CN114890508A - Metal oxide nanowire array mesh electrode material and preparation method thereof - Google Patents
Metal oxide nanowire array mesh electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a metal oxide nanowire array mesh electrode material and a preparation method thereof, and relates to a flexible titanium mesh TiO 2 A nanowire array construction method, a ruthenium iridium tin oxide electrode material, a preparation method thereof and the like. Firstly, the flexible titanium mesh substrate is pretreated by alkali washing, oil removal, acid washing, etching and the like to remove the surface passivation layer of the titanium mesh substrate and improve the surfaceSurface activity; then, adopting an alkaline hydrothermal etching method to obtain the flexible titanium mesh-based TiO 2 A nanowire array; then, the preparation of the metal oxide active layer is repeatedly carried out by adopting a coating pyrolysis method; and finally, obtaining the multilayer electrode material with high catalytic activity and stability by high-temperature sintering. The metal oxide nanowire array mesh electrode material has the advantages of moderate price, simple preparation method, large specific surface area, high activity, good stability and the like, can improve the low-temperature catalytic activity of the oxide anode and improve the low-temperature stability of the oxide anode, and can also provide theoretical support for the development of the electrolysis antifouling technology and the chlor-alkali industry.
Description
Technical Field
The invention relates to a flexible titanium mesh-based metal oxide nanowire array electrode and a preparation method thereof, belongs to the field of chemical energy application, and particularly relates to a flexible titanium mesh TiO nanowire array electrode 2 The ruthenium iridium tin oxide electrode material of the nanowire array matrix is mainly used in the technical direction of ship ballast water electrochemical treatment, and can also be used in the application directions of efficient electrolysis antifouling, efficient electrolysis chlorine preparation and the like.
Background
In the process of sailing, ballast water is generally used for adjusting the balance between the draft and the center of gravity of a ship so as to ensure the safety of sailing. However, off-site ballast water loading and discharge can cause the transmission of harmful aquatic organisms and pathogens, posing serious hazards to marine ecosystems, socioeconomic and public health. The electrochemical treatment method is one of effective ways for treating harmful aquatic organisms and pathogens in the ballast water of the ship, mainly comprises the steps of electrolyzing and oxidizing seawater to generate chlorine on an electrode and generate hypochlorous acid with efficient disinfection effect to kill microorganisms and bacteria.
In the electrochemical treatment technology of ship ballast water, an electrocatalysis electrode is a core component, and the service performance and the service life of the electrocatalysis electrode directly determine the treatment effect of the ballast water. At present, electrodes for electrolyzing seawater in a ship ballast water treatment system are mainly ruthenium iridium metal oxide coating electrodes, have excellent chlorine evolution and oxygen evolution reaction selectivity, high chlorine evolution current efficiency and good corrosion resistance, and achieve better ballast water treatment effect. However, in practical engineering application, it is found that when the electrode works in an extremely low temperature environment, the chlorine evolution efficiency and the working life of the electrode are greatly reduced (preliminary laboratory results show that the reinforced electrolysis life of the electrode at 5 ℃ is only 9% under a normal temperature condition), and serious hidden danger is caused for the normal operation of a ballast water treatment system. Therefore, the service life of the electrode in a low-temperature environment is greatly shortened, which is one of the great challenges faced by the existing ballast water electrochemical treatment technology, and a new breakthrough is urgently needed.
Object of the Invention
The oxide electrode material with a multilayer coating structure and high activity and stability is prepared by combining a simple hydrothermal method and a coating pyrolysis method, has the advantages of moderate price, simple preparation method, large specific surface area, high activity, good low-temperature stability and the like, and can improve the low-temperature stability of a ship ballast water treatment system and reduce energy consumption.
Disclosure of Invention
Aiming at the problems of low-temperature activity, poor stability and the like of the oxide electrode material for electrochemical treatment of ship ballast water, the invention provides the multilayer coating structure electrode material of the flexible titanium mesh-based metal oxide nanowire array, which has high low-temperature activity and stability, and can effectively improve the low-temperature performance of a ship ballast water treatment system and prolong the service period. The material has simple preparation method, can be produced in large scale and has moderate cost.
