CN111547822B - High-catalytic-activity electrode and method for photoelectrocatalytic degradation of active red 195 by using same - Google Patents
High-catalytic-activity electrode and method for photoelectrocatalytic degradation of active red 195 by using same Download PDFInfo
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Abstract
The invention discloses a high catalytic activity electrode and a method for degrading active red 195 through photoelectrocatalysis thereof, belonging to the technical field of photoelectrocatalysis. The electrode is prepared as follows: preparation of Ti/TiO by anodic oxidation 2 NT is reduced and then calcined in nitrogen atmosphere to prepare black Ti/TiO 2 NT(Ti/Black‑TiO 2 NT), and depositing Ni on Ti/Black-TiO by adopting a pulse current deposition method 2 On NT to obtain Ti/Black-TiO 2 NT/Ni, subsequently microwave synthesized on Ti/Black-TiO 2 MOF material ZIF-9 particles are loaded on NT/Ni to obtain Ti/Black-TiO 2 NT/Ni/ZIF-9 electrode. The method for degrading the active red 195 by adopting the electrode comprises the steps of taking the electrode as an anode, taking a copper electrode as a cathode, adopting a constant-current constant-voltage power supply, adopting a 500W xenon lamp as a light source, controlling the temperature to be 25 ℃ and the current density to be 50mA/m 2 The degradation liquid is: 10mg/L active red 195, Ti/Black-TiO prepared by the invention 2 The NT/Ni/ZIF-9 electrode has good electrode stability, and high catalytic efficiency when being used in the process of degrading dye active red 195.
Description
Technical Field
The invention belongs to the technical field of photoelectrocatalysis, and particularly relates to a high-catalytic-activity electrode and a method for photoelectrocatalysis degradation of active red 195 by the high-catalytic-activity electrode.
Background
Dyeing is the most important source of environmental pollution in the textile industry. These processes require large amounts of water and therefore produce large amounts of waste water. It is estimated that 10-15% of the dye is lost during dyeing and is discharged as waste liquid, causing serious pollution to the environment. Reactive red 195 is one of the organic dyes widely used for cotton dyeing and printing. The dye wastewater is common organic wastewater in industry, and has high BOD and COD, high chromaticity, complex chemical structure and biological toxicity of partial dye. It is difficult to completely remove them by conventional biochemical methods. The advanced oxidation technology (AOP) treatment by light, electrocatalytic oxidation and the like is one of the research hotspots of the current dye wastewater treatment technology. The photoelectrocatalysis oxidation technology has the advantages of simple and convenient operation, high degradation efficiency, good environmental compatibility and the like. Photoelectrode materials and catalytic materials are important determinants in photoelectrochemical processes and will directly affect the efficiency and energy consumption of photoelectrochemical processes. Therefore, the search and the research of the anode material with high catalytic activity and long service life are very important.
TiO 2 Is one of the most widely used photocatalytic materials because it has excellent ability to oxidatively decompose organic pollutants, has corrosion resistance, is non-toxic and low-cost, and many studies have been focused on synthesizing TiO having various structures 2 (e.g., nanotube arrays, nanorods, nanowires), wherein the TiO is highly ordered 2 The nanotube array is vertically erected on a Ti substrate, has an ideal form for promoting photocatalytic efficiency, and is combined with other TiO 2 The improved structure provides a shorter carrier diffusion path, i.e., along the tube wall, thereby minimizing charge loss due to electron hopping between nanoparticles, and the nanotubes formed from the Ti substrate can also be used as electrodes, which can achieve high photocatalytic efficiency when a small electrical potential is applied, compared to the stand-alone nanotubes. Most studied TiO 2 The nanotubes are of anatase and rutile structure [6] The anatase structure has a higher photocatalytic activity than the rutile form.
But TiO2 2 The forbidden band width of the crystal is 3.2eV, and the TiO is limited 2 Nanotube ofTo a wider range of applications. TiO due to its large band gap width 2 Nanotubes require UV light irradiation for photocatalysis, which accounts for only a small fraction (5%) of the solar spectrum compared to visible light (52%) and infrared light (43%), and furthermore, the rapid recombination of photogenerated electron-hole pairs also affects TiO 2 One factor in the photocatalytic efficiency of nanotubes, and therefore both of these drawbacks must be addressed to enhance TiO enhancement 2 Photocatalytic activity of the nanotubes.
