CN111235614B - Preparation method and application of multifunctional self-supporting electrode with nitrogen-doped carbon wrapping structure - Google Patents
Preparation method and application of multifunctional self-supporting electrode with nitrogen-doped carbon wrapping structure Download PDFInfo
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Abstract
A preparation method and application of a multifunctional self-supporting electrode with a nitrogen-doped carbon wrapping structure comprise the following steps: pretreating the carbon cloth; carrying out electrodeposition on the pretreated carbon cloth by using electrolyte containing cobalt salt to obtain carbon cloth of a cobalt compound; then carrying out electropolymerization to obtain cobalt compound carbon cloth coated by polyaniline or polypyrrole; the carbon cloth loaded with nitrogen-doped carbon-coated cobalt is obtained by washing, alcohol washing, drying and carbonizing the cobalt compound carbon cloth coated by polyaniline or polypyrrole to serve as a multifunctional self-supporting electrode with a nitrogen-doped carbon coating structure. Can be applied to: catalyzing electrolysis water hydrogen evolution reaction in acidic or alkaline electrolyte; catalyzing electrolysis water oxygen evolution reaction in acidic or alkaline electrolyte; catalyzing and degrading organic pollutants in water, wherein the organic pollutants are one or more than 2 of 2-chlorophenol, bisphenol A, phenol and methylene blue. The preparation method has the characteristics of simplicity, novelty, low raw material cost, large pollutant removal amount and easy recovery of heterogeneous catalysis.
Description
Technical Field
The present invention relates to a self-supporting electrode. In particular to a preparation method and application of a multifunctional self-supporting electrode with a nitrogen-doped carbon coating structure.
Background
With the rapid development of economy and the rapid growth of population since the 21 st century, environment and energy have become two major problems in the world. Traditional fossil energy has been substantially exploited and depleted, and it generates many toxic and harmful gases during use, causing many climatic problems. Therefore, the search for a clean, efficient and renewable energy source becomes a great importance in solving the current energy crisis. Hydrogen gas, as a clean energy source, has a high energy density, and thus is considered as one of green energy sources most likely to replace conventional fossil energy. Among many hydrogen production methods, the hydrogen production method by electrolyzing water and separating out hydrogen becomes a hydrogen production mode with abundant raw materials and low cost, and the noble metal platinum catalyst has excellent performance, but the application and the development of the noble metal platinum catalyst are limited due to high cost. In addition, water body pollution caused by medicines, pesticides and laboratories exists for a long time, and the human health is harmed. Therefore, it is necessary to explore a new high-efficiency, low-cost bifunctional catalyst for a technology and a method for simultaneously solving the problems of energy and environment.
In recent years, a large number of non-noble metal materials have been studied for water decomposition, and in particular, various transition metal-based materials have high activity and stability. Typically including phosphides and sulfides, oxides/hydroxides, phosphides and borides of transition metals, are used on transition metal catalysts. And the transition metal is compounded with the carbon material, so that the conductivity of the material is greatly improved.
In the traditional catalytic degradation reaction, the homogeneous Fenton reaction must meet the requirement of pH 2-3, so that the application of the catalyst is greatly limited, the recovery process is complicated, and the cost is high. For the general heterogeneous catalytic reaction, the continuous consumption and leaching of metals also cause secondary pollution problems, and agglomeration is caused due to the interaction and attraction among particles in the reaction process, so that the catalytic activity is reduced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a multifunctional self-supporting electrode with a nitrogen-doped carbon coating structure, wherein the preparation method is simple and novel, the raw materials are low, and the coating structure can effectively avoid the problem of secondary metal pollution.
The technical scheme adopted by the invention is as follows: a preparation method of a multifunctional self-supporting electrode with a nitrogen-doped carbon wrapping structure comprises the following steps:
1) pretreating the carbon cloth;
2) carrying out electrodeposition on the pretreated carbon cloth by using electrolyte containing cobalt salt to obtain carbon cloth of a cobalt compound;
3) then carrying out electropolymerization to obtain cobalt compound carbon cloth coated by polyaniline or polypyrrole;
4) the carbon cloth loaded with nitrogen-doped carbon-coated cobalt is obtained by washing, alcohol washing, drying and carbonizing the cobalt compound carbon cloth coated by polyaniline or polypyrrole to serve as a multifunctional self-supporting electrode with a nitrogen-doped carbon coating structure.