The invention provides a flexible titanium mesh-based metal oxide nanowire array electrode material, which comprises the following steps:
1) cutting a high-purity titanium mesh sample into a certain size according to experimental requirements, and soaking in NaOH solution with a certain concentration at a certain temperature for alkali washing to remove oil for a period of time;
2) repeatedly ultrasonically cleaning the high-purity titanium mesh sample obtained in the step 1) for a period of time by using deionized water, and thoroughly removing alkaline washing residual liquid on the surface;
3) placing the high-purity titanium mesh sample obtained in the step 2) into oxalic acid solution with a certain concentration, and etching for a period of time at a certain water bath temperature to remove an oxide film on the surface of the titanium wire;
4) repeatedly washing the high-purity titanium mesh sample in the step 3) by adopting ultrapure water, removing titanium oxalate on the surface and residual acid liquor, and then drying for later use;
5) placing the titanium mesh in the step 4) in a high-temperature closed reactor containing a NaOH solution with a certain concentration, and carrying out chemical reaction for a period of time;
6) cleaning the titanium mesh obtained in the step 5) by ultrapure water, and soaking in a hydrochloric acid solution with a certain concentration at room temperature for a period of time;
7) repeatedly washing the titanium mesh sample in the step 6) by adopting ultrapure water, and then placing the titanium mesh sample in a forced air drying oven for drying at a certain temperature;
8) placing the titanium mesh sample obtained in the step 7) in a high-temperature muffle furnace at a certain temperature, and sintering for a period of time;
9) preparing precursor solutions of ruthenium chloride iridium chloroiridate and stannic chloride n-butyl alcohol with certain concentrations, and adjusting the pH value by using hydrochloric acid;
10) dipping the precursor solution obtained in the step 9) by a wool brush, and brushing the precursor solution on the surface of the titanium mesh sample obtained in the step 8);
11) placing the titanium mesh in the step 10) in a blast drying oven for drying, and then sintering for a period of time in a high-temperature muffle furnace;
12) repeating the steps 10) and 11) for a plurality of times, and finally sintering in a high-temperature muffle furnace for a period of time to obtain the flexible titanium mesh substrate metal oxide nanowire array electrode material.
In order to further realize the purpose of the invention, the specification of the titanium mesh in the step 1) is 20-100 meshes, and the concentration range of the NaOH solution is 30-60 wt%.
In order to further realize the aim of the invention, the concentration of the Chinese herbal acid solution in the step 3) is within the range of 10-15 wt%, the temperature range of water bath is 80-100 ℃, and the alkali washing time is 60-180 min; the ultrasonic treatment time of the ultrapure water, the acetone, the absolute ethyl alcohol and the like is respectively 30-120 min, 10-30 min and 10-30 min.
In order to further realize the aim of the invention, the concentration range of the NaOH solution in the step 5) is 4-10 wt%, the reaction temperature is 150-200 ℃, and the reaction time is 12-24 h.
In order to further realize the purpose of the invention, the concentration range of the hydrochloric acid in the step 6) is 2-5 wt%, and the soaking time is 20-40 h.
In order to further realize the aim of the invention, the drying temperature in the step 7) is 80-150 ℃, and the drying time is 15-60 min.
In order to further realize the purpose of the invention, the sintering temperature of the sample in the step 8) is 450-600 ℃, and the time range is 2-4 h.
In order to further achieve the purpose of the invention, the concentration ranges of ruthenium chloride, chloroiridic acid and stannic chloride in the ruthenium iridium tin precursor solution in the step 9) are respectively 0.1-0.15 mol/L, 0.07-0.1 mol/L and 0.15-0.23 mol/L; the pH value range of the precursor solution is 0-1.
In order to further realize the purpose of the invention, the drying temperature in the step 11) is 80-150 ℃, the drying time is 30-120 min, the sintering temperature is 450-600 ℃, and the sintering time is 20-60 min.
In order to further realize the purpose of the invention, the coating times in the step 12) range from 3 to 10 times, the sintering temperature range is from 450 to 600 ℃, and the sintering time is from 60 to 120 min.
The metal oxide nanowire array multilayer coating structure electrode material prepared by the invention has the advantages of large specific surface area, low chlorine evolution potential and good stability.
