CN112250229A - Preparation method and application of electrode with high catalytic activity and stability - Google Patents

Preparation method and application of electrode with high catalytic activity and stability Download PDF

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CN112250229A
CN112250229A CN202011137031.3A CN202011137031A CN112250229A CN 112250229 A CN112250229 A CN 112250229A CN 202011137031 A CN202011137031 A CN 202011137031A CN 112250229 A CN112250229 A CN 112250229A
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electrode
zro
tio
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徐迈
王凤武
王佳奕
方文彦
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Huainan Normal University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols

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Abstract

The invention relates to a preparation method and application of an electrode with high catalytic activity and stability, which comprises the following preparation steps: step 1, pretreating a titanium sheet; step 2, preparing Ti/TiO2An NT electrode; step 3, in (NH)4)2SO4To Ti/TiO in solution2Reducing the NT electrode; step 4, preparing UiO-66 powder as a precursor; step 5, preparing ZrO2-C nanoparticles; step 6, adding a certain amount of ZrO into the electrolyte containing lead nitrate and nitric acid2-C nanoparticles, on Ti/TiO2Performing direct current deposition on the NT electrode to obtain ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2‑C/PbO2The electrode, the preparation method of the electrode with high catalytic activity and stability and the product obtained by applying the electrode provided by the invention can improve the density and the uniformity of a deposited layer and reduce PbO2Void fraction of crystal grainsAnd the specific surface area and the number of active sites of the electrode are increased, the electrocatalysis performance of the electrode is improved, the corrosion resistance of the electrode is higher, the stability of the degradation process is better, and the degradation efficiency is higher than that of a common lead electrode.

Description

Preparation method and application of electrode with high catalytic activity and stability
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a preparation method and application of an electrode with high catalytic activity and stability.
Background
2,4, 6-trinitrobenzenePhenol, also known as picric acid, belongs to nitrophenol compounds, can be used for manufacturing high-strength and strong-toxicity explosives, and is commonly used in chemical industries such as dye, glass, rubber, medicine and the like, 2,4, 6-trinitrophenol not only has potential explosion threat, but also easily causes environmental pollution and health problems, so that the 2,4, 6-trinitrophenol is quickly and effectively removed from industrial sewage, and the electrochemical oxidation method has important significance for environmental protection, water and soil resource cleaning and health promotion, namely, in the electrolytic process, organic pollutants are directly oxidized on the surface of an electrode material with electrocatalytic performance, or the electrode material generates a free radical group with strong oxidation capacity through the electrochemical action to indirectly oxidize the organic pollutants in the waste water, and finally the organic pollutants are completely degraded into harmless CO2And H2O, the electrochemical oxidation method has the advantages of effective removal rate, strong oxidation capacity, convenient mode and the like for oxidizing complex organic pollutants, and is one of the most promising advanced oxidation processes.
The main technical point of electrochemical oxidation is anode material, in recent years, titanium-based lead dioxide anode has been widely researched and applied in the fields of electrolysis and sewage treatment because of its characteristics of good catalytic activity, strong corrosion resistance, long service life, good conductivity, high current efficiency, easy manufacture, low cost and the like, and the electrode surface is modified by doping, i.e. some ions, particles or surfactants are added into the electrodeposition plating solution, so that the microstructure of the electrode active layer is optimized, the particles are more compact, the number of active sites is increased, and the electrocatalytic performance and stability of the electrode are improved.
In the preparation process of the prior various titanium-based lead dioxide anodes, the plating layers have gaps, are uneven and have low adhesive force, so that the titanium-based lead dioxide anodes become very unstable in the electrolytic oxidation process, the specific surface area and the number of active sites of electrolysis are low, the electrocatalysis performance of the electrodes is limited, and the application of the titanium-based lead dioxide anodes in the field of electrocatalysis degradation is greatly reduced.