Step 1) is to soak the mixed solution of concentrated nitric acid and concentrated sulfuric acid at the temperature of 90 ℃ for 6 hours by using the volume ratio of 1:3, then to dry the soaked solution at the temperature of 60 ℃ after respectively cleaning the soaked solution by using ethanol and deionized water.
And step 2) placing the pretreated carbon cloth in a cobalt salt solution with the concentration of 0.05-0.2 mol/L, and performing electrodeposition for 5-20 minutes to obtain the carbon cloth containing the cobalt compound.
The cobalt salt in the step 2) is one of hydrated cobalt nitrate, hydrated cobalt chloride and cobalt acetate.
Step 3) preparing electrolyte, wherein the concentration of sodium perchlorate in the electrolyte is 0.2mol/L, pyrrole or aniline with the volume fraction of 0.5-5% is contained in the electrolyte, and carbon cloth containing a cobalt compound is placed in the electrolyte for electropolymerization to obtain carbon cloth of the cobalt compound wrapped by polyaniline or polypyrrole;
the electropolymerization is carried out under the conditions that the circulating voltage range is-0.8 to-1.2V and the number of circulating circles is 5 to 20.
Step 4) comprises the steps of respectively cleaning cobalt compound carbon cloth wrapped by polyaniline or polypyrrole with ethanol and deionized water, drying at 60 ℃, then putting the cobalt compound carbon cloth into a tubular furnace, and carbonizing in an inert gas atmosphere, wherein the carbonization conditions are as follows: and the temperature is 400-900 ℃, the time is 2-8 hours, and the heating rate is 5-10 ℃/min, so that the nitrogen-doped carbon-coated cobalt compound carbon cloth self-supporting electrode is obtained.
The inert gas is nitrogen or argon.
The application of the multifunctional self-supporting electrode with the nitrogen-doped carbon wrapping structure is specifically applied to:
(1) catalyzing electrolysis water hydrogen evolution reaction in acidic or alkaline electrolyte;
(2) catalyzing electrolysis water oxygen evolution reaction in acidic or alkaline electrolyte;
(3) catalyzing and degrading organic pollutants in water, wherein the organic pollutants are one or more than 2 of 2-chlorophenol, bisphenol A, phenol and methylene blue.
The preparation method and the application of the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure have the advantages of simplicity, novelty, low raw material cost and capability of effectively avoiding the common problem of secondary metal pollution by the coating structure. The prepared multifunctional material can be applied to efficiently preparing clean energy by electrolyzing water, and has the characteristics of high catalytic efficiency, large pollutant removal amount and easy recovery of heterogeneous catalysis in the aspect of electrically-assisted catalytic degradation of pollutant phenol.
Drawings
FIG. 1 is an SEM photograph of the catalyst prepared in example 1;
FIG. 2 is an XRD pattern of the catalyst prepared in example 4;
FIG. 3 is a graph showing the change of the concentration of phenol solution in different periods of time when the catalyst prepared in example 5 degrades phenol.
Detailed Description
The following provides a detailed description of the preparation method and application of the multifunctional self-supporting electrode with a nitrogen-doped carbon-coated structure according to the present invention, with reference to the following embodiments and accompanying drawings.
The invention discloses a preparation method and application of a multifunctional self-supporting electrode with a nitrogen-doped carbon coating structure, which comprises the following steps:
1) pretreating the carbon cloth;
the method comprises the steps of soaking the mixture of concentrated nitric acid and concentrated sulfuric acid at a volume ratio of 1:3 at 90 ℃ for 6 hours, cleaning the mixture with ethanol and deionized water respectively, and drying the mixture at 60 ℃.
2) Carrying out electrodeposition on the pretreated carbon cloth by using electrolyte containing cobalt salt to obtain carbon cloth of a cobalt compound;
the method comprises the steps of placing the pretreated carbon cloth in a cobalt salt solution with the concentration of 0.05-0.2 mol/L, and carrying out electrodeposition for 5-20 minutes to obtain the carbon cloth containing the cobalt compound. Wherein, the cobalt salt is one of hydrated cobalt nitrate, hydrated cobalt chloride and cobalt acetate.
