be remarkably increased by the titanium nano-tube, the doping of the cerium dioxide nano-particles and the titanium nano-tube form a special electronic action mechanism, and meanwhile, oxygen vacancies and defects are introduced on the surface of the electrode by the introduction of the cerium dioxide nano-particles, so that OH is more easily generated, and the electrochemical oxidation reaction process is facilitated.
The invention takes a titanium plate and cerium metal as raw materials, generates a catalyst with high catalytic effect through a series of specific reaction processes, and proves that the catalyst has better catalytic effect than the existing commercialized electrode through degradation experiments and electrochemical characterization data of pollutants.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the preparation process is simple and safe, the prepared electrode has the advantages of low cost, good conductivity and corrosion resistance, and meanwhile, the specific surface area and the charge transfer efficiency of the electrode are increased and the conductivity of the electrode is improved through the simple anodization process.
2. The preparation of the titanium nanotube is realized by an anodic oxidation technology, the stability of the electrode is improved by an anodic reoxidation and high-temperature annealing technology based on phosphoric acid as a stabilizer, the doping of cerium dioxide is realized by an electrochemical deposition technology, more oxygen vacancies are introduced, the oxygen evolution potential, the catalytic activity and the conductivity of the electrode are increased, and the electrochemical oxidation activity and the pollutant degradation capability of the electrode are higher.
3. Experiments prove that the electrode has good electrochemical oxidation potential and good capacitance characteristics. Meanwhile, the electrode prepared by the invention can efficiently degrade the typical dye AO7 through the electrochemical oxidation process, and meanwhile, the electrode has a good mineralization effect (embodied by COD) on an AO7 solution.
4. Compared with several common commercial electrodes, the electrode prepared by the invention has the optimal electrocatalytic activity and pollutant degradation capability for typical dye AO7, and meanwhile, the preparation process is simpler, the environment is more friendly, and the application potential is good.
Drawings
FIG. 1 shows CeO in example 1 of the present invention 2 /TiO 2 The degradation effects of the NTA electrode on the acid orange 7 simulated dye wastewater are compared at different current densities;
FIG. 2 shows CeO in example 1 of the present invention 2 /TiO 2 The NTA electrode is used for carrying out 7-mode treatment on acid orange under different electrolyte concentrationsComparing the degradation effects of the pseudo-dye wastewater;
FIG. 3 shows CeO in example 1 of the present invention 2 /TiO 2 The degradation effect of the NTA electrode changes along with the times when the AO7 is electrolyzed for multiple times;
FIG. 4 is a comparison of the degradation effect of the electrode on AO7 dye wastewater in example 1 and comparative examples 8 to 12 of the present invention;
FIG. 5 is a linear sweep voltammogram of the electrodes of example 1 and comparative example 13 of the present invention;
FIG. 6 is a cyclic voltammogram of different electrodes in example 1 of the present invention and comparative examples 13 to 15.
Detailed Description
The present invention is further illustrated by the following examples.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Boron diamond electrode (BDD), titanium-based tin antimony (Ti/SnO) 2 -Sb 2 O 5 ) Titanium-based iridium tantalum ruthenium iridium (Ti/IrO) 2 -Ta 2 O 5 ) Titanium-based ruthenium-iridium (Ti/RuO) 2 -IrO 2 ) The Ti/pt are commercially available.
