CN113277601B - Foamed nickel/MXene-Co3O4Composite electrode and preparation method thereof - Google Patents

Foamed nickel/MXene-Co3O4Composite electrode and preparation method thereof Download PDF

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CN113277601B
CN113277601B CN202110543707.7A CN202110543707A CN113277601B CN 113277601 B CN113277601 B CN 113277601B CN 202110543707 A CN202110543707 A CN 202110543707A CN 113277601 B CN113277601 B CN 113277601B
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nickel
mxene
foamed nickel
composite electrode
foamed
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CN113277601A (en
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林辉
李唯
李威
吕斯濠
刘倩
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Dongguan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/46109—Electrodes
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    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
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    • B82—NANOTECHNOLOGY
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • 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
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
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    • C21D1/26—Methods of annealing
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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    • 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
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Abstract

The invention discloses foamed nickel/MXene-Co3O4The composite electrode and the preparation method thereof comprise the following steps: (1) pretreatment of foamed nickel: taking foamed nickel, sequentially carrying out ultrasonic cleaning by using sulfuric acid, ethanol and deionized water, and drying at constant temperature; (2) preparing a composite electrode: taking MXene and Co3O4Mixing to obtain mixed powder, coating the mixed powder on the surface of the foamed nickel, and performing vacuum plasma sintering to obtain the composite electrode. The invention adopts foamed nickel, MXene and Co3O4Preparing foam material composite electrode, namely, using the high-temperature and high-pressure action of a vacuum plasma sintering furnace and using foam nickel to mix MXene-Co3O4The mixed powder is stably combined, the use of an adhesive is avoided, the preparation cost is reduced, and the preparation time is only 40-60 min; the MXene has an organ structure, so that the catalyst can be effectively contained and dispersed, the problem of easy agglomeration of the catalyst is solved, the activity and stability of the catalyst are improved, the prepared electrode is large in specific surface area and good in conductivity, and the electrode material with excellent performance can be formed.

Description

Foamed nickel/MXene-Co3O4Composite electrode and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemistry, in particular to foamed nickel/MXene-Co3O4A composite electrode and a method for preparing the same.
Background
With the rapid development of economic society of China, the industrialization and urbanization degree is continuously improved, and the problem of water resource shortage caused by water pollution is increasingly serious. Due to its prevalence in industrial and commercial products and its high water solubility and resistance to biological degradation, 1, 4-dioxane is found in many places as a contaminant in water. At present, the traditional wastewater treatment technology, including air extraction, precipitation and solidification, carbon adsorption and traditional biological treatment, can not effectively remove the 1, 4-dioxane. In recent years, persulfate advanced oxidation technology is a hotspot in the field of refractory water treatment because it can generate active species with strong oxidizing property (such as sulfate radicals, hydroxyl radicals and the like) which can effectively remove refractory organic pollutants. Because persulfate itself is less reactive with organic contaminants, activation techniques are required to activate persulfate to produce active species with strong oxidizing properties. Currently, many methods for activating persulfate are available, and among them, a multivalent transition metal ion activation method represented by a divalent cobalt ion can efficiently activate persulfate, and thus has received much attention. However, drinking water containing cobalt ions causes various health problems such as asthma, pneumonia and other lung diseases. Therefore, in order to avoid introducing cobalt ions into water, researchers have supported cobalt-based catalysts on the surface of some substrates (such as glass, foamed metal) to prepare electrodes. The method not only can effectively activate the persulfate, but also can relatively easily recover and recycle the catalyst. However, the loading of the catalyst onto the substrate is often requiredAdhesives, expensive adhesives, limit the large scale application of these processes. On the other hand, the problem that the catalyst is easy to agglomerate also severely restricts the activity and stability of the catalyst, and in order to uniformly disperse the catalyst on the surface of the substrate, a two-dimensional layered material MXene with an accordion shape is introduced, and the material becomes the key point of research of scientists in recent years due to high specific surface area and excellent electrical conductivity. In the invention, MXene and a catalyst are combined, so that a composite electrode material which is free of an adhesive and excellent in performance is designed. The successful development of the electrode material can reduce the preparation cost, improve the activity and stability of the catalyst and has important practical application value. Therefore, we propose a nickel foam/MXene-Co3O4A composite electrode and a method for preparing the same.