3) Then carrying out electropolymerization to obtain cobalt compound carbon cloth coated by polyaniline or polypyrrole;
preparing electrolyte, wherein the concentration of sodium perchlorate in the electrolyte is 0.2mol/L, pyrrole or aniline with the volume fraction of 0.5-5% is contained in the electrolyte, and carbon cloth containing a cobalt compound is arranged in the electrolyte for electropolymerization to obtain carbon cloth of the cobalt compound wrapped by polyaniline or polypyrrole; the electropolymerization is carried out under the conditions that the circulating voltage range is-0.8 to-1.2V and the number of circulating circles is 5 to 20.
4) The carbon cloth loaded with nitrogen-doped carbon-coated cobalt is obtained by washing, alcohol washing, drying and carbonizing the cobalt compound carbon cloth coated by polyaniline or polypyrrole to serve as a multifunctional self-supporting electrode with a nitrogen-doped carbon coating structure.
The method comprises the following steps of respectively cleaning cobalt compound carbon cloth wrapped by polyaniline or polypyrrole with ethanol and deionized water, drying at 60 ℃, putting the cobalt compound carbon cloth into a tubular furnace, and carbonizing in the atmosphere of inert gas, wherein the inert gas is nitrogen or argon, and the carbonization conditions are as follows: and the temperature is 400-900 ℃, the time is 2-8 hours, and the heating rate is 5-10 ℃/min, so that the nitrogen-doped carbon-coated cobalt compound carbon cloth self-supporting electrode is obtained.
The application of the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure is specifically applied to:
(1) catalyzing electrolysis water hydrogen evolution reaction in acidic or alkaline electrolyte;
(2) catalyzing electrolysis water oxygen evolution reaction in acidic or alkaline electrolyte;
(3) catalyzing and degrading organic pollutants in water, wherein the organic pollutants are one or more than 2 of 2-chlorophenol, bisphenol A, phenol and methylene blue.
Specific examples are given below:
example 1
(1) Soaking carbon cloth at 90 ℃ for 6 hours by using a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:3, cleaning the carbon cloth by using ethanol and deionized water, drying the carbon cloth at 60 ℃, and cutting the carbon cloth into 2cm multiplied by 1cm as substrate carbon cloth for later use;
(2) adding cobalt chloride into water, preparing a cobalt salt solution with the concentration of 0.2mol/L, then ultrasonically mixing uniformly to obtain an electrolyte A, immersing the cleaned carbon cloth into the electrolyte A, and carrying out electrodeposition for 5min to obtain a carbon cloth loaded with a cobalt compound;
(3) electrolyte B was prepared containing sodium perchlorate in a molar concentration of 0.2mol/L and containing 0.5% (volume fraction) of pyrrole solution. Further immersing the carbon cloth material loaded with the cobalt compound in the last step into electrolyte B for electropolymerization by using a cyclic voltammetry, wherein the cyclic voltage range is-0.8 to-1.2V, and the number of cyclic turns is 5, so as to obtain carbon cloth of the cobalt compound wrapped by polyaniline or polypyrrole;
(4) further, the obtained material is respectively washed by ethanol and water and then dried at 60 ℃, and is naturally cooled in a tubular furnace in a nitrogen atmosphere at the heating rate of 5 ℃/min and the temperature of 800 ℃ for 2h, so that the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure is obtained.
(5) Preparing 0.5mol/L sulfuric acid aqueous solution, and performing an electrolytic water hydrogen evolution reaction test by using a traditional three-electrode system, wherein the sweep rate is 5mV/s, and the sweep range is 0 to-1V (vs.
(6) The activity of the electrode material can also be evaluated by the reaction of electrically assisted activation of persulfate for phenol degradation. At room temperature, the initial concentration of 100mL of phenol in the reaction system is 20ppm, 0.1g of trace persulfate is put in, the catalyst is immersed into the reaction system to a depth of about 1mm, and the reaction system is assisted by cyclic voltammetry with a voltage (vs. RHE) of 0-1V in a three-electrode system of a workstation. 0.5mL of methanol was added to 0.5mL of the reaction mixture at regular intervals. The mixture was then aspirated by syringe, filtered and analyzed for phenol content in hplc.