Disclosure of Invention
The invention aims to provide a preparation method and application of an electrode with high catalytic activity and stability, and aims to solve the problems that in the prior art, various titanium-based lead dioxide anodes have gaps, uneven coatings and low adhesive force in the preparation process, so that the titanium-based lead dioxide anodes become unstable in the electrolytic oxidation process, the specific surface area and the number of active sites of electrolysis are low, and the electrocatalytic performance of the electrode is limited.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of an electrode with high catalytic activity and stability comprises the following steps:
step (1), pretreating a titanium sheet:
selecting pure titanium metal as a titanium sheet, firstly, sequentially polishing the titanium sheet by using three different specifications of 600 meshes, 1000 meshes and 2000 meshes of abrasive paper, then, sequentially ultrasonically washing the polished titanium sheet in absolute ethyl alcohol, acetone and deionized water for 10min, then, putting the titanium sheet into a mixed solution of ethylene glycol, hydrofluoric acid and secondary distilled water for polishing for 10min, and finally, cleaning the titanium sheet by using the deionized water;
wherein the volume ratio of the hydrofluoric acid to the secondary distilled water to the ethylene glycol is 1: 6: 10;
step (2), Ti/TiO2Preparation of NT electrode:
preparing a titanium dioxide nanotube by adopting an anodic oxidation method, putting the titanium dioxide nanotube into ethylene glycol electrolyte, wherein the ethylene glycol electrolyte contains 0.1-0.7 wt% of NH4F and H with the volume fraction of 1-8V%2O, performing anodic oxidation on a Cu sheet serving as a counter electrode at room temperature, wherein the oxidation voltage is 70V, the oxidation time is 7-8 h, the magnetic stirring is kept in the oxidation process, the sample is soaked in absolute ethyl alcohol for 2h after the oxidation is finished, then the sample is ultrasonically cleaned in the absolute ethyl alcohol solution for 1-2 min, and after the cleaning is finished, the annealing treatment is performed in the air, the annealing temperature is 450-500 ℃, the annealing treatment is kept at the temperature for 2h, and the Ti/TiO is prepared2An NT electrode;
step (3), Ti/TiO2Reduction of NT electrode:
the prepared Ti/TiO2The NT electrode is used as a cathode, the Pt sheet is used as an anode, the saturated KCl electrode is used as a reference electrode, and 1mol/L (NH) is added4)2SO4Reducing Ti in the solution for 20s at-1.5V4+Reduction to Ti3+；
And (4) preparing precursor UiO-66 powder:
0.45mmol of ZrCl4Dissolving 0.45mmol of terephthalic acid in 15mLDMF, adding 4.5mmol of acetic acid after complete dissolution, ultrasonically treating the mixed solution for 5min, pouring the treated mixed solution into a stainless steel high-pressure reaction kettle with a 25mL polytetrafluoroethylene bottle as an inner liner, transferring the stainless steel high-pressure reaction kettle into a drying oven for heating, washing the obtained product with DMF and ethanol for multiple times, putting the product into a vacuum drying oven, and drying the product at the temperature of 60 ℃ to obtain UiO-66 powder;
step (5), ZrO2-preparation of nanoparticles of C:
the prepared UiO-66 powder is flatly laid in a quartz porcelain boat, put in a tubular furnace to be heated to 800 ℃, carbonized for 2-3 h at constant temperature, and the ZrO is obtained2-C nanoparticles;
step (6), ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2Preparing an electrode:
reducing the reduced Ti/TiO2NT is a working electrode, a platinum sheet is a counter electrode, a saturated calomel electrode is a reference electrode, and the working electrode, the platinum sheet and the saturated calomel electrode are placed into electroplating solution, and the components of the electroplating solution are Pb (NO) with 0.5mol/L3)20.02mol/L NaF and 2-6 g/L ZrO2-C nanoparticles and 1.0mol/L HNO3Adjusting the pH value of the electroplating solution to 1-2 at 50-60 mA/cm2Depositing by constant current direct current to obtain ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2And an electrode.