Disclosure of Invention
The invention aims to provide foamed nickel/MXene-Co3O4A composite electrode and a preparation method thereof, which aim to solve the problems proposed in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: foamed nickel/MXene-Co3O4The preparation method of the composite electrode comprises the following steps:
(1) pretreatment of foamed nickel: taking foamed nickel, sequentially carrying out ultrasonic cleaning by using sulfuric acid, ethanol and deionized water, and drying at constant temperature;
(2) preparing a composite electrode: taking MXene and Co3O4Mixing to obtain mixed powder, coating the mixed powder on the surface of the foamed nickel, and performing vacuum plasma sintering to obtain the composite electrode.
Further, the step (1) comprises the steps of:
taking foamed nickel, sequentially carrying out ultrasonic cleaning for 2-3 times by using sulfuric acid, ethanol and deionized water, and drying in a constant-temperature oven at the drying temperature of 49.5-50.5 ℃ for 1-1.5 hours.
Further, the step (2) comprises the following steps:
taking MXene and Co3O4Mixing, oscillating for 2-4 min by using a vortex oscillator to prepare mixed powder, and uniformly coating the mixed powder on a foamed nickel surfaceSurface, vacuum plasma sintering, the sintering process is as follows: and (3) carrying out vacuum at 25-55 Pa, sintering at 400-600 ℃, applying pressure at 1-2 MPa, and sintering for 10-15 min to obtain the composite electrode.
Further, MXene and Co3O4The mass ratio is 1 (4-6), and the mass of the mixed powder is 0.05-0.1 g.
Further, the Co3O4The average particle diameter of (A) is 20 to 80 nm.
Furthermore, the diameter of the foamed nickel plate is 2-3 cm, the aperture is 100-200 mu m, and the thickness is 3-4 mm.
Further, the nickel foam surface in the step (1) is loaded with nickel nanotubes, and the preparation process of the nickel foam comprises the following steps:
(1) preparing a foamed nickel matrix:
placing polyurethane foam plastic in a mixed solution of hydrogen peroxide and sulfuric acid for coarsening for 100-140 s, and cleaning with deionized water; putting the mixture into a mixed solution of nickel sulfate and hydrochloric acid for 9-12 min, taking out and filtering to dry; placing the mixture in a mixed solution of sodium hydroxide and potassium borohydride for activating for 17-25 s, taking out and filtering to dry;
preparing a solution from nickel chloride, nickel sulfate and boric acid, adjusting the pH value to 1.8-2.4 to prepare a plating solution, wherein polyurethane foam plastic is used as a cathode, a nickel plate is used as an anode, and the pH value is 8-10A/dm2Carrying out electrodeposition on the current density to prepare a foamed nickel plate;
taking a foamed nickel plate to be calcined, annealing in a reducing atmosphere at the annealing temperature of 600-1200 ℃, cleaning and drying to obtain a foamed nickel matrix;
(2) preparing foamed nickel:
adding deionized water into hexadecyl trimethyl ammonium bromide, heating to 28-32 ℃, stirring and dissolving, adding ammonia water, stirring, slowly adding butyl orthosilicate, stirring for 4-5 hours, keeping the temperature at 100 ℃ for 48-50 hours, filtering, drying, and sintering at 540-560 ℃ for 5-6 hours; adding a nickel chloride solution, uniformly mixing, placing a foamed nickel matrix in the mixture, performing ultrasonic treatment for 7-9 days, performing suction filtration, washing for 2-3 times, drying, heating to 900-950 ℃ at the speed of 5-6 ℃/min, roasting for 30-40 min, cooling, placing in hydrofluoric acid, and stirring for 2-3 h to obtain a nickel nanotube, thereby preparing foamed nickel.
In the technical scheme, the nickel nano tube is loaded on the surface of the foamed nickel, so that the strength, the heat conduction and the electric conductivity of the prepared composite electrode can be improved; then carrying out surface treatment on the nickel nano tube, and loading MXene and Co on the nickel nano tube3O4Forming a dendritic structure, foaming nickel and MXene, Co3O4The affinity between the metal and the metal is improved, the contact area is increased, and the metal and the MXene and Co are mixed3O4The bonding strength between the composite electrode and the foamed nickel is enhanced, the area specific capacitance of the prepared composite electrode is increased, the transmission capability of electrons and reaction solution in the prepared composite electrode can be enhanced, and the cycle performance of the prepared battery is improved.