Compared with the prior art, the metal oxide nanowire array mesh electrode material and the preparation method thereof have the beneficial effects that:
1. the preparation method of the flexible titanium mesh-based nanowire array metal oxide electrode provided by the invention is simple to operate, low in equipment requirement and high in reproducibility, and can be used for batch production, and the surface of the obtained metal oxide electrode material is of a multi-layer coated nanowire array structure, so that the reaction activity of the electrode material is favorably improved;
2. the invention can realize effective regulation and control of different shapes of the metal oxide electrode by regulating the reaction temperature;
3. the nanowire array metal oxide mesh electrode material provided by the invention has low chlorine evolution potential and high electrocatalytic chlorine evolution activity, particularly still has higher chlorine evolution performance and stability at lower temperature, and is suitable for electrochemical treatment of ship ballast water of ocean-going ships in different sea areas;
4. the metal oxide nanowire array multilayer coating structure electrode material prepared by the invention has the advantages of large specific surface area, low chlorine evolution potential and good stability. The nano-wire array metal oxide electrode material provided by the invention has wide application, not only can be used for electrochemical treatment of ship ballast water, but also can be used for electrolytic antifouling and chlor-alkali industries, and can also be used for preparing disinfectant water by electrolyzing saline water in life.
Drawings
FIG. 1 is a picture of a 30-mesh flexible high-purity titanium mesh.
FIG. 2 shows TiO obtained by hydrothermal etching with NaOH solution 2 SEM image of nanowire alignment.
2 0.2 0.2 0.6 2 FIG. 3 shows a TiO nanowire @ RuIrSnO cladding structure SEMFigure (a).
FIG. 4 is 2 2 0.2 0.2 0.6 2 TiO nanowire TEM and TiO nanowire @ RuIrSnO coated structure TEM。
FIG. 5 is TiO 2 @Ru 0.23 Ir 0.17 Sn 0.6 O 2 EDS-Mapping plots of electrodes.
FIG. 6 is TiO 2 @Ru 0.23 Ir 0.17 Sn 0.6 O 2 Cyclic voltammogram of the electrode in 3.5% naCl solution.
FIG. 7 is TiO 2 @Ru 0.23 Ir 0.17 Sn 0.6 O 2 Linear sweep voltammogram of the electrode in 3.5% naCl solution.
Detailed Description
Example 1
Cutting 80-mesh high-purity titanium net into 5cm by 5cm according to experiment requirements, putting the net into NaOH solution with the concentration of 40wt%, and soaking and alkaline washing the net at the temperature of 100 ℃ for 1h to remove oil. And then, repeatedly carrying out ultrasonic cleaning for a period of time by using deionized water, and completely removing the alkaline washing residual liquid on the surface. And then, putting the titanium mesh into oxalic acid solution with the concentration of 10wt%, and etching for 1h at the water bath temperature of 80 ℃ to remove the oxide film on the surface of the titanium wire. And repeatedly washing the etched high-purity titanium mesh sample by adopting ultrapure water, removing titanium oxalate on the surface and residual acid liquor, and then drying for later use.
And (3) placing the pretreated titanium mesh in a high-temperature closed reactor containing 10wt% of NaOH solution, and carrying out chemical reaction for 24 hours at the temperature of 200 ℃. After the reaction was completed, the reaction mixture was washed with ultrapure water and immersed in a 2wt% hydrochloric acid solution at room temperature for 30 hours. Repeatedly washing with ultrapure water, placing in a forced air drying oven, and drying at 120 deg.C. Then, placing the titanium net in a muffle furnace at a high temperature of 600 ℃ and sintering for 4h to obtain the flexible titanium net-based TiO 2 And (4) nano arrays.
Preparing precursor solutions of ruthenium chloride, iridium chloroiridate and stannic chloride n-butanol, wherein the concentrations are 0.12mol/L, 0.1mol/L and 0.2mol/L respectively, and regulating the pH value to 0 by using hydrochloric acid. Then, a goat hair brush is used for dipping the precursor solution and is coated on the titanium mesh-based TiO 2 And (4) nano array sample surface. The coated titanium mesh was dried in a forced air drying oven at 120 ℃ and then sintered in a high temperature muffle furnace at 500 ℃ for 30 min. And repeating the coating and sintering process for 5 times, and finally sintering for 1.5h in a 600 ℃ high-temperature muffle furnace to obtain the flexible titanium mesh substrate metal oxide nanowire array electrode material.
Example 2
Cutting a 100-mesh high-purity titanium net into 10cm by 10cm according to the experimental requirements, putting the net into NaOH solution with the concentration of 60wt%, and soaking and alkaline washing the net at the temperature of 90 ℃ for 2 hours to remove oil. And then, repeatedly carrying out ultrasonic cleaning for a period of time by using deionized water, and completely removing the alkaline washing residual liquid on the surface. And then, putting the titanium mesh into an oxalic acid solution with the concentration of 12wt%, and etching for 2 hours at the water bath temperature of 90 ℃ to remove the oxide film on the surface of the titanium wire. And repeatedly washing the etched high-purity titanium mesh sample by adopting ultrapure water, removing titanium oxalate on the surface and residual acid liquor, and then drying for later use.
