CN113594476B - Carbon nitride modified methanol electrocatalyst and preparation method and application thereof - Google Patents

Carbon nitride modified methanol electrocatalyst and preparation method and application thereof Download PDF

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CN113594476B
CN113594476B CN202110863663.6A CN202110863663A CN113594476B CN 113594476 B CN113594476 B CN 113594476B CN 202110863663 A CN202110863663 A CN 202110863663A CN 113594476 B CN113594476 B CN 113594476B
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carbon nitride
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江彬彬
汪谢
周菊红
唐文韬
王涛
高迎春
庞韬
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Shanxi Oubeim Nanotechnology Co ltd
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Abstract

The invention provides a carbon nitride modified methanol electrocatalyst and a preparation method and application thereof. Replaces the traditional noble metal catalyst, and provides an electrocatalyst which is cheap and easy to obtain and has outstanding electrocatalytic activity for the methanol fuel cell.

Description

Carbon nitride modified methanol electrocatalyst and preparation method and application thereof
Technical Field
The invention relates to the field of preparation and application of carbon nitride-based nano materials, in particular to a carbon nitride modified methanol electrocatalyst and a preparation method and application thereof, and specifically relates to preparation of a carbon nitride modified NiMn bimetal oxide nano material and application thereof in a methanol fuel cell.
Background
With the increasing energy crisis and environmental pollution, people need to develop a clean and sustainable novel energy source urgently. Methanol fuel cells are receiving wide attention due to their high energy density and low environmental pollution. At present, the key point of the preparation of the methanol fuel cell is to design and construct an electrocatalyst with high electrocatalytic activity, low price and easy obtainment so as to replace the traditional noble metal catalyst.
Double metal hydroxides are currently considered to be one of the most competitive candidates for methanol oxidation electrocatalysts. Among them, the NiMn double metal hydroxide (NiMn LDH) also shows a certain electrocatalytic activity. However, the activity of NiMn LDH cannot meet commercial requirements due to poor conductivity and slow mass transfer rate.
Disclosure of Invention
The invention aims to provide a carbon nitride modified methanol electrocatalyst and a preparation method thereof, which is a NiMn bimetallic oxide nano material modified by carbon nitride rich in oxygen vacancies, uses a nitrogen-containing compound as a nitrogen source and a carbon material as a carrier to firstly prepare a carbon nitride material, and then deposits NiMn bimetallic hydroxide on the carbon nitride material through hydrothermal reaction to prepare the carbon nitride modified methanol electrocatalyst. In the catalyst, the NiMn bimetal hydroxide generates oxygen vacancy due to the strong adsorption effect of carbon nitride on hydroxyl, and the content of the oxygen vacancy reaches 40 percent; the preparation method is simple and the product has uniform appearance.
Still another object of the present invention is to provide an application of the carbon nitride modified methanol electrocatalyst in the aspect of methanol fuel cells.
The specific technical scheme of the invention is as follows:
a preparation method of a carbon nitride modified methanol electrocatalyst comprises the following steps:
A. dispersing a carbon material and a nitrogen-containing compound in water, uniformly stirring, freeze-drying, and calcining the obtained mixture to obtain a carbon nitride/carbon material;
B. dispersing carbon nitride/carbon material in a mixed solvent to form a uniformly dispersed dispersion liquid;
C. and D, dropwise adding the nickel-manganese mixed solution into the dispersion liquid prepared in the step B under the stirring state, then adding urea, and carrying out hydrothermal reaction to obtain the carbon nitride modified NiMn double metal hydroxide/carbon nano composite material.
In the step A, the water is deionized water;
in step A, the freeze-drying conditions are as follows: drying at-40-80 deg.C under vacuum degree of 0.1-30Pa for 12-48 h;
in the step A, the carbon material and the nitrogen-containing chemical can be fully and uniformly mixed by freeze drying, so that the nitrogen-containing compound is not volatilized;
the carbon material in the step A comprises one or more of carbon black, graphene or carbon nano tubes; the nitrogen-containing chemical compound is one or more of urea, dicyandiamide or melamine;
the mass ratio of the carbon material to the nitrogen-containing compound in step A is 2: 1-1: 3, or more;
the dosage ratio of the carbon material to the water in the step A is 0.2-5 mg/ml;
in the step A, the calcining temperature ranges from 400 ℃ to 700 ℃ and the calcining time is 0.5h to 2 h.