The SEM image of the catalyst prepared in example 1 is shown in FIG. 1.
Example 2
(1) Soaking carbon cloth at 90 ℃ for 6 hours by using a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:3, cleaning the carbon cloth by using ethanol and deionized water, drying the carbon cloth at 60 ℃, and cutting the carbon cloth into 2cm multiplied by 1cm as substrate carbon cloth for later use;
(2) adding cobalt nitrate into water, preparing a cobalt salt solution with the concentration of 0.2mol/L, then ultrasonically mixing uniformly to obtain an electrolyte A, immersing the cleaned carbon cloth into the electrolyte A, and carrying out electrodeposition for 10min to obtain a carbon cloth loaded with a cobalt compound;
(3) electrolyte B was prepared containing sodium perchlorate in a molar concentration of 0.2mol/L and containing 1% (volume fraction) of pyrrole solution. Further immersing the carbon cloth material loaded with the cobalt compound in the last step into electrolyte B for electropolymerization by using a cyclic voltammetry, wherein the cyclic voltage range is-0.8 to-1.2V, and the number of cyclic turns is 5, so as to obtain carbon cloth of the cobalt compound wrapped by polyaniline or polypyrrole;
(4) further, the obtained material is respectively washed by ethanol and water and then dried at 60 ℃, heated at a rate of 5 ℃/min in a tube furnace under the argon atmosphere and at a temperature of 600 ℃ for 2h, and naturally cooled to obtain the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure.
(5) Preparing 0.5mol/L sulfuric acid aqueous solution, and performing an electrolytic water hydrogen evolution reaction test by using a traditional three-electrode system, wherein the sweep rate is 5mV/s, and the sweep range is 0 to-1V (vs.
(6) The activity of the electrode material can also be evaluated by the reaction of electrically assisted activation of persulfate for phenol degradation. At room temperature, the initial concentration of 100mL of phenol in the reaction system is 20ppm, 0.1g of trace persulfate is put in, the catalyst is immersed into the reaction system to a depth of about 1mm, and the reaction system is assisted by cyclic voltammetry with a voltage (vs. RHE) of 0-1V in a three-electrode system of a workstation. 0.5mL of methanol was added to 0.5mL of the reaction mixture at intervals. The mixture was then aspirated by syringe, filtered and analyzed for phenol content in hplc.
Example 3
(1) Soaking carbon cloth at 90 ℃ for 6 hours by using a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:3, cleaning the carbon cloth by using ethanol and deionized water, drying the carbon cloth at 60 ℃, and cutting the carbon cloth into 2cm multiplied by 1cm as substrate carbon cloth for later use;
(2) adding cobalt acetate into water to prepare a cobalt salt solution with the concentration of 0.2mol/L, then ultrasonically mixing uniformly to obtain an electrolyte A, immersing the cleaned carbon cloth into the electrolyte A, and carrying out electrodeposition for 12min to obtain a carbon cloth loaded with a cobalt compound;
(3) electrolyte B was prepared containing sodium perchlorate in a molar concentration of 0.2mol/L and 0.5% (volume fraction) of aniline solution. Further immersing the carbon cloth material loaded with the cobalt compound in the last step into electrolyte B for electropolymerization by using a cyclic voltammetry, wherein the cyclic voltage range is-0.8 to-1.2V, and the number of cyclic turns is 5, so as to obtain carbon cloth of the cobalt compound wrapped by polyaniline or polypyrrole;
(4) further, the obtained material is respectively washed by ethanol and water and then dried at 60 ℃, and is naturally cooled in a tubular furnace in a nitrogen atmosphere at the heating rate of 5 ℃/min and the temperature of 600 ℃ for 2h, so that the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure is obtained.
(5) Preparing 0.5mol/L sulfuric acid aqueous solution, and performing an electrolytic water hydrogen evolution reaction test by using a traditional three-electrode system, wherein the sweep rate is 5mV/s, and the sweep range is 0 to-1V (vs.