In recent years, metal-organic framework Materials (MOFs) have attracted the attention of many scholars, and Zeolitic imidazole-like framework materials (Zeolitic imidazole frameworks ZIFs) are novel metal-organic framework coordination polymers having a zeolite topology, which combine the advantages of both zeolite and metal-organic framework materials, and have large specific surface area and high stability. Co-ZIF-9 is a zeolite-like structure novel material synthesized by taking Co as a metal node and benzimidazole as an organic ligand in an organic solvent DMF through a solvothermal method. TiO2 2 Combined with metal-organic framework Materials (MOFs), the specific surface area can be increased, more active sites are provided, and the photoelectrocatalytic activity is improved.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the defects of the prior art, provides a high-catalytic-activity electrode and a method for preparing Ti/Black-TiO 195 by a microwave method through photoelectrocatalytic degradation of the high-catalytic-activity electrode 2 Compared with other methods, the NT/Ni/ZIF-9 electrode is simple to operate, improves the purity, density and uniformity of a deposited layer, reduces the void ratio, improves the stability and the photoelectric catalytic performance of the electrode, and is prepared from the Ti/Black-TiO 2 The method provided by the invention has the advantages that the efficiency of removing the active red 195 by oxidative degradation is high, the electrode corrosion resistance is good, the stability of the degradation process is good, the degradation efficiency is higher than that of a common titanium dioxide nanotube electrode, the decolorization rate of the active red 195 reaches 99.1-99.9%, the degradation rate of COD reaches 95.8-97.2%, the degradation side reaction is less, and the degradation efficiency is guaranteed to be high, so that the degradation is less, and the method has the advantages of high efficiency and low costRate, belonging to the green chemical moiety.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to a high catalytic activity electrode, which adopts an anodic oxidation method to prepare Ti/TiO 2 NT is reduced and then calcined in nitrogen atmosphere to prepare black Ti/TiO 2 NT(Ti/Black-TiO 2 NT), and depositing Ni on Ti/Black-TiO by adopting a pulse current deposition method 2 On NT to obtain Ti/Black-TiO 2 NT/Ni, subsequently microwave synthesized on Ti/Black-TiO 2 MOF material ZIF-9 particles are loaded on NT/Ni to obtain Ti/Black-TiO 2 NT/Ni/ZIF-9 electrode.
As a further improvement of the invention, the preparation method comprises the following specific steps:
the first step,
Selecting pure titanium metal as a titanium sheet, firstly polishing the titanium sheet by three different specifications of 600 meshes, 800 meshes and 1000 meshes of abrasive paper in sequence, then ultrasonically washing the polished titanium sheet in absolute ethyl alcohol, acetone and deionized water for 10min in sequence, then putting the titanium sheet into a mixed solution of ethylene glycol, hydrofluoric acid and secondary distilled water for corrosion treatment for 20min, wherein the surface of the corroded titanium sheet is a white pitted surface, and cleaning the corroded titanium sheet by using deionized water, wherein: hydrofluoric acid, wherein the volume ratio of the ethylene glycol to the secondary distilled water is 2: 6: 10;
step two,