A sewage advanced treatment method is characterized in that: the method of claim 9 is adopted for preparing the foamed nickel/MXene-Co3O4The composite electrode is a cathode for activating persulfate, and electrolyzing and degrading the 1, 4-dioxane.
Compared with the prior art, the invention has the following beneficial effects:
1. foamed nickel/MXene-Co of the invention3O4The composite electrode is prepared by foaming nickel, MXene and Co3O4Preparing foam material composite electrode, namely, MXene/Co is mixed with foamed nickel under the action of high temperature and high pressure of a vacuum plasma sintering furnace3O4The mixed powder is stably combined, the use of an adhesive is avoided, the preparation cost is reduced, and the preparation time is only 40-60 min; the MXene has an organ structure, so that the catalyst can be effectively contained and dispersed, the problem of easy agglomeration of the catalyst is solved, the activity and stability of the catalyst are improved, the prepared electrode is large in specific surface area and good in conductivity, and the electrode material with excellent performance can be formed.
2. Foamed nickel/MXene-Co of the invention3O4A composite electrode and a preparation method thereof, and the prepared nickel foam/MXene-Co3O4A composite electrode, provides a method for treating organic pollutants difficult to degrade, the prepared composite electrode is used as a cathode, a ruthenium iridium electrode is used as an anode, and 1, 4-containing persulfateThe dioxane solution is used as electrolyte, and when the electrolytic cell is used, persulfate can be activated to generate a large amount of free radicals OH, 1, 4-dioxane in water can be effectively degraded, and the degradation rate is over 95% in 20min under the optimal experimental condition.
3. Foamed nickel/MXene-Co of the invention3O4The composite electrode and the preparation method thereof can improve the strength, heat conduction and electric conduction performance of the prepared composite electrode by loading the nickel nano tube on the surface of the foamed nickel; then carrying out surface treatment on the nickel nano tube, and loading MXene and Co on the nickel nano tube3O4Forming a dendritic structure, foaming nickel and MXene, Co3O4The affinity between the metal and the metal is improved, the contact area is increased, and the metal and the MXene and Co are mixed3O4The bonding strength between the composite electrode and the foamed nickel is enhanced, the area specific capacitance of the prepared composite electrode is increased, the transmission capability of electrons and reaction solution in the prepared composite electrode can be enhanced, and the cycle performance of the prepared battery is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows MXene and Co in example 2 of the present invention3O4Electron microscope images of the mixed powders;
FIG. 2 is a comparison of the degradation efficiency of 1, 4-dioxane according to example 2, comparative example 1 and comparative example 2 of the present invention;
FIG. 3 shows a nickel foam/MXene-Co of example 2 of the present invention3O4Performing stability experiment on the composite electrode;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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
Taking foamed nickel, sequentially carrying out ultrasonic cleaning for 3 times by using sulfuric acid, ethanol and deionized water, and drying in a constant-temperature oven at the drying temperature of 50 ℃ for 1 h; MXene, Co3O4Mixing, oscillating for 2min by using a vortex oscillator to prepare mixed powder, uniformly coating the mixed powder on the surface of the foamed nickel, and sintering by using vacuum plasma, wherein the sintering process comprises the following steps: vacuum 25Pa, sintering temperature 600 ℃, applied pressure 1MPa, and sintering time 10min to obtain a composite electrode;
wherein the diameter of the foam nickel is 2cm, the pore diameter is 100 μm, and the thickness is 3 mm; MXene and Co3O4The mass ratio is 1:6, the mass of the mixed powder is 0.05g, Co3O4Has an average particle diameter of 20 nm.