Example 1
Firstly, preparing an electrode, wherein the preparation process of the electrode comprises the following steps: (1) The titanium plate is polished into a titanium sheet by using sand paper, a concentrated sulfuric acid/concentrated nitric acid mixed solution with the molar ratio of 1. And (3) placing the etched titanium sheet in acetone and ethanol solution in sequence, soaking and ultrasonically treating for 60 minutes, and then placing the titanium sheet in a 60 ℃ drying oven for drying for 12 hours. (2) Preparing an anodizing electrolyte solution containing 0.25wt% of ammonium fluoride and 2wt% 2 Ethylene glycol solution of O in a teflon beaker. Taking the electrode treated in the step (1), taking the electrode as an anode, taking a platinum sheet electrode as a cathode, taking the solution as electrolyte, carrying out anodic oxidation for 5 hours at 50V by adopting a constant voltage method, taking the anode electrode out after the reaction is finished, washing the surface of the electrode obtained after the anodic oxidation by using ethanol, washing by using ultrapure water, and drying. (3) Preparing 0.25wt% phosphoric acid-containing ethylene glycol solution as electrolyte, using the obtained electrode as anode, and platinum as anodeThe sheet electrode is used as a cathode, the reaction is carried out for 1h under the constant voltage of 50V, then the obtained electrode is put into a muffle furnace and calcined for 2h at the high temperature of 500 ℃, and the titanium dioxide nanotube electrode, namely TiO, is obtained 2 NTA electrode. (4) And preparing a 5mmol/L cerium nitrate aqueous solution as an electrodeposition solution, performing electrochemical deposition with constant potential by using the electrode as a working electrode, a platinum sheet electrode as a reference electrode and a saturated calomel electrode as a counter electrode, wherein the potential is 0.8V Vs.SCE, and the reaction time is 15min. The obtained electrode is annealed and calcined for 2h at the temperature of 500 ℃ to obtain a cerium dioxide doped titanium nanotube electrode, namely CeO 2 /TiO 2 NTA。
Test 1: electrochemical oxidation degradation of acid orange 7 simulated dye wastewater: preparing a simulated dye wastewater solution containing 50mg/L of acid orange 7 (AO 7). 200mL of simulated dye wastewater is taken as electrolyte in an electrochemical reactor, a cerium dioxide doped titanium nanotube electrode is taken as an anode, a platinum sheet electrode is taken as a cathode, the reaction is carried out under constant current density of 10mA/cm 2 The electrolyte is 0.05mol/L sodium sulfate, the stirring speed is 500r/min, and the reaction time is 2h. And after the reaction, the concentration of AO7 and COD in the water sample are measured, and the concentration of AO7 is detected by adopting an ultraviolet spectrophotometer. The result shows that the degradation rate of reaction 2h, AO7 reaches 90.12%, and the COD degradation rate reaches 82.18%.
And (3) testing 2: adopting a three-electrode cyclic voltammetry test system and respectively adopting the electrode CeO 2 /TiO 2 NTA electrode and TiO 2 The NTA electrode is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, the test electrolyte solution is 0.05mol/L sodium sulfate solution, the scanning speed is 100mV/s, and the potential window is-0.5-1.5V vs. The test results are shown in FIG. 5. FIG. 5 shows that CeO 2 The CV curve of the electrode obtained after doping is approximately rectangular, which shows that CeO 2 /TiO 2 The NTA electrode has excellent capacitance characteristic and high electrocatalytic oxidation-reduction activity.
And (3) testing: adopting a three-electrode linear volt-ampere test system and respectively adopting the prepared electrode CeO 2 /TiO 2 NTA electrode or other electrodes as working electrodesAnd a calomel electrode as a reference electrode, a platinum electrode as a counter electrode, a test electrolyte solution of 0.5mol/L sulfuric acid solution, a scanning speed of 5mV/min and a potential window of 0-4.0V vs. The test results are shown in fig. 6. CeO was obtained by analysis in FIG. 6 2 /TiO 2 The NTA electrode has a higher oxygen evolution potential (i.e., the potential corresponding to the coordinates where the diagonal of the LSV curve extends to the intersection with the X-axis), shown on the far right side of the graph, significantly higher than the other electrodes.
Example 2
The preparation method of the ceria-doped titanium nanotube electrode is the same as that of example 1. Electrochemical degradation the current density in this example was changed to 1mA/cm 2 Other reaction conditions were the same as those described in example 1. After reaction 2h, the AO7 degradation rate is 46.53 percent, and the COD degradation rate is 37.78 percent.
Example 3
The ceria-doped titanium nanotube electrode was prepared in the same manner as in example 1, except that the current density was changed to 2.5mA/cm 2 Other reaction conditions were the same as those described in example 1. The reaction 2h, AO7 degradation rate is 58.65%, COD degradation rate is 48.42%.