(6) The activity of the electrode material can also be evaluated by the reaction of electrically assisted activation of persulfate for bisphenol a degradation. At room temperature, the initial concentration of 100mL of bisphenol A in the reaction system is 20ppm, 0.1g of trace persulfate is put in, the catalyst is immersed into the reaction system to a depth of about 1mm, and the reaction system is assisted by a cyclic voltammetry method with a voltage (vs.RHE) of 0-1V in a three-electrode system of a workstation. 0.5mL of methanol was added to 0.5mL of the reaction mixture at regular intervals. The mixture was then aspirated by syringe, filtered and analyzed for bisphenol a content in hplc.
Example 4
(1) Soaking carbon cloth at 90 ℃ for 6 hours by using a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:3, cleaning the carbon cloth by using ethanol and deionized water, drying the carbon cloth at 60 ℃, and cutting the carbon cloth into 2cm multiplied by 1cm as substrate carbon cloth for later use;
(2) adding cobalt chloride into water, preparing a cobalt salt solution with the concentration of 0.1mol/L, then ultrasonically mixing uniformly to obtain an electrolyte A, immersing the cleaned carbon cloth into the electrolyte A, and carrying out electrodeposition for 5min to obtain a carbon cloth loaded with a cobalt compound;
(3) electrolyte B was prepared containing sodium perchlorate in a molar concentration of 0.2mol/L and containing 1% (volume fraction) of pyrrole solution. Further immersing the carbon cloth material loaded with the cobalt compound in the last step into electrolyte B for electropolymerization by using a cyclic voltammetry, wherein the cyclic voltage range is-0.8 to-1.2V, and the number of cyclic turns is 10, so as to obtain carbon cloth of the cobalt compound wrapped by polyaniline or polypyrrole;
(4) further, the obtained material is respectively washed by ethanol and water and then dried at 60 ℃, the temperature is raised at 10 ℃/min and maintained at 900 ℃ for 2h in a tube furnace in the argon atmosphere, and the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure is obtained by natural cooling.
(5) Preparing 0.5mol/L sulfuric acid aqueous solution, and performing an electrolytic water hydrogen evolution reaction test by using a traditional three-electrode system, wherein the sweep rate is 5mV/s, and the sweep range is 0 to-1V (vs.
(6) The activity of the electrode material can also be evaluated by the reaction of electrically assisted activation of persulfate for phenol degradation. At room temperature, the initial concentration of 100mL of phenol in the reaction system is 20ppm, 0.1g of micro persulfate is placed, the catalyst is immersed into the reaction system to a depth of about 1mm, and the reaction system is assisted by cyclic voltammetry with a voltage (vs. RHE) of 0-1V in a three-electrode system of a workstation. 0.5mL of methanol was added to 0.5mL of the reaction mixture at regular intervals. The mixture was then aspirated by syringe, filtered and analyzed for phenol content in a high performance liquid chromatograph.
The XRD of the catalyst prepared in example 4 is shown in fig. 2.
Example 5
(1) Soaking carbon cloth at 90 ℃ for 6 hours by using a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:3, cleaning the carbon cloth by using ethanol and deionized water, drying the carbon cloth at 60 ℃, and cutting the carbon cloth into 2cm multiplied by 1cm as substrate carbon cloth for later use;
(2) adding cobalt nitrate into water to prepare a cobalt salt solution with the concentration of 0.1mol/L, then ultrasonically mixing uniformly to obtain an electrolyte A, immersing the cleaned carbon cloth into the electrolyte A, and carrying out electrodeposition for 5min to obtain a carbon cloth loaded with a cobalt compound;
(3) electrolyte B was prepared containing sodium perchlorate in a molar concentration of 0.2mol/L and 2% (volume fraction) of pyrrole solution. Further immersing the carbon cloth material loaded with the cobalt compound in the last step into electrolyte B for electropolymerization by using a cyclic voltammetry, wherein the cyclic voltage range is-0.8 to-1.2V, and the number of cyclic turns is 20, so as to obtain carbon cloth of the cobalt compound wrapped by polyaniline or polypyrrole;
(4) further, the obtained material is respectively washed by ethanol and water and then dried at 60 ℃, and is naturally cooled in a tube furnace in nitrogen atmosphere at the heating rate of 8 ℃/min and the temperature of 800 ℃ for 2h, so that the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure is obtained.