Example 2
Ultrasonically cleaning foamed nickel for 2 times by using sulfuric acid, ethanol and deionized water in sequence, and drying in a constant-temperature drying oven at the drying temperature of 50 ℃ for 1.2 h; MXene, Co3O4Mixing, oscillating for 2min by using a vortex oscillator to prepare mixed powder, uniformly coating the mixed powder on the surface of the foamed nickel, and sintering by using vacuum plasma, wherein the sintering process comprises the following steps: vacuum is 30Pa, sintering temperature is 500 ℃, applied pressure is 1.6MPa, and sintering time is 12min, so as to prepare the composite electrode;
wherein the diameter of the foam nickel is 3cm, the pore diameter is 200 μm, and the thickness is 3.5 mm; MXene and Co3O4The mass ratio is 1:5, the mass of the mixed powder is 0.07g, Co3O4Has an average particle diameter of 80 nm.
Example 3
Ultrasonically cleaning foamed nickel for 3 times by using sulfuric acid, ethanol and deionized water in sequence, and drying in a constant-temperature drying oven at the drying temperature of 50 ℃ for 1.5 hours; MXene, Co3O4Mixing, oscillating for 4min by using a vortex oscillator to prepare mixed powder, uniformly coating the mixed powder on the surface of the foamed nickel, and sintering by using vacuum plasma, wherein the sintering process comprises the following steps: vacuum 55Pa, sintering temperature 600 ℃, applied pressure 2MPa, sintering time 15min, and preparing a composite electrode;
wherein the nickel foam has a diameter of 2.5cm, a pore diameter of 150 μm, and a thickness of 4mm; MXene and Co3O4The mass of the mixed powder was 0.1g, Co in a mass ratio of 1:43O4Has an average particle diameter of 50 nm.
Example 4
Placing polyurethane foam plastic in a mixed solution of hydrogen peroxide and sulfuric acid for coarsening for 100s, and cleaning with deionized water; placing in mixed solution of nickel sulfate and hydrochloric acid for 9min, taking out, and filtering to dry; activating in a mixed solution of sodium hydroxide and potassium borohydride for 17s, taking out and filtering to dry; preparing solution from nickel chloride, nickel sulfate and boric acid, adjusting pH to 2.4 to obtain plating solution, wherein polyurethane foam plastic is used as cathode, nickel plate is used as anode, and 8A/dm is used2Carrying out electrodeposition on the current density to prepare a foamed nickel plate; taking a foamed nickel plate to be calcined, annealing in a reducing atmosphere at the annealing temperature of 600 ℃, cleaning and drying to obtain a foamed nickel matrix;
adding deionized water into hexadecyl trimethyl ammonium bromide, heating to 28 ℃, stirring and dissolving, adding ammonia water, stirring, slowly adding n-butyl silicate, stirring for 4 hours, keeping the temperature at 100 ℃ for 48 hours, filtering, drying, and sintering at 540 ℃ for 5-6 hours; adding a nickel chloride solution, uniformly mixing, placing a foamed nickel matrix in the nickel chloride solution, performing ultrasonic treatment for 7d, performing suction filtration, washing for 2 times, drying, heating to 900 ℃ at the speed of 5 ℃/min, roasting for 30min, cooling, placing in hydrofluoric acid, and stirring for 2h to obtain a nickel nanotube, thereby preparing foamed nickel;
ultrasonically cleaning foamed nickel for 2 times by using sulfuric acid, ethanol and deionized water in sequence, and drying in a constant-temperature drying oven at the drying temperature of 50 ℃ for 1.2 h; MXene, Co3O4Mixing, oscillating for 2min by using a vortex oscillator to prepare mixed powder, uniformly coating the mixed powder on the surface of the foamed nickel, and sintering by using vacuum plasma, wherein the sintering process comprises the following steps: vacuum is 30Pa, sintering temperature is 500 ℃, applied pressure is 1.6MPa, and sintering time is 12min, so as to prepare the composite electrode;
wherein the diameter of the foam nickel is 3cm, the pore diameter is 200 μm, and the thickness is 3.5 mm; MXene and Co3O4The mass ratio is 1:5, the mass of the mixed powder is 0.07g, Co3O4Has an average particle diameter of 80 nm.