Example 4
The preparation method of the cerium oxide doped titanium nanotube electrode is the same as that of example 1, and the current density in this example is changed to 5mA/cm 2 The other reaction conditions were the same as described in example 1. After reaction 2h, the AO7 degradation rate is 76.87 percent, and the COD degradation rate is 61.37 percent.
Example 5
The preparation method of the cerium oxide doped titanium nanotube electrode is the same as that of example 1, and the current density in this example is changed to 20mA/cm 2 The other reaction conditions were the same as described in example 1. After reaction for 2h, the AO7 degradation rate is 94.28 percent, and the COD degradation rate is 84.21 percent.
Example 6
The ceria-doped titanium nanotube electrode was prepared in the same manner as in example 1, except that the electrolyte concentration was changed to 0.01mol/L and the reaction conditions were the same as in example 1. After reaction 2h, the AO7 degradation rate is 74.79 percent, and the COD degradation rate is 64.12 percent.
Example 7
The preparation method of the ceria-doped titanium nanotube electrode was the same as that of example 1, the electrolyte concentration in this example was changed to 0.025mol/L, and the other reaction conditions were the same as those described in example 1. After reaction for 2h, the AO7 degradation rate is 83.89%, and the COD degradation rate is 71.45%.
Example 8
The preparation method of the cerium oxide doped titanium nanotube electrode is the same as that of example 1, the electrolyte concentration in the example is changed to 0.075mol/L, and other reaction conditions are the same as those in example 1. The reaction 2h, AO7 degradation rate is 92.15%, COD degradation rate reaches 83.13%.
Example 9
The ceria-doped titanium nanotube electrode was prepared in the same manner as in example 1, except that the electrolyte concentration was changed to 0.1mol/L and the reaction conditions were the same as in example 1. After reaction for 2h, the AO7 degradation rate is 92.88 percent, and the COD degradation rate is 84.25 percent.
From examples 1 to 9, with reference to fig. 1 and fig. 2, it can be seen that the prepared ceria-doped titanium nanotube electrode has a good electrochemical oxidative degradation effect on acid orange 7 simulated dye wastewater, and it is found that electrochemical oxidative degradation parameters such as current density and electrolyte concentration have a large influence on the electrochemical oxidation process, and the influence of factors such as conductivity and competitive reaction is analyzed. Considering the economic factor and the degradation efficiency factor, the reaction cost is increased significantly due to the increase of the current density and the electrolyte concentration, and when the current density is more than 10mA/cm 2 And when the electrolyte concentration is more than 0.05mol/L, the AO7 degradation rate is hardly improved or the improvement range is very small, so that the optimal parameters of the electrochemical oxidation process are determined as follows: the optimal degradation current density is 10mA/cm 2 The optimum electrolyte concentration was 0.05mol/L sodium sulfate solution, which is the parameter in example 1.
Example 10
The preparation method of the cerium dioxide doped titanium nanotube electrode and the parameters of electrochemical oxidative degradation of AO7 simulated dye wastewater are the same as those in example 1. In order to measure the stability of the electrode, 7 times of degradation experiments of AO7 were repeated by using the electrode prepared in example 1 under the condition that other parameters were not changed, and the degradation rates of AO7 in the 7 times of experiments were 90.12, 89.99, 89.56, 89.29, 89.17, 88.26 and 87.97%, respectively, and the COD degradation rates were 82.18, 82.07, 82.00, 81.89, 81.58 and 81.40%, respectively.
According to the attached figure 3 and the AO7 degradation and COD degradation rates in the example 10, after 7 times of recycling, the electrode prepared by the invention still has good degradation effect on AO7 simulated dye wastewater, which shows that the electrode has good stability and good application potential in the actual wastewater treatment.
Comparative example 1
By adopting the method of example 1, the electrode preparation process only passes through (1), and does not carry out the steps (2), (3) and (4), the obtained electrode is a titanium sheet electrode, the electrode does not contain a titanium nanotube structure and does not contain cerium dioxide particles for doping, and the electrochemical oxidation degradation process is the same as that of example 1. After reaction for 2h, the degradation rate of AO7 reaches 10.15 percent, and the degradation rate of COD reaches 3.57 percent.