Preferably, the pure titanium metal in the step (1) is pure titanium metal of TA1 type, and the purity of the pure titanium metal is 99.9%.
Preferably, the constant-current and constant-voltage power supply used for preparing the titanium dioxide nanotube by the anodic oxidation method in the step (2) is a HYL-A type constant-current and constant-voltage power supply.
Preferably, the rates of temperature rise and temperature fall of the annealing treatment in the step (2) are both set to be 2 ℃/min.
Preferably, the heating temperature of the stainless steel autoclave in the step (4) in the oven is 100-120 ℃, and the heating time is 24 h.
Preferably, in the step (5), the UiO-66 powder is carbonized in a nitrogen atmosphere, and the temperature rise rate is 2 ℃/min.
Preferably, the deposition time in the step (6) is 20min, and the deposition temperature is 65 ℃.
The application of high-catalytic-activity and high-stability electrode is prepared by using ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode is used as an anode, the platinum electrode is used as a cathode, and the electrode is put into degradation liquid, wherein the degradation liquid comprises 20-60 mg/L of 2,4, 6-trinitrophenol and 0.1mol/L of Na2SO4A constant-current constant-voltage power supply is adopted, and the current density is 40-80 mA/m2At a temperature of 25 ℃, ZrO under different current density, initial concentration and pH value conditions are explored2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode has the degradation performance on 2,4, 6-trinitrophenol in wastewater.
The invention has at least the following beneficial effects:
(1) the invention provides a preparation method and application of an electrode with high catalytic activity and stability, wherein ZrO is obtained by carbonizing a synthesized metal organic framework UiO-66 serving as a precursor2-C nanoparticles, ZrO2Doping of C nanoparticles to PbO2The crystal grains become small, the specific surface area is increased, the electrocatalytic active sites are increased, the catalytic performance of the electrode is improved, the corrosion resistance of the electrode is improved, and the electrode is similar to pure Ti/TiO2NT/PbO2Compared with the prior art, the electrode has the advantages that the electrocatalytic activity is enhanced, and the electrode is high in activity and high in catalytic efficiency;
(2) the invention provides a preparation method and application of an electrode with high catalytic activity and stability, which adopts an anodic oxidation method to prepare TiO on a titanium sheet substrate2NT, compared with titanium sheet, the specific surface area is obviously increased, and more deposition points are provided;
(3) the invention provides a preparation method and application of an electrode with high catalytic activity and stability, which is prepared by mixing Ti/TiO2The NT electrode is used as an anode, the Pt sheet is used as a cathode, the saturated KCl electrode is used as a reference electrode, and the materials are put into the reactorContaining ZrO2Preparation of Ti/TiO by galvanostatic deposition in an acidic lead nitrate electroplating bath of-C nanoparticles2NT/ZrO2-C/PbO2Compared with other methods, the electrode is simple to operate, the purity, density and uniformity of a deposition layer are improved, the void ratio is reduced, and the stability and catalytic performance of the electrode are improved;
(4) the preparation method of the electrode with high catalytic activity and stability and the product obtained by application are used for treating 2,4, 6-trinitrophenol in wastewater by electrocatalytic oxidation, the preparation process of the electrode is simple, the operation is simple, the equipment is easy to obtain, the process flow is simple, the investment cost is low, the electrode corrosion resistance is stronger, the stability of the degradation process is better, the degradation efficiency is higher than that of a common lead electrode, the degradation rate of the 2,4, 6-trinitrophenol reaches more than 94.48 percent, the degradation rate of TOC reaches more than 69.7 percent, the energy consumption is greatly reduced, the average current efficiency is improved to more than 18.18 percent, the degradation side reaction is less, and the high degradation efficiency is ensured.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of an electrode with high catalytic activity and stability comprises the following steps:
step (1), pretreating a titanium sheet:
selecting TA1 type pure titanium metal with the purity of 99.9 percent as a titanium sheet, firstly, sequentially polishing the titanium sheet by three kinds of abrasive paper with different specifications of 600 meshes, 1000 meshes and 2000 meshes, then, sequentially ultrasonically washing the polished titanium sheet in absolute ethyl alcohol, acetone and deionized water for 10min, then, putting the titanium sheet into a mixed solution of ethylene glycol, hydrofluoric acid and secondary distilled water for polishing for 10min, and finally, cleaning the titanium sheet by using the deionized water;
wherein the volume ratio of the hydrofluoric acid to the secondary distilled water to the ethylene glycol is 1: 6: 10;
step (2), Ti/TiO2Preparation of NT electrode:
preparing a titanium dioxide nanotube by adopting an anodic oxidation method, putting the titanium dioxide nanotube into ethylene glycol electrolyte, wherein the ethylene glycol electrolyte contains 0.1-0.7 wt% of NH4F and H with the volume fraction of 1-8V%2O, performing anodic oxidation on a Cu sheet serving as an electrode at room temperature, adopting a HYL-A type constant-current constant-voltage power supply, enabling the oxidation voltage to be 70V, the oxidation time to be 7-8 h, keeping magnetic stirring in the oxidation process, soaking a sample for 2h by using absolute ethyl alcohol after the oxidation is finished, performing ultrasonic cleaning in an absolute ethyl alcohol solution for 1-2 min, performing annealing treatment in the air after the cleaning is finished, setting the annealing temperature to be 450-500 ℃, setting the heating and cooling rates of the annealing treatment to be 2 ℃/min, and keeping the temperature for annealing treatment for 2h to obtain the Ti/TiO2An NT electrode;
step (3), Ti/TiO2Reduction of NT electrode:
the prepared Ti/TiO2The NT electrode is used as a cathode, the Pt sheet is used as an anode, the saturated KCl electrode is used as a reference electrode, and 1mol/L (NH) is added4)2SO4Reducing Ti in the solution for 20s at-1.5V4+Reduction to Ti3+；
And (4) preparing precursor UiO-66 powder:
0.45mmol of ZrCl4Dissolving 0.45mmol of terephthalic acid in 15mLDMF, adding 4.5mmol of acetic acid after complete dissolution, ultrasonically treating the mixed solution for 5min, pouring the treated mixed solution into a stainless steel high-pressure reaction kettle with a 25mL polytetrafluoroethylene bottle as an inner liner, transferring the mixed solution into a drying oven, heating for 24h at 100 ℃, finally, washing the obtained product for multiple times by using DMF and ethanol, putting the product into a vacuum drying oven, and drying at 60 ℃ to obtain UiO-66 powder;
step (5), ZrO2-preparation of nanoparticles of C:
spreading the prepared UiO-66 powder in a quartz ceramic boat, putting the quartz ceramic boat in a tubular furnace, heating to 800 ℃, and heating at a rate ofAt the constant temperature of 2 ℃/min, carbonizing for 2 hours in the nitrogen atmosphere to obtain ZrO2-C nanoparticles;
step (6), ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2Preparing an electrode:
reducing the reduced Ti/TiO2NT is a working electrode, a platinum sheet is a counter electrode, a saturated calomel electrode is a reference electrode, and the working electrode, the platinum sheet and the saturated calomel electrode are placed into electroplating solution, and the components of the electroplating solution are Pb (NO) with 0.5mol/L3)20.02mol/L NaF and 2-6 g/L ZrO2-C nanoparticles and 1.0mol/L HNO3Adjusting the pH value of the electroplating solution to 1-2 at 50mA/cm2Depositing with constant current direct current for 20min at 65 deg.C to obtain ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2And an electrode.
The application of high-catalytic-activity and high-stability electrode is prepared by using ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode is used as an anode, the platinum electrode is used as a cathode, and the electrode is put into degradation liquid, wherein the degradation liquid comprises 20mg/L of 2,4, 6-trinitrophenol and 0.1mol/L of Na2SO4A constant-current constant-voltage power supply is adopted, and the current density is 60mA/m2At a temperature of 25 ℃, ZrO was investigated2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode has the degradation performance on 2,4, 6-trinitrophenol in wastewater.