And (3) placing the pretreated titanium mesh in a high-temperature closed reactor containing 6wt% of NaOH solution, and carrying out chemical reaction for 20 hours at 180 ℃. After the reaction is completed, the reaction is carried out by using a catalystWashed with pure water and soaked in a 4wt% hydrochloric acid solution at room temperature for 20 h. Repeatedly washing with ultrapure water, placing in a forced air drying oven, and drying at 80 deg.C. Then, placing the titanium net in a muffle furnace at the high temperature of 450 ℃ and sintering for 3h to obtain the flexible titanium net-based TiO 2 And (4) nano arrays.
Preparing ruthenium chloride iridium chloroiridate and stannic chloride n-butanol precursor solutions with the concentrations of 0.1mol/L, 0.08 mol/L and 0.22mol/L respectively, and adjusting the pH value to 1 by using hydrochloric acid. Then, a goat hair brush is used for dipping the precursor solution and is coated on the titanium mesh-based TiO 2 And (4) nano array sample surface. And (3) placing the coated titanium mesh in a forced air drying oven for drying at 150 ℃, and then sintering in a high-temperature muffle furnace at 600 ℃ for 20 min. And repeating the coating and sintering process for 3 times, and finally sintering for 1h in a muffle furnace at the high temperature of 550 ℃ to obtain the flexible titanium mesh substrate metal oxide nanowire array electrode material.
Example 3
Cutting a 20-mesh high-purity titanium net into 10cm by 10cm according to the experimental requirements, putting the net into NaOH solution with the concentration of 30wt%, and soaking and alkaline washing the net at the temperature of 100 ℃ for 3 hours to remove oil. And then, repeatedly carrying out ultrasonic cleaning for a period of time by using deionized water, and completely removing the alkaline washing residual liquid on the surface. And then, putting the titanium mesh into an oxalic acid solution with the concentration of 10wt%, and etching for 2h at the water bath temperature of 100 ℃ to remove the oxide film on the surface of the titanium wire. And repeatedly washing the etched high-purity titanium mesh sample by adopting ultrapure water, removing titanium oxalate on the surface and residual acid liquor, and then drying for later use.
And (3) placing the pretreated titanium mesh in a high-temperature closed reactor containing a 4wt% NaOH solution, and carrying out chemical reaction for 12 hours at the temperature of 150 ℃. After the reaction was completed, it was washed with ultrapure water and immersed in a 5wt% hydrochloric acid solution at room temperature for 40 hours. Repeatedly washing with ultrapure water, placing in a forced air drying oven, and drying at 100 deg.C. Then, placing the titanium net in a muffle furnace at a high temperature of 500 ℃ and sintering for 2h to obtain the flexible titanium net-based TiO 2 And (4) nano arrays.
Preparing ruthenium chloride iridium chloroiridate and stannic chloride n-butanol precursor solutions with the concentrations of 0.15mol/L, 0.1mol/L and 0.15mol/L respectively, and adjusting the pH value to 0 by using hydrochloric acid. Then, the precursor solution is dipped by using a goat hair brush and coated on the titaniumTiO net base 2 And (4) nano array sample surface. And (3) placing the coated titanium mesh in a forced air drying oven to be dried at the temperature of 80 ℃, and then sintering the titanium mesh in a high-temperature muffle furnace at the temperature of 450 ℃ for 60 min. Repeating the coating and sintering process for 10 times, and finally sintering for 2h in a muffle furnace at the high temperature of 450 ℃ to obtain the flexible titanium mesh substrate metal oxide nanowire array electrode material.