Preparing Ti/TiO by anode oxidation method 2 NT, 0.3-0.5 wt% NH and 2-5V% H at room temperature 2 In O glycol electrolyte, a Ti sheet is used as an anode, a Cu sheet is used as a cathode, anodic electrooxidation is carried out, the oxidation voltage is 60-100V, the oxidation time is 7-10 h, magnetic stirring is carried out all the time in the oxidation process, a sample is soaked in absolute ethyl alcohol for 2h after the oxidation is finished, the absolute ethyl alcohol is used for carrying out ultrasonic cleaning for 2min, and then the temperature is controlled to be 2-4 mol.L -1 Na 2 SO 4 To Ti/TiO in solution 2 Reduction of NT electrode to obtain Ti 4+ Reduction to Ti 3+ Finally, annealing treatment is carried out in nitrogen atmosphere, the annealing temperature is 500-550 ℃, and heat preservation is carried out for 4 hours, thus obtaining the Ti/Black-TiO 2 An NT electrode;
step three,
Annealing the Ti/Black-TiO annealed in the second step 2 The NT electrode is used as a working electrode, the Pt sheet is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, and the electrode is placed in NiSO mixed with 200-400 g/L 4 ·6H 2 O, NiCl of 20-41 g/L 2 ·6H 2 O and 10-32 g/L H 3 BO 3 In the electroplating solution, the temperature is controlled to be 25 ℃, the stirring speed is 600rpm, and Ni is modified on the nanotube by pulse electrodeposition for 10min to prepare Ti/Black-TiO 2 NT/Ni electrode;
step four,
0.1-0.7 g Co (NO) 3 ) 2 And 0.5-0.8 g of benzimidazole is dissolved in 10-40 ml of N, N-dimethylformamide, and the Ti/Black-TiO is added 2 Putting NT/Ni into the solution, then putting the solution into a microwave reactor for reaction for 10-20 min at the reaction temperature of 200-230 ℃, taking out the solution after the reaction is finished, washing the solution for several times by using DMF (dimethyl formamide), and then putting the solution into a vacuum drying oven at the temperature of 90 ℃ for drying overnight to obtain the Ti/Black-TiO further modified by the MOF material 2 NT/Ni/ZIF-9 electrodes.
The invention relates to a method for degrading active red 195 by high catalytic activity electrode photoelectrocatalysis, which comprises the following steps:
1) preparation of highly catalytically active electrodes
Preparation of Ti/TiO by anodic oxidation 2 NT is reduced and then calcined in nitrogen atmosphere to prepare black Ti/TiO 2 NT(Ti/Black-TiO 2 NT), then adopting a pulse current deposition method to deposit Ni on Ti/Black-TiO 2 On NT to obtain Ti/Black-TiO 2 NT/Ni, subsequently microwave synthesized on Ti/Black-TiO 2 MOF material ZIF-9 particles are loaded on NT/Ni to obtain Ti/Black-TiO 2 NT/Ni/ZIF-9 electrode;
2) photoelectrocatalysis degradation active red 195
The Ti/Black-TiO with high catalytic activity prepared in the step 1) 2 The NT/Ni/ZIF-9 electrode is used as an anode, the copper electrode is used as a cathode, a constant-current constant-voltage power supply is adopted, a 500W xenon lamp is adopted as a light source, the temperature is 25 ℃, and the current density is 50mA/m 2 The degradation liquid is:10mg/L active Red 195.
As a further improvement of the invention, the Ti/Black-TiO with high catalytic activity is prepared in the step 1) 2 The specific steps of the NT/Ni/ZIF-9 electrode are as follows:
the first step,
Selecting pure titanium metal as a titanium sheet, firstly polishing the titanium sheet by three different specifications of 600 meshes, 800 meshes and 1000 meshes of abrasive paper in sequence, then ultrasonically washing the polished titanium sheet in absolute ethyl alcohol, acetone and deionized water for 10min in sequence, then putting the titanium sheet into a mixed solution of ethylene glycol, hydrofluoric acid and secondary distilled water for corrosion treatment for 20min, wherein the surface of the corroded titanium sheet is a white pitted surface, and cleaning the corroded titanium sheet by using deionized water, wherein: hydrofluoric acid, wherein the volume ratio of the ethylene glycol to the secondary distilled water is 2: 6: 10;
step two,