The mixed solvent in the step B is a mixed solvent of water and alcohol;
the mixed solvent of water and alcohol in the step B is beneficial to the dispersion of the carbon nitride/carbon composite material;
b, forming uniformly dispersed dispersion liquid by ultrasonic treatment for 0.5-2 h;
in the mixed solvent of water and alcohol in the step B, the volume ratio of alcohol to water is 1: 0.1-1: 10;
the alcohol in the step B is selected from any one or a combination of more of ethylene glycol, ethanol and methanol.
In the step B, the dosage ratio of the carbon nitride/carbon material to the mixed solvent is 0.2-2 mg/ml;
the preparation method of the nickel-manganese mixed solution in the step C comprises the following steps: dissolving nickel salt and manganese salt in a mixed solvent of water and alcohol; the nickel salt is selected from nickel chloride hexahydrate, nickel nitrate hexahydrate, nickel sulfate hexahydrate or nickel acetate tetrahydrate; the manganese salt is soluble manganese salt selected from manganese nitrate, manganese sulfate monohydrate, manganese acetate tetrahydrate or manganese chloride tetrahydrate; the ratio of the total mass of the nickel salt and the manganese salt to the dosage of the mixed solvent is 1-10 mg/mL; the molar ratio of the nickel salt to the manganese salt is 2:1-25: 1;
the volume ratio of the nickel-manganese mixed solution in the step C to the dispersion liquid in the step B is 0.1: 1-10: 1;
the mixed solvent of water and alcohol in the step C is the same as the mixed solvent in the step B;
the function of the urea in the step C is to provide a weak alkaline environment;
dropwise adding in the step C to enable the metal salt to be uniformly dissolved in the dispersion liquid prepared in the step B;
in the step C, the ratio of the urea consumption to the total mass of the nickel salt and the manganese salt is 1: 1-100: 1;
the hydrothermal reaction in the step C refers to: reacting for 4-48 hours at 70-180 ℃;
in the step C, after the hydrothermal reaction is finished, precipitating, cooling, separating, washing the precipitate with water, then washing with alcohol, and drying in vacuum at 40-60 ℃ to constant weight to obtain the carbon nitride modified NiMn bimetal hydroxide/carbon nano composite material, namely the carbon nitride modified methanol electrocatalyst;
c, the NiMn double metal hydroxide/carbon nano composite material modified by the carbon nitride is rich in oxygen vacancies;
and step C, controlling the dosage of carbon nitride by adjusting the concentration of the dispersion liquid in the step B and the dosage ratio of the metal salt in the step C, wherein the carbon nitride adsorbs hydroxyl of the NiMn double metal hydroxide by an electronegativity principle to obtain oxygen vacancy samples with different contents, and the content of the oxygen vacancies is 5-40%.
And C, the NiMn double metal hydroxide/carbon nano composite material modified by the carbon nitride is of a sheet structure. The size is between 100nm and 500 nm.
The invention provides a carbon nitride modified methanol electrocatalyst which is prepared by the method, wherein the prepared carbon nitride modified NiMn bimetal hydroxide/carbon nano composite material is of a sheet structure, namely the carbon nitride modified methanol electrocatalyst.
The invention provides an application of a carbon nitride modified methanol electrocatalyst in the aspect of methanol electrocatalysis.