Comparative example 2
By adopting the method of the embodiment 1, the electrode preparation process only passes through the steps (1) and (4) without the steps (2) and (3), the obtained electrode is the ceria-doped Ti/CeO2 electrode, the electrode does not contain a titanium nanotube structure, and the electrochemical oxidation degradation process is the same as the embodiment 1. After reaction for 2h, the degradation rate of AO7 reaches 32.15 percent, and the degradation rate of COD reaches 22.57 percent.
Comparative example 3
By adopting the method of example 1, the electrode preparation process only passes (1) and (2), and does not carry out the steps (3) and (4), the obtained electrode is the titanium nanotube electrode, the electrode does not pass the anode stabilization process and does not contain cerium dioxide particle doping, and the electrochemical oxidation degradation process is the same as that of example 1. After reaction for 2h, the degradation rate of AO7 reaches 50.14 percent, and the COD degradation rate reaches 42.57 percent.
Comparative example 4
By adopting the method of example 1, the electrode preparation process only passes (1), (2) and (3) without the step (4), and the obtained electrode is the titanium dioxide nanotube electrode which is subjected to anode stabilization and is not subjected to electrodeposition, namely TiO 2 NTA electrode, electricityThe chemical oxidative degradation process was the same as in example 1. After reaction for 2h, the degradation rate of AO7 reaches 65.56 percent, and the COD degradation rate reaches 57.13 percent.
Comparative example 5
By adopting the method of example 1, the electrode preparation process only passes (1), (2) and (4), and step (3) is not carried out, and the obtained electrode is the cerium dioxide doped electrode which does not pass through the anode stabilization process, and the electrochemical oxidative degradation process is the same as that of example 1. After reaction for 2h, the degradation rate of AO7 reaches 71.15 percent, and the degradation rate of COD reaches 61.34 percent.
Comparative example 6
By adopting the method of the example 1, the electrode preparation process only passes through (1) and (2) without steps (3) and (4), and the obtained electrode is an unstable titanium dioxide nanotube electrode without electrodeposition and is named as Un-TiO 2 NTA electrode, electrochemical oxidation degradation process as in example 1. For determining the stability of the electrodes, the use of Un-TiO with unchanged other degradation parameters 2 The NTA electrode is repeatedly used for 7 times of AO7 degradation experiments, and the AO7 degradation rates in the 7 times of experiments are respectively 50.14, 45.15, 40.48, 33.47, 31.27, 30.18 and 21.18 percent, and the COD degradation rates are respectively 42.57, 35.25, 30.15, 25.45, 23.28 and 15.18 percent.
Comparative example 7
By adopting the method of the embodiment 1, the electrode preparation process only passes through the steps (1), (2) and (3) and does not pass through the step (4), and the obtained electrode is a titanium dioxide nanotube electrode which is subjected to anode stabilization and is not subjected to electrodeposition, namely TiO 2 NTA electrode, electrochemical oxidation degradation process as in example 1. For determining the stability of the electrodes, un-TiO was used without changing other degradation parameters 2 The NTA electrode is repeatedly used for 7 times of AO7 degradation experiments, and the AO7 degradation rates in the 7 times of experiments are 65.56, 64.32, 63.17, 62.52, 60.25, 58.17 and 56.15 percent respectively, and the COD degradation rates are 57.13, 56.25, 55.12, 54.27, 53.15 and 52.18 percent respectively.
Combining example 1 and comparative examples 1 to 5, it can be seen that steps (2), (3) and (4) proposed in the present invention can significantly improve the catalytic ability of the electrode, none of the four key steps of the electrode preparation can be replaced, and if no step is performed, the performance of the electrode can be significantly reduced. The purpose of step (2) isIn order to form a titanium nanotube structure on the surface of an electrode, the results of comparative examples 1 to 2 and example 1 show that the catalytic ability of the electrode suddenly decreases without the step (2), which proves the necessity of the step (2); the purpose of step (3) is mainly to stabilize the electrode, remove surface impurities and the like. It can be seen from comparative examples 6 to 7 that the stability of the electrode is significantly improved and the catalytic performance is also increased after the step (3). Electrodes not subjected to steps (3) and (4) in the production process, i.e. Un-TiO 2 The AO7 degradation rate and the COD degradation rate of the NTA electrode become significantly lower after multiple reactions, which indicates that TiO 2 The NTA electrode has poor stability, and the surface structure of the electrode is damaged after multiple reactions. The purpose of the step (4) is mainly to dope cerium dioxide nano particles, introduce oxygen vacancies and improve the catalytic activity and the stability of the electrode. In combination with example 1, comparative example 4 shows that the catalyst performance is significantly improved in step (4), and example 10 and comparative example 7 show that the electrode stability is improved after doping with the ceria nanoparticles.