Preparing Ti/TiO by anode oxidation method 2 NT, 0.3-0.5 wt% NH and 2-5V% H at room temperature 2 In O glycol electrolyte, a Ti sheet is used as an anode, a Cu sheet is used as a cathode, anodic electrooxidation is carried out, the oxidation voltage is 60-100V, the oxidation time is 7-10 h, magnetic stirring is carried out all the time in the oxidation process, a sample is soaked in absolute ethyl alcohol for 2h after the oxidation is finished, the absolute ethyl alcohol is used for carrying out ultrasonic cleaning for 2min, and then the temperature is controlled to be 2-4 mol.L -1 Na 2 SO 4 To Ti/TiO in solution 2 Reduction of NT electrode to obtain Ti 4+ Reduction to Ti 3+ Finally, annealing treatment is carried out in the nitrogen atmosphere, the annealing temperature is 500-550 ℃, and heat preservation is carried out for 4 hours, so that the Ti/Black-TiO can be prepared 2 An NT electrode;
step three,
Annealing the Ti/Black-TiO annealed in the second step 2 The NT electrode is used as a working electrode, the Pt sheet is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, and the electrode is placed in NiSO mixed with 200-400 g/L 4 ·6H 2 O, NiCl of 20-41 g/L 2 ·6H 2 O and 10-32 g/L H 3 BO 3 In the electroplating solution, the temperature is controlled to be 25 ℃, the stirring speed is 600rpm, and Ni is modified on the nanotube by pulse electrodeposition for 10min to prepare Ti/Black-TiO 2 NT/Ni electrode;
step four,
0.1-0.7 g Co (NO) 3 ) 2 And 0.5-0.8 g of benzimidazole is dissolved in 10-40 ml of N, N-dimethylformamide, and the Ti/Black-TiO is added 2 Putting NT/Ni into the solution, then putting the solution into a microwave reactor for reaction for 10-20 min at the reaction temperature of 200-230 ℃, taking out the solution after the reaction is finished, washing the solution for several times by using DMF (dimethyl formamide), and then putting the solution into a vacuum drying oven at the temperature of 90 ℃ for drying overnight to obtain the Ti/Black-TiO further modified by the MOF material 2 NT/Ni/ZIF-9 electrode.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) the high catalytic activity electrode can improve Ti/Black-TiO content by doping metal Ni through pulse electrodeposition 2 The conductivity of NT/Ni/ZIF-9, and part of Ni is oxidized into NiO during the electroplating process, and the NiO can be mixed with TiO 2 Further forming p-n semiconductor heterojunction, thereby improving Ti/Black-TiO 2 NT photocatalytic activity.
(2) The ZIF-9 of the high catalytic activity electrode has high photoelectrocatalysis activity and high specific surface area, and the ZIF-9 modified Ti/Black-TiO is prepared by a microwave synthesis technology 2 The NT/Ni electrode is simple to operate, the prepared ZIF-9 particles are small (nano-scale) and uniform in size, the catalytic activity is high, and meanwhile, the microwave method can improve the purity, density and uniformity of a ZIF-9 deposition layer and reduce the void ratio of the ZIF-9 deposition layer, so that the stability and the photoelectrocatalysis performance of the composite electrode are further improved.
(3) The method for photoelectrocatalytic degradation of active red 195 by the high-catalytic-activity electrode has the advantages of simple electrode preparation, simple operation, easy equipment acquisition, simple process flow, low investment cost, good degradation effect of the active red 195, good electrode corrosion resistance, good degradation process stability, higher degradation efficiency than that of a common titanium dioxide nanotube electrode, 99.1-99.9% of the decolorization rate of the active red 195 and 95.8-97.2% of the degradation rate of COD.
Detailed Description
For a further understanding of the present invention, reference will now be made in detail to the following examples.