Wherein, the degradation rate of the 2,4, 6-trinitrophenol in the electrolytic process reaches 94.48 percent, the degradation rate of the TOC reaches 69.7 percent, and the average current efficiency reaches 22.1 percent.
Example 2
A method for preparing an electrode with high catalytic activity and stability, which is substantially the same as that of example 1, except that:
and (4) preparing precursor UiO-66 powder:
0.45mmol of ZrCl4And 0.45mmol of terephthalic acid are dissolved in 15mLDMF, 4.5mmol of acetic acid is added after complete dissolution, and the solution is mixedPerforming ultrasonic treatment for 5min, pouring into a stainless steel high-pressure reaction kettle with a 25mL polytetrafluoroethylene bottle as an inner liner, transferring into an oven for heating at 120 ℃ for 24h, washing the obtained product with DMF and ethanol for multiple times, putting into a vacuum drying oven, and drying at 60 ℃ to obtain UiO-66 powder;
step (5), ZrO2-preparation of nanoparticles of C:
the prepared UiO-66 powder is spread in a quartz porcelain boat, put into a tubular furnace to be heated to 800 ℃, the heating rate is 2 ℃/min, and the powder is carbonized for 3 hours at constant temperature in the nitrogen atmosphere to obtain ZrO2-C nanoparticles;
step (6), ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2Preparing an electrode:
reducing the reduced Ti/TiO2NT is a working electrode, a platinum sheet is a counter electrode, a saturated calomel electrode is a reference electrode, and the working electrode, the platinum sheet and the saturated calomel electrode are placed into electroplating solution, and the components of the electroplating solution are Pb (NO) with 0.5mol/L3)20.02mol/L NaF and 2-6 g/L ZrO2-C nanoparticles and 1.0mol/L HNO3Adjusting the pH value of the electroplating solution to 1-2 at 60mA/cm2Depositing with constant current direct current for 20min at 65 deg.C to obtain ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2And an electrode.
The application of high-catalytic-activity and high-stability electrode is prepared by using ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode is used as an anode, the platinum electrode is used as a cathode, and the electrode is put into degradation liquid, wherein the degradation liquid comprises 20mg/L of 2,4, 6-trinitrophenol and 0.1mol/L of Na2SO4A constant-current constant-voltage power supply is adopted, and the current density is 60mA/m2At a temperature of 25 ℃, ZrO was investigated2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode has the degradation performance on 2,4, 6-trinitrophenol in wastewater.
Wherein, the degradation rate of the 2,4, 6-trinitrophenol in the electrolytic process reaches 94.48 percent, the degradation rate of the TOC reaches 69.7 percent, and the average current efficiency reaches 22.1 percent.
Example 3
A method for preparing an electrode with high catalytic activity and stability, which is the same as that of example 2.
The application of high-catalytic-activity and high-stability electrode is prepared by using ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode is used as an anode, the platinum electrode is used as a cathode, and the electrode is put into degradation liquid, wherein the degradation liquid comprises 20mg/L of 2,4, 6-trinitrophenol and 0.1mol/L of Na2SO4A constant-current constant-voltage power supply is adopted, and the current density is 70mA/m2At a temperature of 25 ℃, ZrO was investigated2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode has the degradation performance on 2,4, 6-trinitrophenol in wastewater.
Wherein, the degradation rate of 2,4, 6-trinitrophenol in the electrolytic process reaches 96.63%, the degradation rate of TOC reaches 71.8%, and the average current efficiency reaches 18.97%.
Example 4
A method for preparing an electrode with high catalytic activity and stability, which is the same as that of example 2.
The application of high-catalytic-activity and high-stability electrode is prepared by using ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode is used as an anode, the platinum electrode is used as a cathode, and the electrode is put into degradation liquid, wherein the degradation liquid comprises 20mg/L of 2,4, 6-trinitrophenol and 0.1mol/L of Na2SO4A constant-current constant-voltage power supply is adopted, and the current density is 80mA/m2At a temperature of 25 ℃, ZrO was investigated2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode has the degradation performance on 2,4, 6-trinitrophenol in wastewater.