Example 5
Placing polyurethane foam plastic in a mixed solution of hydrogen peroxide and sulfuric acid for coarsening for 120s, and cleaning with deionized water; placing in mixed solution of nickel sulfate and hydrochloric acid for 10min, taking out, and filtering to dry; activating in mixed solution of sodium hydroxide and potassium borohydride for 21s, taking out and filtering to dry; preparing solution from nickel chloride, nickel sulfate and boric acid, adjusting pH to 2.1 to obtain plating solution, and preparing the plating solution by using polyurethane foam as a cathode, a nickel plate as an anode and 9A/dm2Carrying out electrodeposition on the current density to prepare a foamed nickel plate; taking a foamed nickel plate to be calcined, annealing in a reducing atmosphere, wherein the annealing temperature is 800 ℃, cleaning and drying to obtain a foamed nickel matrix;
adding deionized water into hexadecyl trimethyl ammonium bromide, heating to 30 ℃, stirring for dissolving, adding ammonia water, stirring, slowly adding n-butyl silicate, stirring for 4.5h, keeping the temperature at 100 ℃ for 49h, filtering, drying, and sintering at 550 ℃ for 5.5 h; adding nickel chloride solution, mixing uniformly, placing the foamed nickel matrix in the foamed nickel matrix, performing ultrasonic treatment for 8d, performing suction filtration, washing for 2 times, drying, heating to 925 ℃ at the speed of 5.5 ℃/min, roasting for 35min, cooling, placing in hydrofluoric acid, and stirring for 2.5h to obtain a nickel nanotube, thereby preparing foamed nickel;
ultrasonically cleaning foamed nickel for 2 times by using sulfuric acid, ethanol and deionized water in sequence, and drying in a constant-temperature drying oven at the drying temperature of 50 ℃ for 1.2 h; MXene, Co3O4Mixing, oscillating for 2min by using a vortex oscillator to prepare mixed powder, uniformly coating the mixed powder on the surface of the foamed nickel, and sintering by using vacuum plasma, wherein the sintering process comprises the following steps: vacuum is 30Pa, sintering temperature is 500 ℃, applied pressure is 1.6MPa, and sintering time is 12min, so as to prepare the composite electrode;
wherein the diameter of the foam nickel is 3cm, the pore diameter is 200 μm, and the thickness is 3.5 mm; MXene and Co3O4The mass ratio is 1:5, the mass of the mixed powder is 0.07g, Co3O4Has an average particle diameter of 80 nm.
Example 6
Placing polyurethane foam plastic in a mixed solution of hydrogen peroxide and sulfuric acid for roughening for 140s, and cleaning with deionized water; placing in mixed solution of nickel sulfate and hydrochloric acid for 12min, taking out and draining; activating in mixed solution of sodium hydroxide and potassium borohydride for 25s, taking out and filtering to dry; preparing solution from nickel chloride, nickel sulfate and boric acid, adjusting pH to 1.8 to obtain plating solution, wherein polyurethane foam plastic is used as cathode, nickel plate is used as anode, and 10A/dm is used2Carrying out electrodeposition on the current density to prepare a foamed nickel plate; taking a foamed nickel plate to be calcined, annealing in a reducing atmosphere at the annealing temperature of 1200 ℃, and cleaning and drying to obtain a foamed nickel matrix;
adding deionized water into hexadecyl trimethyl ammonium bromide, heating to 32 ℃, stirring for dissolving, adding ammonia water, stirring, slowly adding n-butyl silicate, stirring for 5 hours, keeping the temperature at 100 ℃ for 50 hours, filtering, drying, and sintering at 560 ℃ for 6 hours; adding a nickel chloride solution, uniformly mixing, placing a foamed nickel matrix in the nickel chloride solution, performing ultrasonic treatment for 9d, performing suction filtration, washing for 3 times, drying, heating to 950 ℃ at the speed of 6 ℃/min, roasting for 40min, cooling, placing in hydrofluoric acid, and stirring for 3h to obtain a nickel nanotube, thereby preparing foamed nickel;
ultrasonically cleaning foamed nickel for 2 times by using sulfuric acid, ethanol and deionized water in sequence, and drying in a constant-temperature drying oven at the drying temperature of 50 ℃ for 1.2 h; MXene, Co3O4Mixing, oscillating for 2min by using a vortex oscillator to prepare mixed powder, uniformly coating the mixed powder on the surface of the foamed nickel, and sintering by using vacuum plasma, wherein the sintering process comprises the following steps: vacuum is 30Pa, sintering temperature is 500 ℃, applied pressure is 1.6MPa, and sintering time is 12min, so as to prepare the composite electrode;
wherein the diameter of the foam nickel is 3cm, the pore diameter is 200 μm, and the thickness is 3.5 mm; MXene and Co3O4The mass ratio is 1:5, the mass of the mixed powder is 0.07g, Co3O4Has an average particle diameter of 80 nm.