Example 1
The method for photocatalytically degrading active red 195 by the high-catalytic-activity electrode comprises the following specific steps:
the first step,
Selecting pure titanium metal as a titanium sheet, firstly polishing the titanium sheet by three different specifications of 600 meshes, 800 meshes and 1000 meshes of abrasive paper in sequence, then ultrasonically washing the polished titanium sheet in absolute ethyl alcohol, acetone and deionized water for 10min in sequence, then putting the titanium sheet into a mixed solution of ethylene glycol, hydrofluoric acid and secondary distilled water for corrosion treatment for 20min, wherein the surface of the corroded titanium sheet is a white pitted surface, and cleaning the corroded titanium sheet by using deionized water, wherein: hydrofluoric acid, wherein the volume ratio of the ethylene glycol to the secondary distilled water is 2: 6: 10;
step two,
Preparing Ti/TiO by anode oxidation method 2 NT, 0.3 wt% NH and 2V% H at room temperature 2 In O glycol electrolyte, a Ti sheet is taken as an anode, a Cu sheet is taken as a cathode, anodic electrooxidation is carried out, the oxidation voltage is 60V, the oxidation time is 7h, magnetic stirring is always carried out in the oxidation process, the sample is soaked in absolute ethyl alcohol for 2h after the oxidation is finished, the absolute ethyl alcohol is used for carrying out ultrasonic cleaning for 2min, and then the solution is subjected to 2 mol.L -1 Na 2 SO 4 To Ti/TiO in solution 2 Reduction of NT electrode by first reducing Ti 4+ Reduction to Ti 3+ Finally annealing treatment is carried out in nitrogen atmosphere, the annealing temperature is 500 ℃, and the heat preservation is carried out for 4 hours, thus obtaining the Ti/Black-TiO 2 An NT electrode;
step three,
The Ti/Black-TiO annealed in the second step 2 NT electrode as working electrode, Pt sheet as counter electrode, saturated calomel electrode as reference electrode, placed in NiSO mixed with 200g/L 4 ·6H 2 O, 20g/L NiCl 2 ·6H 2 O and 10g/L of H 3 BO 3 In the electroplating solution, the temperature is controlled to be 25 ℃, the stirring speed is 600rpm, and Ni is modified on the nanotube by pulse electrodeposition for 10min to prepare Ti/Black-TiO 2 NT/Ni electrode;
step four,
0.1g of Co (NO) 3 ) 2 And 0.5g benzimidazole in 10ml N, N-dimethylformamide, and adding Ti/Black-TiO 2 Putting NT/Ni into the solution, then putting the solution into a microwave reactor for reaction for 10min at the reaction temperature of 200 ℃, taking the solution out after the reaction is finished, washing the solution with DMF for several times, and then putting the solution into a vacuum drying oven at the temperature of 90 ℃ for drying overnight to obtain the Ti/Black-TiO further modified by the MOF material 2 NT/Ni/ZIF-9 electrode. It should be noted that: the nano-sized ZIF-9 particles can be obtained by microwave synthesis, and meanwhile, the ZIF-9 particles can be uniformly distributed on Ti/Black-TiO 2 NT/Ni electrode.
Step five,
The Ti/Black-TiO prepared in the fourth step 2 The NT/Ni/ZIF-9 electrode is used as an anode, the copper electrode is used as a cathode, a constant-current constant-voltage power supply is adopted, a 500W xenon lamp is adopted as a light source, the temperature is 25 ℃, and the current density is 50mA/m 2 The degradation liquid is: 10mg/L active Red 195. After the photoelectric degradation process, the decolorization rate of the active red 195 reaches 99.5 percent, and the degradation rate of COD reaches 96.8 percent.
Example 2
The method for photocatalytically degrading active red 195 by the high-catalytic-activity electrode comprises the following specific steps:
the first step,
Selecting pure titanium metal as a titanium sheet, firstly polishing the titanium sheet by three different specifications of 600 meshes, 800 meshes and 1000 meshes of abrasive paper in sequence, then ultrasonically washing the polished titanium sheet in absolute ethyl alcohol, acetone and deionized water for 10min in sequence, then putting the titanium sheet into a mixed solution of ethylene glycol, hydrofluoric acid and secondary distilled water for corrosion treatment for 20min, and cleaning the surface of the corroded titanium sheet by using deionized water, wherein: hydrofluoric acid, wherein the volume ratio of ethylene glycol to secondary distilled water is 2: 6: 10;
step two,