Comparative example 8
The method of example 1 was adopted, the anode of step (2) was changed to be a boron-doped diamond electrode (BDD), and other reaction conditions were the same as those described in example 1, wherein the acid orange 7 simulated dye wastewater was electrochemically degraded. After reaction for 2h, the degradation rate of AO7 is 78.12%, and the degradation rate of COD is 71.03%. The AO7 degradation rate is shown in FIG. 4.
Comparative example 9
The method of example 1 was used, except that the anode in step (2) was Ti-based tin antimony (Ti/SnO) 2 -Sb 2 O 5 ) The electrode, other reaction conditions were the same as described in example 1 for electrochemical degradation of acid orange 7 mock dye wastewater. After reaction 2h, the AO7 degradation rate is 64.52 percent, and the COD degradation rate is 55.98 percent. The AO7 degradation rate is shown in FIG. 4.
Comparative example 10
The method of example 1 is adopted, and the anode in the step (2) is changed into titanium-based iridium tantalum ruthenium iridium (Ti/IrO) 2 -Ta 2 O 5 ) The electrode, other reaction conditions were the same as described in example 1 for electrochemical degradation of acid orange 7 mock dye wastewater. The reaction is 2h, the degradation rate of AO7 is 59.64 percent, and the degradation rate of COD is 51.98 percent. AOThe degradation rate of 7 is shown in figure 4.
Comparative example 11
Using the method of example 1, the anode of step (2) was changed to Ti-based ruthenium iridium (Ti/RuO) 2 -IrO 2 ) Electrode, other reaction conditions were the same as described in example 1 for electrochemically degrading acid orange 7 mock dye wastewater. In the reaction 2h, the AO7 degradation rate is 45.52 percent, and the COD degradation rate is 51.21 percent. The AO7 degradation rate is shown in FIG. 4.
Comparative example 12
The method of example 1 is adopted, the anode of step (2) is changed into a platinum sheet electrode (Ti/Pt), and other reaction conditions are the same as those described in example 1 for electrochemically degrading the acid orange 7 simulated dye wastewater. After reaction 2h, the AO7 degradation rate is 35.52 percent, and the COD degradation rate is 26.85 percent. The AO7 degradation rate is shown in FIG. 4.
From the example 1 and the comparative examples 8 to 12, and the attached figure 4, it can be seen that the electrode provided by the invention has the best degradation effect on AO7 simulated dye wastewater, the oxidation catalytic capability of the electrode exceeds that of various commercial electrodes on the market, and the performance of the electrode is superior to that of a boron-doped diamond electrode (an electrode with top performance recognized in the field) with excellent electrochemical oxidation performance recognized at present, which indicates that the electrochemical oxidation treatment dye wastewater field has good application prospects.
Comparative example 13
By adopting the method of example 1, the electrode preparation process only passes (1), (2) and (3) without the step (4), and the obtained electrode is the titanium dioxide nanotube electrode which is not subjected to electrodeposition after anode stabilization, namely TiO 2 NTA electrode. The three-electrode cyclic voltammetry test system of test 2 of example 1 was used, as TiO 2 NTA is a working electrode, a saturated calomel electrode is a reference electrode, a platinum electrode is a counter electrode, a test electrolyte solution is 0.05mol/L sodium sulfate solution, the scanning speed is 100mV/s, and a potential window is-0.5-1.5V vs. The test results are shown in FIG. 5.