Claims (10)
1. A flexible titanium mesh-based metal oxide nanowire array electrode material is characterized in that the preparation process comprises the following steps:
1) cutting a high-purity titanium mesh sample into a certain size according to experimental requirements, and soaking in NaOH solution with a certain concentration at a certain temperature for alkali washing to remove oil for a period of time;
2) repeatedly ultrasonically cleaning the high-purity titanium mesh sample obtained in the step 1) for a period of time by using deionized water, and thoroughly removing alkaline washing residual liquid on the surface;
3) placing the high-purity titanium mesh sample obtained in the step 2) into oxalic acid solution with a certain concentration, and etching for a period of time at a certain water bath temperature to remove an oxide film on the surface of the titanium wire;
4) repeatedly washing the high-purity titanium mesh sample in the step 3) by adopting ultrapure water, removing titanium oxalate on the surface and residual acid liquor, and then drying for later use;
5) placing the titanium mesh in the step 4) in a high-temperature closed reactor containing a NaOH solution with a certain concentration, and carrying out chemical reaction for a period of time;
6) cleaning the titanium mesh obtained in the step 5) by ultrapure water, and soaking in a hydrochloric acid solution with a certain concentration at room temperature for a period of time;
7) repeatedly washing the titanium mesh sample in the step 6) by adopting ultrapure water, and then placing the titanium mesh sample in a forced air drying oven for drying at a certain temperature;
8) placing the titanium mesh sample obtained in the step 7) in a high-temperature muffle furnace at a certain temperature, and sintering for a period of time;
9) preparing precursor solutions of ruthenium chloride iridium chloroiridate and stannic chloride n-butyl alcohol with certain concentrations, and adjusting the pH value by using hydrochloric acid;
10) dipping the precursor solution obtained in the step 9) by a wool brush, and coating the surface of the titanium mesh sample obtained in the step 8) with the solution;
11) placing the titanium mesh in the step 10) in a blast drying oven for drying, and then sintering for a period of time in a high-temperature muffle furnace;
12) repeating the steps 10) and 11) for a plurality of times, and finally sintering in a high-temperature muffle furnace for a period of time to obtain the flexible titanium mesh substrate metal oxide nanowire array electrode material.
2. The flexible titanium mesh-based metal oxide nanowire array electrode material as claimed in claim 1, wherein the titanium mesh specification in step 1) is 20-100 mesh, and the concentration of NaOH solution is in the range of 30-60 wt%.
3. The flexible titanium mesh-based metal oxide nanowire array electrode material as claimed in claim 1, wherein the concentration of the solution in step 3) is in the range of 10wt% to 15wt%, the temperature of the water bath is in the range of 80 to 100 ℃, and the alkali washing time is 60 to 180 min; the ultrasonic treatment time of ultrapure water, acetone, absolute ethyl alcohol and the like is respectively 30-120 min, 10-30 min and 10-30 min.
4. The flexible titanium mesh-based metal oxide nanowire array electrode material as claimed in claim 1, wherein the concentration of NaOH solution in step 5) is in the range of 4wt% to 10wt%, the reaction temperature is in the range of 150 ℃ to 200 ℃, and the reaction time is in the range of 12h to 24 h.
5. The flexible titanium mesh-based metal oxide nanowire array electrode material as claimed in claim 1, wherein the hydrochloric acid concentration in the step 6) is in the range of 2wt% to 5wt%, and the soaking time is 20 to 40 h.
6. The flexible titanium mesh-based metal oxide nanowire array electrode material as claimed in claim 1, wherein the drying temperature in step 7) is 80-150 ℃ and the drying time is 15-60 min.
7. The flexible titanium mesh-based metal oxide nanowire array electrode material as claimed in claim 1, wherein the sample sintering temperature in step 8) is 450-600 ℃ and the time is 2-4 h.
8. The flexible titanium mesh-based metal oxide nanowire array electrode material as claimed in claim 1, wherein the concentration ranges of ruthenium chloride, chloroiridic acid and tin chloride in the ruthenium iridium tin precursor solution in the step 9) are 0.1-0.15 mol/L, 0.07-0.1 mol/L and 0.15-0.23 mol/L respectively; the pH value range of the precursor solution is 0-1.
9. The flexible titanium mesh-based metal oxide nanowire array electrode material as claimed in claim 1, wherein the drying temperature in step 11) is in the range of 80-150 ℃, the drying time is in the range of 30-120 min, the sintering temperature is in the range of 450-600 ℃, and the sintering time is in the range of 20-60 min.
10. The flexible titanium mesh-based metal oxide nanowire array electrode material as claimed in claim 1, wherein the coating times in step 12) are in the range of 3-10, the sintering temperature is in the range of 450-600 ℃, and the sintering time is in the range of 60-120 min.
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| JP2020059917A (en) * | 2018-10-12 | 2020-04-16 | トヨタ自動車株式会社 | Tricobalt tetroxide array/titanium mesh electrode for water decomposition oxygen evolution and manufacturing method thereof |
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