Preparation of Ti/TiO by anodic oxidation 2 NT, 0.4 wt% NH and 4V% H at room temperature 2 In the glycol electrolyte of O, Ti sheet is used as anode and Cu sheet is used as cathode to make anodic electrooxidation, oxidation voltageThe oxidation time is 8h, magnetic stirring is carried out all the time in the oxidation process, the sample is soaked in absolute ethyl alcohol for 2h after the oxidation is finished, the absolute ethyl alcohol is subjected to ultrasonic cleaning for 2min, and then the temperature is controlled to be 3 mol.L -1 Na 2 SO 4 To Ti/TiO in solution 2 Reduction of NT electrode to obtain Ti 4+ Reduction to Ti 3+ Finally annealing treatment is carried out in nitrogen atmosphere, the annealing temperature is 530 ℃, and heat preservation is carried out for 4 hours, thus obtaining the Ti/Black-TiO 2 An NT electrode;
step three,
Annealing the Ti/Black-TiO annealed in the second step 2 NT electrode as working electrode, Pt sheet as counter electrode, saturated calomel electrode as reference electrode, placing in NiSO mixed with 300g/L 4 ·6H 2 O, 30g/L NiCl 2 ·6H 2 O and 25g/L of H 3 BO 3 In the electroplating solution, the temperature is controlled to be 25 ℃, the stirring speed is 600rpm, and Ni is modified on the nanotube by pulse electrodeposition for 10min to prepare Ti/Black-TiO 2 NT/Ni electrode;
step four,
0.5g of Co (NO) 3 ) 2 And 0.7g benzimidazole in 30ml N, N-dimethylformamide and adding Ti/Black-TiO 2 Putting NT/Ni into the solution, then putting the solution into a microwave reactor for reaction for 15min, wherein the reaction temperature is 210 ℃, taking out the solution after the reaction is finished, washing the solution with DMF for several times, and then putting the solution into a vacuum drying oven at the temperature of 90 ℃ for drying overnight to obtain the Ti/Black-TiO further modified by the MOF material 2 NT/Ni/ZIF-9 electrode.
Step five,
The Ti/Black-TiO prepared in the fourth step 2 The NT/Ni/ZIF-9 electrode is used as an anode, the copper electrode is used as a cathode, a constant-current constant-voltage power supply is adopted, a 500W xenon lamp is adopted as a light source, the temperature is 25 ℃, and the current density is 50mA/m 2 The degradation liquid is: 10mg/L active Red 195. After the photoelectric degradation process, the decolorization rate of the active red 195 reaches 99.9 percent, and the degradation rate of COD reaches 97.2 percent.
Example 3
The method for photocatalytically degrading active red 195 by the high-catalytic-activity electrode comprises the following specific steps:
the first step,
Selecting pure titanium metal as a titanium sheet, firstly polishing the titanium sheet by three different specifications of 600 meshes, 800 meshes and 1000 meshes of abrasive paper in sequence, then ultrasonically washing the polished titanium sheet in absolute ethyl alcohol, acetone and deionized water for 10min in sequence, then putting the titanium sheet into a mixed solution of ethylene glycol, hydrofluoric acid and secondary distilled water for corrosion treatment for 20min, wherein the surface of the corroded titanium sheet is a white pitted surface, and cleaning the corroded titanium sheet by using deionized water, wherein: hydrofluoric acid, wherein the volume ratio of the ethylene glycol to the secondary distilled water is 2: 6: 10;
step two,
Preparing Ti/TiO by anode oxidation method 2 NT, 0.5wt% NH and 5V% H at room temperature 2 In O glycol electrolyte, a Ti sheet is taken as an anode, a Cu sheet is taken as a cathode, anodic electrooxidation is carried out, the oxidation voltage is 100V, the oxidation time is 10h, magnetic stirring is carried out all the time in the oxidation process, the sample is soaked in absolute ethyl alcohol for 2h after the oxidation is finished, the absolute ethyl alcohol is used for carrying out ultrasonic cleaning for 2min, and then the solution is subjected to 4 mol.L -1 Na 2 SO 4 To Ti/TiO in solution 2 Reduction of NT electrode to obtain Ti 4+ Reduction to Ti 3+ Finally annealing treatment is carried out in nitrogen atmosphere, the annealing temperature is 550 ℃, and heat preservation is carried out for 4 hours, thus obtaining the Ti/Black-TiO 2 An NT electrode;
step three,
Annealing the Ti/Black-TiO annealed in the second step 2 NT electrode as working electrode, Pt sheet as counter electrode, saturated calomel electrode as reference electrode, placed in NiSO mixed with 400g/L 4 ·6H 2 O, 41g/L NiCl 2 ·6H 2 O and 32g/L of H 3 BO 3 In the electroplating solution, the temperature is controlled to be 25 ℃, the stirring speed is 600rpm, and Ni is modified on the nanotube by pulse electrodeposition for 10min to prepare Ti/Black-TiO 2 NT/Ni electrode;
step four,
0.7g of Co (NO) 3 ) 2 And 0.8g benzimidazole in 40ml N, N-dimethylformamide and adding Ti/Black-TiO 2 NT/Ni is put into the solution and then put into a microwave reactor for reaction for 20min at the reaction temperature of 230 ℃, and the reaction is finishedThen taking out and washing with DMF for several times, and then putting the mixture into a vacuum drying oven at 90 ℃ for drying overnight to obtain the Ti/Black-TiO further modified by the MOF material 2 NT/Ni/ZIF-9 electrode.