Cyclic voltammetry analysis can be used to test the electrochemically active surface area of the electrodes. Example 1 and comparative example 13 referring to FIG. 5, tiO 2 The cyclic voltammogram of NTA shows a triangular shape, which is due to the higher potential of the anodeAnd resistance, resulting in higher current density in the electrolysis process. CeO (CeO) 2 The CV curve of the resulting electrode after doping was rectangular, indicating that CeO 2 /TiO 2 The NTA electrode has excellent capacitance characteristics, ceO 2 The doping increases the conductivity of the electrode, and has higher electrocatalytic oxidation-reduction activity and pollutant degradation potential.
Comparative example 14
The method of example 1 was adopted, the electrode preparation process was only (1), (2) and (3) without step (4), and the obtained electrode was a titanium dioxide nanotube electrode without electrodeposition after anode stabilization, i.e., tiO 2 NTA electrode. The three-electrode linear voltammetry test system in test 3 of example 1 was used, as was TiO 2 The NTA electrode is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, the test electrolyte solution is 0.5mol/L sulfuric acid solution, the scanning speed is 5mV/min, and the potential window is 0-4.0V vs. The test results are shown in FIG. 6.
Comparative example 15
Using the three-electrode linear voltammetry test system of test 3 of example 1, the commercial electrodes used in comparative examples 8-12, i.e., boron diamond electrode (BDD), titanium-based tin antimony (Ti/SnO) 2 -Sb 2 O 5 ) Titanium-based iridium tantalum ruthenium iridium (Ti/IrO) 2 -Ta 2 O 5 ) Titanium-based ruthenium-iridium (Ti/RuO) 2 -IrO 2 ) The test electrolyte solution is 0.5mol/L sulfuric acid solution, the scanning speed is 5mV/min, and the potential window is 0-4.0V vs. The test results are shown in FIG. 6.
Comparative examples 13 to 15 in conjunction with fig. 6, it can be seen that some side reactions occur during electrocatalytic oxidation, with the oxygen evolution side reaction being most pronounced. Generally, the more oxygen evolution side reactions that occur, the less current efficient the electrode for treating contaminants and the less electrocatalytic activity the electrode exhibits, and therefore electrodes for electrocatalytic oxidative degradation of contaminants are required to have a higher oxygen evolution potential, thereby reducing the occurrence of oxygen evolution side reactions. FIG. 6 shows CeO 2 /TiO 2 NTA、TiO 2 NTA and commercial electrodeBDD、Ti/SnO 2 -Sb 2 O 5 、Ti/IrO 2 -Ta 2 O 5 、Ti/RuO 2 -IrO 2 And the linear voltammetry curve of Ti/Pt, and CeO can be obtained by analyzing the graph 2 /TiO 2 The highest oxygen evolution potential of the NTA electrode is obviously higher than that of the TiO 2 NTA electrode and BDD electrode, significantly higher than other commercial electrodes. This indicates that CeO 2 /TiO 2 The NTA electrode has high electrocatalytic oxidation capacity and good pollutant degradation potential.
Example 11
The preparation process of example 1 was used, with the difference that:
preparing a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a molar ratio of 1 in the step (1), and etching the titanium sheet at 40 ℃. The anodic oxidation electrolyte in step (2) contains 0.1wt% of ammonium fluoride and 1wt% of H 2 A glycol solution of O; anodizing for 6h at 50V by using a constant voltage method. The reaction in the step (3) is carried out for 2 hours under the constant voltage of 50V; the high-temperature calcination is high-temperature calcination at 450 ℃ for 3 hours. The concentration of cerium ions in the electrodeposition solution in the step (4) is 1mmol/L; the potential of electrochemical deposition is 0.4V Vs.SCE, the reaction time is 30min, and the annealing calcination is carried out for 2h at 450 ℃. The electrochemical oxidative degradation process was the same as in example 1.