Wherein, the degradation rate of 2,4, 6-trinitrophenol in the electrolytic process reaches 99.14 percent, the degradation rate of TOC reaches 76.5 percent, and the average current efficiency reaches 18.18 percent.
In summary, the use in examples 1 to 4Ti/TiO2NT/ZrO2-C/PbO2The method for treating the 2,4, 6-trinitrophenol in the wastewater by the electrocatalytic oxidation of the electrode has the advantages of simple electrode preparation, simple operation, easy equipment acquisition, simple process flow, low investment cost, stronger electrode corrosion resistance, better stability of the degradation process, higher degradation efficiency than that of a common lead electrode, more than 94.48 percent of the degradation rate of the 2,4, 6-trinitrophenol, more than 69.7 percent of the degradation rate of TOC, greatly reduced energy consumption, more than 18.18 percent of average current efficiency, less side degradation reaction and high degradation efficiency guarantee.
The Ti/TiO with high catalytic activity and stability of the invention2NT/ZrO2-C/PbO2Preparing an electrode, namely carbonizing a synthesized metal organic framework UiO-66 serving as a precursor to obtain ZrO2-C nanoparticles of ZrO prepared by galvanic deposition2-C nanoparticles with PbO2Uniform co-deposition on the substrate, ZrO2Doping of C nanoparticles so that PbO2The crystal grains become small, the specific surface area is increased, the electrocatalytic active sites are increased, the catalytic performance of the electrode is improved, the corrosion resistance of the electrode is improved, and the electrode is compatible with undoped Ti/TiO2NT/PbO2Compared with the electrode, the electrode has enhanced electrocatalytic activity and is an electrode with high activity and high catalytic efficiency.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

1. A preparation method of an electrode with high catalytic activity and stability is characterized by comprising the following steps:
step (1), pretreating a titanium sheet:
selecting pure titanium metal as a titanium sheet, firstly, sequentially polishing the titanium sheet by using three different specifications of 600 meshes, 1000 meshes and 2000 meshes of abrasive paper, then, sequentially ultrasonically washing the polished titanium sheet in absolute ethyl alcohol, acetone and deionized water for 10min, then, putting the titanium sheet into a mixed solution of ethylene glycol, hydrofluoric acid and secondary distilled water for polishing for 10min, and finally, cleaning the titanium sheet by using the deionized water;
wherein the volume ratio of the hydrofluoric acid to the secondary distilled water to the ethylene glycol is 1: 6: 10;
step (2), Ti/TiO2Preparation of NT electrode:
preparing a titanium dioxide nanotube by adopting an anodic oxidation method, putting the titanium dioxide nanotube into ethylene glycol electrolyte, wherein the ethylene glycol electrolyte contains 0.1-0.7 wt% of NH4F and H with the volume fraction of 1-8V%2O, performing anodic oxidation on a Cu sheet serving as a counter electrode at room temperature, wherein the oxidation voltage is 70V, the oxidation time is 7-8 h, the magnetic stirring is kept in the oxidation process, the sample is soaked in absolute ethyl alcohol for 2h after the oxidation is finished, then the sample is ultrasonically cleaned in the absolute ethyl alcohol solution for 1-2 min, and after the cleaning is finished, the annealing treatment is performed in the air, the annealing temperature is 450-500 ℃, the annealing treatment is kept at the temperature for 2h, and the Ti/TiO is prepared2An NT electrode;
step (3), Ti/TiO2Reduction of NT electrode:
the prepared Ti/TiO2The NT electrode is used as a cathode, the Pt sheet is used as an anode, the saturated KCl electrode is used as a reference electrode, and 1mol/L (NH) is added4)2SO4Reducing Ti in the solution for 20s at-1.5V4+Reduction to Ti3+；
And (4) preparing precursor UiO-66 powder:
will be 0.45mmol of ZrCl4Dissolving 0.45mmol of terephthalic acid in 15mLDMF, adding 4.5mmol of acetic acid after complete dissolution, ultrasonically treating the mixed solution for 5min, pouring the treated mixed solution into a stainless steel high-pressure reaction kettle with a 25mL polytetrafluoroethylene bottle as an inner liner, transferring the stainless steel high-pressure reaction kettle into a drying oven for heating, washing the obtained product with DMF and ethanol for multiple times, putting the product into a vacuum drying oven, and drying the product at the temperature of 60 ℃ to obtain UiO-66 powder;
step (5), ZrO2-preparation of nanoparticles of C:
the prepared UiO-66 powder is flatly laid in a quartz porcelain boat, put in a tubular furnace to be heated to 800 ℃, carbonized for 2-3 h at constant temperature, and the ZrO is obtained2-C nanoparticles;
step (6), ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2Preparing an electrode:
reducing the reduced Ti/TiO2NT is a working electrode, a platinum sheet is a counter electrode, a saturated calomel electrode is a reference electrode, and the working electrode, the platinum sheet and the saturated calomel electrode are placed into electroplating solution, and the components of the electroplating solution are Pb (NO) with 0.5mol/L3)20.02mol/L NaF and 2-6 g/L ZrO2-C nanoparticles and 1.0mol/L HNO3Adjusting the pH value of the electroplating solution to 1-2 at 50-60 mA/cm2Depositing by constant current direct current to obtain ZrO2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2And an electrode.
2. The method for preparing an electrode with high catalytic activity and stability as claimed in claim 1, wherein the pure titanium metal in step (1) is TA1 pure titanium metal with a purity of 99.9%.
3. The method for preparing an electrode with high catalytic activity and stability as claimed in claim 1, wherein the constant current and voltage source used for preparing the titanium dioxide nanotube by the anodic oxidation in the step (2) is a HYL-A type constant current and voltage source.
4. The method for preparing an electrode with high catalytic activity and stability as claimed in claim 1, wherein the rate of temperature increase and temperature decrease of the annealing treatment in the step (2) are set to be 2 ℃/min.
5. The method for preparing the electrode with high catalytic activity and stability according to claim 1, wherein the stainless steel autoclave in the step (4) is heated in an oven at 100-120 ℃ for 24 h.
6. The method for preparing an electrode with high catalytic activity and stability as claimed in claim 1, wherein in the step (5), the UiO-66 powder is carbonized in a nitrogen atmosphere at a temperature rising rate of 2 ℃/min.
7. The method for preparing an electrode with high catalytic activity and stability as claimed in claim 1, wherein the deposition time in step (6) is 20min, and the deposition temperature is 65 ℃.
8. The application of the electrode with high catalytic activity and stability is characterized in that ZrO is added2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode is used as an anode, the platinum electrode is used as a cathode, and the electrode is put into degradation liquid, wherein the degradation liquid comprises 20-60 mg/L of 2,4, 6-trinitrophenol and 0.1mol/L of Na2SO4A constant-current constant-voltage power supply is adopted, and the current density is 40-80 mA/m2At a temperature of 25 ℃, ZrO under different current density, initial concentration and pH value conditions are explored2-C nanoparticle doped modified Ti/TiO2NT/ZrO2-C/PbO2The electrode has the degradation performance on 2,4, 6-trinitrophenol in wastewater.
CN202011137031.3A 2020-10-22 2020-10-22 Preparation method and application of electrode with high catalytic activity and stability Withdrawn CN112250229A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113684516A (en) * 2021-08-04 2021-11-23 淮南师范学院 Ti/TiO2NT/ZrO2-C/PbO2Preparation method and application of electrode

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113684516A (en) * 2021-08-04 2021-11-23 淮南师范学院 Ti/TiO2NT/ZrO2-C/PbO2Preparation method and application of electrode

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