Step five,
The Ti/Black-TiO prepared in the fourth step 2 The NT/Ni/ZIF-9 electrode is used as an anode, the copper electrode is used as a cathode, a constant-current constant-voltage power supply is adopted, a 500W xenon lamp is adopted as a light source, the temperature is 25 ℃, and the current density is 50mA/m 2 The degradation liquid is: 10mg/L active Red 195. After the photoelectric degradation process, the decolorization rate of the active red 195 reaches 99.1 percent, and the degradation rate of COD reaches 95.8 percent.
The high catalytic activity electrode can improve Ti/Black-TiO content by doping metal Ni through pulse electrodeposition 2 The conductivity of NT/Ni/ZIF-9, and part of Ni is oxidized into NiO during the electroplating process, and the NiO can be mixed with TiO 2 Further forming p-n semiconductor heterojunction, thereby improving Ti/Black-TiO 2 NT photocatalytic activity. The ZIF-9 has high photoelectrocatalysis activity and high specific surface area, the ZIF-9 modified Ti/Black-TiO2NT/Ni electrode is prepared by a microwave synthesis technology, the operation is simple, the prepared ZIF-9 has small (nano) particles, uniform size and high catalytic activity, and meanwhile, the microwave method can also improve the purity, density and uniformity of a ZIF-9 deposition layer and reduce the porosity of the ZIF-9 deposition layer, so that the stability and the photoelectrocatalysis performance of the composite electrode are further improved.
Modified Ti/Black-TiO by doping in examples 1-3 2 The method provided by the invention has the advantages that the efficiency of removing the active red 195 through oxidative degradation is high, the corrosion resistance of the electrode is good, the stability of the degradation process is good, the degradation efficiency is higher than that of a common titanium dioxide nanotube electrode, the decolorization rate of the active red 195 reaches 99.1-99.9%, the degradation rate of COD reaches 95.8-97.2%, the degradation side reaction is less, the energy consumption is low, and the method belongs to a green chemical part.
The above examples are only intended to illustrate the technical solution of the present invention and are not intended to be limiting. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention.