Comparative example 1
Ultrasonically cleaning foamed nickel for 3 times by using sulfuric acid, ethanol and deionized water in sequence, and drying in a constant-temperature drying oven at the drying temperature of 50 ℃ for 1.2 h; taking Co3O4Uniformly coating powder on the surface of the foamed nickel, and sintering in vacuum plasma, wherein the sintering process comprises the following steps: vacuum of 30Pa, sintering temperature of 500 ℃, applied pressure of 1.6MPa, and sintering time of 12min, preparing a composite electrode;
wherein the diameter of the foam nickel is 3cm, the pore diameter is 200 μm, and the thickness is 3.5 mm; co3O4Has a mass of 0.01g, Co3O4Has an average particle diameter of 80 nm.
Comparative example 2
Ultrasonically cleaning foamed nickel for 2 times by using sulfuric acid, ethanol and deionized water in sequence, and drying in a constant-temperature drying oven at the drying temperature of 50 ℃ for 1-1.5 h; uniformly coating MXene powder on the surface of foamed nickel, and performing vacuum plasma sintering, wherein the sintering process comprises the following steps: vacuum is 30Pa, sintering temperature is 500 ℃, applied pressure is 1.6MPa, and sintering time is 12min, so as to prepare the composite electrode;
wherein the diameter of the foam nickel is 23cm, the pore diameter is 200 μm, and the thickness is 3.5 mm; MXene had a mass of 0.04 g.
Comparative example 3
Placing polyurethane foam plastic in a mixed solution of hydrogen peroxide and sulfuric acid for coarsening for 120s, and cleaning with deionized water; placing in mixed solution of nickel sulfate and hydrochloric acid for 10min, taking out, and filtering to dry; activating in a mixed solution of sodium hydroxide and potassium borohydride for 21s, taking out and filtering to dry; preparing solution from nickel chloride, nickel sulfate and boric acid, adjusting pH to 2.1 to obtain plating solution, and preparing the plating solution by using polyurethane foam as a cathode, a nickel plate as an anode and 9A/dm2Carrying out electrodeposition on the current density to prepare a foamed nickel plate; taking a foamed nickel plate to be calcined, annealing in a reducing atmosphere, wherein the annealing temperature is 800 ℃, cleaning and drying to obtain a foamed nickel matrix;
placing a foam nickel substrate in a reaction kettle, taking normal hexane as a carbon source, ferrocene as a catalyst and thiophene as an additive in a hydrogen atmosphere, performing catalytic pyrolysis at 1100 ℃, and depositing a carbon nano tube on the surface of the foam nickel substrate to prepare foam nickel;
ultrasonically cleaning foamed nickel for 2 times by using sulfuric acid, ethanol and deionized water in sequence, and drying in a constant-temperature drying oven at the drying temperature of 50 ℃ for 1.2 h; MXene, Co3O4Mixing, oscillating for 2min by using a vortex oscillator to prepare mixed powder, uniformly coating the mixed powder on the surface of the foamed nickel, and sintering by using vacuum plasma, wherein the sintering process comprises the following steps: vacuum 30Pa, sinteringThe temperature is 500 ℃, the applied pressure is 1.6MPa, and the sintering time is 12min, so as to prepare the composite electrode;
wherein the diameter of the foam nickel is 3cm, the pore diameter is 200 μm, and the thickness is 3.5 mm; MXene and Co3O4The mass ratio is 1:5, the mass of the mixed powder is 0.07g, Co3O4Has an average particle diameter of 80 nm.