(5) Preparing 0.5mol/L sulfuric acid aqueous solution, and performing an electrolytic water hydrogen evolution reaction test by using a traditional three-electrode system, wherein the sweep rate is 5mV/s, and the sweep range is 0 to-1V (vs.
(6) The activity of the electrode material can also be evaluated by the reaction of electrically assisted activation of persulfate for phenol degradation. At room temperature, the initial concentration of 100mL of phenol in the reaction system is 20ppm, 0.1g of trace persulfate is put in, the catalyst is immersed into the reaction system to a depth of about 1mm, and the reaction system is assisted by cyclic voltammetry with a voltage (vs. RHE) of 0-1V in a three-electrode system of a workstation. 0.5mL of methanol was added to 0.5mL of the reaction mixture at regular intervals. The mixture was then aspirated by syringe, filtered and analyzed for phenol content in hplc.
The concentration of the phenol solution in different periods of time when the catalyst prepared in example 5 degrades phenol is changed as shown in fig. 3.
Example 6
(1) Soaking carbon cloth at 90 ℃ for 6 hours by using a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:3, cleaning the carbon cloth by using ethanol and deionized water, drying the carbon cloth at 60 ℃, and cutting the carbon cloth into 2cm multiplied by 1cm as substrate carbon cloth for later use;
(2) adding one of cobalt salts such as cobalt acetate into water, preparing a cobalt salt solution with the concentration of 0.1mol/L, then ultrasonically mixing uniformly to obtain an electrolyte A, immersing the cleaned carbon cloth into the electrolyte A, and performing electrodeposition for 5min to obtain a carbon cloth loaded with a cobalt compound;
(3) electrolyte B was prepared containing sodium perchlorate in a molar concentration of 0.2mol/L and 3% (volume fraction) of aniline solution. Further immersing the carbon cloth material loaded with the cobalt compound in the last step into electrolyte B for electropolymerization by using a cyclic voltammetry, wherein the cyclic voltage range is-0.8 to-1.2V, and the number of cyclic turns is 20, so as to obtain carbon cloth of the cobalt compound wrapped by polyaniline or polypyrrole;
(4) further, the obtained material is respectively washed by ethanol and water and then dried at 60 ℃, heated at a rate of 8 ℃/min in a tube furnace under the argon atmosphere and at a temperature of 800 ℃ for 8h, and naturally cooled to obtain the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure.
(5) Preparing 0.5mol/L sulfuric acid aqueous solution, and performing an electrolytic water hydrogen evolution reaction test by using a traditional three-electrode system, wherein the sweep rate is 5mV/s, and the sweep range is 0 to-1V (vs.
(6) The activity of the electrode material can also be evaluated by the reaction of electrically assisted activation of persulfate for phenol degradation. At room temperature, the initial concentration of 100mL of phenol in the reaction system is 20ppm, 0.1g of trace persulfate is put in, the catalyst is immersed into the reaction system to a depth of about 1mm, and the reaction system is assisted by cyclic voltammetry with a voltage (vs. RHE) of 0-1V in a three-electrode system of a workstation. 0.5mL of methanol was added to 0.5mL of the reaction mixture at regular intervals. The mixture was then aspirated by syringe, filtered and analyzed for phenol content in hplc.
Example 7
(1) Soaking carbon cloth at 90 ℃ for 6 hours by using a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:3, cleaning the carbon cloth by using ethanol and deionized water, drying the carbon cloth at 60 ℃, and cutting the carbon cloth into 2cm multiplied by 1cm as substrate carbon cloth for later use;
(2) adding cobalt chloride into water, preparing a cobalt salt solution with the concentration of 0.05mol/L, then ultrasonically mixing uniformly to obtain an electrolyte A, immersing the cleaned carbon cloth into the electrolyte A, and carrying out electrodeposition for 20min to obtain a carbon cloth loaded with a cobalt compound;
(3) electrolyte B was prepared containing sodium perchlorate in a molar concentration of 0.2mol/L and containing 5% (volume fraction) of pyrrole solution. Further immersing the carbon cloth material loaded with the cobalt compound in the last step into electrolyte B for electropolymerization by using a cyclic voltammetry, wherein the cyclic voltage range is-0.8 to-1.2V, and the number of cyclic turns is 20, so as to obtain carbon cloth of the cobalt compound wrapped by polyaniline or polypyrrole;
(4) further, the obtained material is respectively washed by ethanol and water and then dried at 60 ℃, and is naturally cooled in a tubular furnace in a nitrogen atmosphere at the heating rate of 5 ℃/min and the temperature of 400 ℃ for 6h, so that the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure is obtained.