Claims (2)
1. A high catalytic activity electrode is characterized in that Ti/TiO2NT is prepared by an anodic oxidation method, and is reduced firstly,
calcining in nitrogen atmosphere to obtain Black Ti/Black-TiO2NT, and depositing Ni by pulse current deposition
Depositing on Ti/Black-TiO2NT to obtain Ti/Black-TiO2NT/Ni, and microwave synthesizing on Ti/Black-TiO2NT/Ni
MOF material ZIF-9 particles are loaded on the substrate to obtain a Ti/Black-TiO2NT/Ni/ZIF-9 electrode;
wherein the preparation method comprises the following specific steps:
the first step,
Selecting pure titanium metal as a titanium sheet, and firstly using three kinds of sands with different specifications of 600 meshes, 800 meshes and 1000 meshes for the titanium sheet in sequence
Polishing paper, then ultrasonically washing the polished titanium sheet in absolute ethyl alcohol, acetone and deionized water for 10min in sequence, and then cleaning the titanium sheet
Placing into mixed solution of ethylene glycol, hydrofluoric acid and secondary distilled water for corrosion treatment for 20min, wherein the surface of the corroded titanium sheet is white
And (3) pitting and cleaning with deionized water, wherein: hydrofluoric acid, wherein the volume ratio of the ethylene glycol to the secondary distilled water is 2: 6: 10;
step two,
Preparing Ti/TiO2NT by an anodic oxidation method at room temperature with the mass fraction of 0.3-0.5 wt% of NH and 2-5V% of H2O
In the ethylene glycol electrolyte, a Ti sheet is taken as an anode, a Cu sheet is taken as a cathode, anodic electrooxidation is carried out, the oxidation voltage is 60-100V,
the oxidation time is 7-10 h, magnetic stirring is carried out all the time in the oxidation process, the sample is soaked in absolute ethyl alcohol for 2h after the oxidation is finished, and absolute ethyl alcohol
Alcohol ultrasonic cleaning for 2min, reducing the Ti/TiO2NT electrode in 2-4 mol.L-1 Na2SO4 solution, and reducing Ti4+ into
Ti3+, finally annealing in nitrogen atmosphere at 500-550 ℃, and keeping the temperature for 4h to obtain Ti/Black-TiO2NT
An electrode;
step three,
Taking the Ti/Black-TiO2NT electrode annealed in the second step as a working electrode, taking a Pt sheet as a counter electrode and taking a saturated calomel electrode
As reference electrodes, the reference electrodes are placed on NiCl 2.6H2O mixed with 200-400 g/L of NiSO 4.6H2O, 20-41 g/L of NiCl 2.6H2O and 10-32 g/L
The plating solution of H3BO3 (9) is prepared by controlling the temperature at 25 ℃, the stirring speed at 600rpm, and performing pulse electrodeposition for 10min to repair Ni
Decorating on the nanotube to obtain a Ti/Black-TiO2NT/Ni electrode;
step four,
Dissolving 0.1-0.7 g Co (NO3)2 and 0.5-0.8 g benzimidazole in 10-40 ml N, N-dimethylformamide
Putting Ti/Black-TiO2NT/Ni into the solution, and then putting the solution into a microwave reactor for reaction for 10-20 min at the reaction temperature of
Taking out the mixture after the reaction is finished and washing the mixture for several times by using DMF (dimethyl formamide), then putting the mixture into a vacuum drying oven at the temperature of 90 ℃ for drying overnight,
then the Ti/Black-TiO2NT/Ni/ZIF-9 electrode with further modified MOF material is obtained.
2. The method for photoelectrocatalytic degradation of active red 195 by using the electrode with high catalytic activity as claimed in claim 1, wherein the electrode with high catalytic activity is used for photoelectrocatalytic degradation of active red 195
The method comprises the following steps:
1) preparation of highly catalytically active electrodes
Preparing Ti/TiO2NT by adopting an anodic oxidation method, reducing, calcining in a nitrogen atmosphere, preparing Black Ti/Black-TiO2NT, depositing Ni on Ti/Black-TiO2NT by adopting a pulse current deposition method to obtain Ti/Black-TiO2NT/Ni, and then loading MOF material ZIF-9 particles on Ti/Black-TiO2NT/Ni by microwave synthesis to obtain a Ti/Black-TiO2NT/Ni/ZIF-9 electrode;
2) photoelectrocatalysis degradation active red 195
Taking the Ti/Black-TiO2NT/Ni/ZIF-9 electrode with high catalytic activity prepared in the step 1) as an anode and a copper electrode as a cathode, adopting a constant-current constant-voltage power supply, adopting a 500W xenon lamp as a light source, controlling the temperature at 25 ℃ and the current density at 50mA/m2, and obtaining a degradation liquid: 10mg/L active Red 195.
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| Co-ZIF-9-TiO2纳米的制备及其CO2光还原性能研究;闫神锁;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20180630;第34、49-50页 * |
| Preparation and characterization of a novel Ce doped PbO2 electrode based on NiO modified Ti/TiO2NTs substrate for the electrocatalytic degradation of phenol wastewater;Zhicheng Wang等;《Electrochimica Acta》;20170710;第535页摘要、第536页第2.1节、第537-540页第2.2-2.3节，第541-546页第3.1-3.4节、第4节 * |
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