Example 12
The preparation method of example 1 was used, except that: preparing a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a molar ratio of 1. The anodic oxidation electrolyte in step (2) contains 0.75wt% of ammonium fluoride and 3wt% of H 2 A glycol solution of O; anodizing the glass tube by using a constant voltage method at 70V for 2h. The reaction in the step (3) under the constant voltage is a reaction for 1h under the constant voltage of 70V; the high-temperature calcination is high-temperature calcination at 800 ℃ for 2h. The concentration of cerium ions in the electrodeposition solution in the step (4) is 10mmol/L; the potential of the electrochemical deposition is 1.2V Vs.SCE, the reaction time is 5min, and the annealing calcination is carried out at 800 ℃ for 1h. The electrochemical oxidative degradation process was the same as in example 1.
Claims (10)
1. A preparation method of a cerium dioxide doped titanium nanotube electrode is characterized by comprising the following steps:
(1) Polishing a titanium plate, a titanium rod or a titanium net into a titanium sheet, and etching the titanium sheet by adopting a mixed solution of concentrated sulfuric acid and concentrated nitric acid; soaking the etched titanium sheet in ultrasonic wave, and drying to obtain an electrode anode;
(2) Taking the electrode obtained in the step (1) as an anode, taking a platinum sheet electrode as a cathode, preparing an anodic oxidation electrolyte, carrying out anodic oxidation, taking out the anode electrode after the reaction is finished, washing and drying;
(3) Taking the electrode obtained in the step (2) as an anode and a platinum sheet electrode as a cathode, reacting under constant voltage, and then calcining the obtained electrode at high temperature to obtain a titanium dioxide nanotube electrode, namely TiO 2 An NTA electrode;
(4) Preparing a solution containing one or two of cerium sulfate or cerium nitrate as an electrodeposition solution, performing constant-potential electrochemical deposition on the electrode obtained in the step (3) as a working electrode, a platinum sheet electrode as a reference electrode and a saturated calomel electrode as a counter electrode, and annealing and calcining the obtained electrode to obtain a cerium dioxide doped titanium nanotube electrode, namely a CeO 2 /TiO 2 NTA。
2. The preparation method of the cerium dioxide doped titanium nanotube electrode according to claim 1, wherein a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a molar ratio of 1.
3. The method of preparing a ceria-doped titanium nanotube electrode according to claim 1, wherein the anodic oxidation electrolyte in step (2) is 0.1-0.75wt% ammonium fluoride and 1-3wt% H 2 Glycol solution of O.
4. The method for preparing the cerium oxide-doped titanium nanotube electrode according to claim 1, wherein the anodic oxidation in the step (2) is performed by a constant voltage method at 50-70V for 2-6h.
5. The method for preparing the cerium oxide-doped titanium nanotube electrode according to claim 1, wherein the reaction at the constant voltage of the step (3) is a reaction at a constant voltage of 50 to 70V for 1 to 2 hours.
6. The method for preparing the cerium oxide-doped titanium nanotube electrode according to claim 1, wherein the high-temperature calcination of the step (3) is high-temperature calcination at 450 to 800 ℃ for 2 to 3 hours.
7. The method of preparing a ceria-doped titanium nanotube electrode according to claim 1, wherein the concentration of cerium ions in the electrodeposition solution of the step (4) is 1 to 10mmol/L.
8. The method for preparing the ceria-doped titanium nanotube electrode according to claim 1, wherein the potential of the electrochemical deposition in the step (4) is 0.4-1.2v vs.sce, the reaction time is 5-30min, and the annealing and calcination is performed at 450-800 ℃ for 1-2h.
9. Application of the cerium oxide doped titanium nanotube electrode prepared by the preparation method of claim 1 in electrochemical oxidative degradation of acid orange 7 dye wastewater.
10. The application according to claim 9, characterized in that the specific steps of the application are as follows: taking the waste water solution containing acid orange 7 as electrolyte, taking a ceric oxide-doped titanium nanotube electrode as an anode and a platinum sheet electrode as a cathode, and carrying out degradation treatment under constant current density of 1-20 mA/cm 2 The electrolyte is 0.01-0.1 mol/L sodium sulfate, the stirring speed is 500-1000r/min, and the reaction time is 1-2h.
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| LE THI THANH TUYEN 等: "Synthesis of CeO2TiO2 nanotubes and heterogeneous photocatalytic degradation of methylene blue", JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING, pages 5999 - 6011 * |
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