Experiment of
The composite electrodes obtained in examples 1 to 6 and comparative examples 1 to 3 were used to prepare samples, and the properties thereof were measured and the results were recorded:
measuring the tensile strength of the test sample by using an electronic tensile testing machine, calculating the ratio of the maximum load when the test sample is broken to the initial section area of the test sample according to the maximum load when the test sample is broken, and recording the ratio as the tensile strength;
taking a sample as a cathode and a ruthenium iridium electrode as an anode, and placing the sample in a reaction solution, wherein the initial concentration of 1, 4-dioxane is 5mM, the concentration of potassium hydrogen peroxymonosulfate is 25mM, and a supporting electrolyte is 20mM NaSO4The current density is 20mA/cm2The distance between the anode and the cathode is 1 cm; detecting the final content of the 1, 4-dioxane after the operation for 20min, calculating the ratio of the amount of the degraded substances of the 1, 4-dioxane within 20min to the amount of the initial substances of the 1, 4-dioxane, and recording as the degradation rate for 20 min;
and (4) recycling the electrolytic cell, and detecting the cycle times when the 20min degradation rate is 60%, and recording the cycle life.
Degradation Rate at 20min (%) Tensile strength (MPa) Cycle life
Example 1 95 0.57 >500
Example 2 99 0.65 >500
Example 3 98 0.62 >500
Example 4 98 0.68 >600
Example 5 99 0.71 >600
Example 6 99 0.73 >600
Comparative example 1 96 0.46 >100
Comparative example 2 56 0.34 >300
Comparative example 3 96 0.67 >400
From the data in the table above, it is clear that the following conclusions can be drawn:
the composite electrodes obtained in examples 1 to 6 and the composite electrodes obtained in comparative examples 1 to 3 are compared, and the detection results show that the composite electrodes obtained in examples 1 to 6 have high tensile strength, cycle life and 20min degradation rate data, which fully indicates that the composite electrode prepared by the method has high degradation rate and good stability for 1, 4-dioxane;
compared with example 2, the degradation rate of the 1, 4-dioxane prepared in the comparative example 1 can reach more than 95% in 20min, but the stability is poor, and the loss of cobalt ions is serious; the degradation rate of the composite electrode prepared in the comparative example 2 to 1, 4-dioxane is only 56% at 20min, and the stability is poor; the improvement of the degradation performance of the composite electrode 1, 4-dioxane is fully realized; the carbon nano tube is loaded on the surface of the foam nickel base in the comparative example 3, the data of tensile strength, cycle life and 20min degradation rate are reduced, and the arrangement of the nickel nano tube is beneficial to improving the performance of the prepared composite electrode.
And MXene and Co in embodiment 2 of the invention according to FIG. 13O4Electron microscopy of the mixed powders shows that Co3O4Successfully loaded on the two-dimensional layered structure of MXene accordion appearance.
From FIG. 2, comparing the degradation efficiency of example 2, comparative example 1 and comparative example 2 of the present invention to 1, 4-dioxane, it can be seen that: 1. foamed nickel/Co from comparative example 13O4The composite electrode can advance to 1, 4-dioxaneThe degradation is carried out, and the degradation rate of the 1, 4-dioxane is equal to that of the foamed nickel/MXene-Co prepared in example 2 when the foamed nickel/MXene-Co is used for 20min3O4The composite electrode has no large difference, but the initial degradation rate is slow; 2. the degradation rate of the foamed nickel/MXene composite electrode prepared in the comparative example 2 on the 1, 4-dioxane is obviously different from that of the foamed nickel/MXene composite electrode prepared in the example 2 and the comparative example 1 in the data expression of the degradation rate of the 1, 4-dioxane after 20 min;
FIG. 3 shows Ni foam/MXene-Co of example 2 of the present invention3O4Stability test of composite electrode: the foamed nickel/MXene-Co prepared by the invention3O4When the composite electrode is circulated, the change range of the degradation rate of the 1, 4-dioxane is small, and the stability of the composite electrode prepared by the method is excellent.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. Foamed nickel/MXene-Co3O4Method for producing composite electrode, and composite electrodeIs characterized in that: the method comprises the following steps:
(1) pretreatment of foamed nickel: taking foamed nickel, sequentially carrying out ultrasonic cleaning by using sulfuric acid, ethanol and deionized water, and drying at constant temperature;
(2) preparing a composite electrode: taking MXene and Co3O4Mixing to obtain mixed powder, coating the mixed powder on the surface of the foamed nickel, and performing vacuum plasma sintering to obtain a composite electrode;
the nickel foam surface in the step (1) is loaded with nickel nano tubes, and the preparation process of the nickel foam comprises the following steps:
(1) preparing foamed nickel:
placing polyurethane foam plastic in a mixed solution of hydrogen peroxide and sulfuric acid for coarsening for 100-140 s, and cleaning with deionized water; putting the mixture into a mixed solution of nickel sulfate and hydrochloric acid for 9-12 min, taking out and filtering to dry; placing the mixture in a mixed solution of sodium hydroxide and potassium borohydride for activating for 17-25 s, taking out and filtering to dry;
preparing a solution from nickel chloride, nickel sulfate and boric acid, adjusting the pH value to 1.8-2.4 to prepare a plating solution, wherein polyurethane foam plastic is used as a cathode, a nickel plate is used as an anode, and the pH value is 8-10A/dm 2Carrying out electrodeposition on the current density to prepare a foamed nickel plate;
taking a foamed nickel plate to be calcined, annealing in a reducing atmosphere at the annealing temperature of 600-1200 ℃, cleaning and drying to obtain a foamed nickel matrix;
(2) preparing foamed nickel:
adding deionized water into hexadecyl trimethyl ammonium bromide, heating to 28-32 ℃, stirring and dissolving, adding ammonia water, stirring, slowly adding butyl orthosilicate, stirring for 4-5 hours, keeping the temperature at 100 ℃ for 48-50 hours, filtering, drying, and sintering at 540-560 ℃ for 5-6 hours; adding a nickel chloride solution, uniformly mixing, placing a foamed nickel matrix in the mixture, performing ultrasonic treatment for 7-9 days, performing suction filtration, washing for 2-3 times, drying, heating to 900-950 ℃ at the speed of 5-6 ℃/min, roasting for 30-40 min, cooling, placing in hydrofluoric acid, and stirring for 2-3 h to obtain a nickel nanotube, thereby preparing foamed nickel.
2. The nickel foam/MXene-Co of claim 13O4The preparation method of the composite electrode is characterized by comprising the following steps: the step (1) comprises the following steps:
taking foamed nickel, sequentially carrying out ultrasonic cleaning for 2-3 times by using sulfuric acid, ethanol and deionized water, and drying in a constant-temperature oven at the drying temperature of 49.5-50.5 ℃ for 1-1.5 hours.
3. The nickel foam/MXene-Co of claim 13O4The preparation method of the composite electrode is characterized by comprising the following steps: the step (2) comprises the following steps:
taking MXene and Co3O4Mixing, oscillating for 2-4 min by using a vortex oscillator to prepare mixed powder, uniformly coating the mixed powder on the surface of the foamed nickel, and sintering by using vacuum plasma, wherein the sintering process comprises the following steps: and (3) carrying out vacuum at 25-55 Pa, sintering at 400-600 ℃, applying pressure at 1-2 MPa, and sintering for 10-15 min to obtain the composite electrode.
4. The nickel foam/MXene-Co of claim 13O4The preparation method of the composite electrode is characterized by comprising the following steps: the MXene and Co3O4The mass ratio is 1 (4-6), and the mass of the mixed powder is 0.05-0.1 g.
5. The nickel foam/MXene-Co of claim 13O4The preparation method of the composite electrode is characterized by comprising the following steps: the Co3O4The average particle diameter of (A) is 20 to 80 nm.
6. The nickel foam/MXene-Co of claim 13O4The preparation method of the composite electrode is characterized by comprising the following steps: the diameter of the foamed nickel is 2-3 cm, the pore diameter is 100-200 mu m, and the thickness is 3-4 mm.
7. A foamed nickel/MXene-Co according to any one of claims 1-63O4Foamed nickel/MXene-Co prepared by preparation method of composite electrode3O4And (3) a composite electrode.
8. A sewage advanced treatment method is characterized in that: the method of claim 7 is adopted for preparing the foamed nickel/MXene-Co3O4The composite electrode is a cathode for activating persulfate, and electrolyzing and degrading the 1, 4-dioxane.
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