(5) Preparing 0.5mol/L sulfuric acid aqueous solution, and performing an electrolytic water hydrogen evolution reaction test by using a traditional three-electrode system, wherein the sweep rate is 5mV/s, and the sweep range is 0 to-1V (vs.
(6) The activity of the electrode material can also be evaluated by the reaction of electrically assisted activation of persulfate for methylene blue degradation. At room temperature, the initial concentration of 100mL of methylene blue in the reaction system is 20ppm, 0.1g of trace persulfate is placed, the catalyst is immersed into the reaction system to a depth of about 1mm, and the reaction system is assisted by a cyclic voltammetry method with a voltage (vs.RHE) of 0-1V in a three-electrode system of a workstation. 0.5mL of methanol was added to 0.5mL of the reaction mixture at regular intervals. The mixture was then aspirated by syringe, filtered and analyzed for methylene blue content in hplc.
Claims (5)
1. The application of the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure is characterized by being specifically applied to: catalytically degrading organic pollutants in water, wherein the organic pollutants are one or more than 2 of 2-chlorophenol, bisphenol A, phenol and methylene blue; the preparation method of the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure comprises the following steps:
1) pretreating the carbon cloth;
2) carrying out electrodeposition on the pretreated carbon cloth by using electrolyte containing cobalt salt to obtain carbon cloth of a cobalt compound; the cobalt salt is one of hydrated cobalt nitrate, hydrated cobalt chloride and cobalt acetate;
3) then carrying out electropolymerization to obtain cobalt compound carbon cloth wrapped by polyaniline or polypyrrole; preparing electrolyte, wherein the concentration of sodium perchlorate in the electrolyte is 0.2mol/L, pyrrole or aniline with the volume fraction of 0.5-5% is contained in the electrolyte, and carbon cloth containing a cobalt compound is arranged in the electrolyte for electropolymerization to obtain carbon cloth of the cobalt compound wrapped by polyaniline or polypyrrole;
4) washing cobalt compound carbon cloth wrapped by polyaniline or polypyrrole with water, washing with alcohol, drying and carbonizing to obtain carbon cloth loaded with nitrogen-doped carbon-wrapped cobalt as a multifunctional self-supporting electrode with a nitrogen-doped carbon-wrapped structure; the method comprises the following steps of respectively cleaning cobalt compound carbon cloth wrapped by polyaniline or polypyrrole with ethanol and deionized water, drying at 60 ℃, putting the cobalt compound carbon cloth into a tubular furnace, and carbonizing in an inert gas atmosphere, wherein the carbonization conditions are as follows: the temperature is 400-900 ℃, the time is 2-8 hours, and the heating rate is 5-10 ℃/min, so that the nitrogen-doped carbon-coated cobalt compound carbon cloth self-supporting electricity is obtained.
2. The application of the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure as claimed in claim 1, wherein the step 1) is to soak the mixed solution of concentrated nitric acid and concentrated sulfuric acid at a volume ratio of 1:3 at 90 ℃ for 6 hours, then to clean the electrode with ethanol and deionized water, and to dry the electrode at 60 ℃.
3. The application of the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure as claimed in claim 1, wherein the step 2) comprises the steps of placing the pretreated carbon cloth in a cobalt salt solution with the concentration of 0.05-0.2 mol/L, and performing electrodeposition for 5-20 minutes to obtain the carbon cloth containing the cobalt compound.
4. The application of the multifunctional self-supporting electrode with the nitrogen-doped carbon coating structure as claimed in claim 1, wherein the electropolymerization is carried out under the conditions that the cycling voltage range is-0.8 to-1.2V and the cycle number is 5 to 20 cycles.
5. The use of the nitrogen-doped carbon wrapped structure multifunctional self-supporting electrode according to claim 1, wherein the inert gas is nitrogen or argon.
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