The electrocatalysis performance test method comprises the following steps:
1) ultrasonically dispersing a carbon nitride modified methanol electrocatalyst in deionized water to prepare a dispersion solution;
2) preparing 0.1M KOH and 0.1M methanol solution by using deionized water; then, absorbing the dispersion solution of the carbon nitride modified methanol electrocatalyst, dripping the dispersion solution on the surface of the glassy carbon electrode, and placing the glassy carbon electrode for natural drying;
3) and recording the electrocatalysis process of the electrochemical workstation on methanol between 0.0-0.8V vs. Ag/AgCl by adopting the electrochemical workstation.
Carbon nitride (C)3N4) Has good chemical stability and unique electronic structureHas certain research potential in the field of catalysis. C3N4The conductivity of the target material can be improved through the coupling effect between the double metals, a large number of oxygen vacancies are generated, and the catalytic activity of the material is improved. For the invention C3N4The modified NiMn LDH/carbon nano composite material with the content of oxygen vacancies is used as a methanol oxidation electrocatalyst.
The invention takes carbon material and nitrogen-containing compound as precursor, carbon nitride/carbon material is prepared after uniform mixing and high-temperature calcination, and nickel salt, manganese salt and urea are added into the mixed solution of water and alcohol by taking the carbon nitride/carbon material as matrix, and then the NiMn double-metal hydroxide/carbon nano composite material modified by carbon nitride can be prepared after hydrothermal reaction, and the material is rich in oxygen vacancy and shows excellent electrocatalytic activity to methanol.
Compared with the prior art, the method for preparing the NiMn bimetal hydroxide/carbon nano composite material modified by the carbon nitride is simple and uniform in appearance, and the NiMn bimetal hydroxide composite material generates a large amount of oxygen vacancies with the highest content of 40 percent due to the strong adsorption effect of the carbon nitride on hydroxyl. The NiMn bimetal hydroxide/carbon nano composite material modified by the carbon nitride prepared by the method has excellent electrocatalytic activity on methanol, and the activity on 0.1M methanol in 0.1M KOH solution is up to 64 mA-cm-2. In addition, the electrocatalytic activity of the catalyst relative to the NiMn double metal hydroxide/carbon nano composite material is improved by 5 to 32 times due to the action of oxygen vacancies.
The invention takes transition metal compound as raw material, and carbon nitride is modified, thus replacing traditional noble metal catalyst, and providing an electrocatalyst with low cost, easy obtaining and outstanding electrocatalytic activity for methanol fuel cells. The nano composite catalyst also has the advantages of simple preparation method, uniform appearance and the like, is applied to the field of methanol electrocatalysis, and can provide a practical thought for solving the current increasingly serious energy crisis and environmental pollution problems.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of the carbon nitride modified NiMn double metal hydroxide/graphene nanomaterial prepared in example 1;
FIG. 2 is a SEM photograph of the NiMn double metal hydroxide/graphene nano material modified by carbon nitride obtained in example 1;
FIG. 3 is an XPS plot of the carbon nitride modified NiMn double metal hydroxide/graphene nanomaterial obtained in example 1;
FIG. 4 is a surface elemental analysis chart of the NiMn double metal hydroxide/carbon graphene nanomaterial modified by carbon nitride obtained in example 1;
FIG. 5 shows electron paramagnetic resonance spectra of NiMn double metal hydroxide/graphene nanomaterial and NiMn double metal hydroxide/graphene nanomaterial modified by carbon nitride obtained in example 1;
FIG. 6 is an oxygen high resolution XPS plot of the carbon nitride modified NiMn double metal hydroxide/graphene nanomaterial obtained in example 1;
FIG. 7 is a graph of CV of methanol oxidation of the NiMn double metal hydroxide/graphene nanomaterial modified by carbon nitride obtained in example 1;
fig. 8 is a graph of CV of methanol oxidation of the NiMn double metal hydroxide/graphene nanomaterial obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of a carbon nitride modified methanol electrocatalyst comprises the following steps:
A. mixing: at room temperature, adding 100mg of urea and 100mg of graphene into 50mL of deionized water, performing ultrasonic treatment to uniformly disperse the urea and the graphene, and drying the urea and the graphene for 40 hours at the temperature of minus 40 ℃ and the vacuum degree of 0.5 Pa; calcining at 550 ℃ for 2h in an air atmosphere after freeze drying; cooling to obtain the carbon nitride/graphene composite material;
B. dispersing: weighing 8mg of carbon nitride/graphene composite material in a volume ratio of 10mL to 1: 1, dispersing the mixture in a mixed solvent of ethylene glycol and water by ultrasonic treatment for 0.5 h;
C. preparation: adding 0.0470g of nickel chloride hexahydrate and 0.0025g of manganese chloride tetrahydrate into 10mL of mixed solution of ethylene glycol and water (the specific volume is 1: 1) at room temperature, then dropwise and slowly adding the solution into the dispersion liquid in the step B under the action of stirring, then adding 150mg of urea, and finally heating the prepared solution to 120 ℃ and reacting for 10 hours;
D. and (3) drying: cooling and separating the reacted system, washing the precipitate with water and then alcohol, and drying the precipitate in vacuum at 60 ℃ to constant weight, namely the carbon nitride modified NiMn double metal hydroxide/graphene composite material (NiMn LDH/C)3N4/G), EPR test shows that NiMn LDH/C3N4the/G composite contains a large number of oxygen vacancies (fig. 5) and a content of oxygen vacancies of up to 40% (fig. 6), i.e. a carbon nitride modified methanol electrocatalyst.
And (3) testing the electrocatalytic performance:
NiMn LDH/C obtained in example 13N4The catalyst is used for electrocatalytic reaction of methanol:
firstly, weighing a certain amount of NiMn LDH/C3N4the/G nano material is ultrasonically dispersed in deionized water to prepare a 4mg/L dispersion solution; secondly, preparing 0.1M KOH and 0.1M methanol solution by using deionized water; then, 6 mu L of 4mg/L dispersion solution is absorbed and dripped on the surface of a glassy carbon electrode and naturally dried; and finally, recording the electrocatalysis process of the electrochemical workstation on methanol in 0.1M KOH solution at a potential window of 0.0-0.8V vs. Ag/AgCl. It can be seen that under 0.0M methanol conditions, NiMn LDH/C3N4the/G nano composite material has only weak background current, and NiMn LDH/C is obtained after 0.1M methanol is added3N4the/G nano composite material has good electro-catalytic reaction on methanol, and the catalytic current of the material can reach 64 mA-cm-2(FIG. 7).
Meanwhile, NiMn LDH/G nanocomposite material was prepared for comparison, and the preparation procedure was as follows
A. Dispersing: weighing 8mg of graphene in 10mL of a volume ratio of 1: 1, dispersing the mixture in a mixed solvent of ethylene glycol and water by ultrasonic waves;
B. preparation: adding 0.0470g of nickel chloride hexahydrate and 0.0025g of manganese chloride tetrahydrate into 10mL of mixed solution of ethylene glycol and water (the specific volume is 1: 1) at room temperature, then slowly dropwise adding the solution into the dispersion liquid obtained in the step B under the action of stirring, adding 150mg of urea, and finally heating the prepared solution to 120 ℃ for 10 hours;
C. and (3) drying: and cooling and separating the reacted system, washing the precipitate with water and then with alcohol, and drying the precipitate at 60 ℃ in vacuum to constant weight, namely the NiMn double metal hydroxide/graphene composite material (NiMn LDH/G), wherein EPR shows that the oxygen vacancy content of the material is almost negligible (figure 5). In 0.1M KOH solution, the response current of NiMn LDH/G is weak under the condition of 0.0M methanol concentration, and the catalytic current of the NiMn LDH/G is only 2 mA-cm for 0.1M methanol-2(FIG. 8). In comparison, NiMn LDH/C3N4The electrocatalytic current of the/G nano composite material is improved by 32 times.
Example 2
A preparation method of a carbon nitride modified methanol electrocatalyst comprises the following steps:
A. mixing: at room temperature, adding 50mg of melamine and 50mg of carbon black into 30mL of deionized water, performing ultrasonic treatment to uniformly disperse the melamine and the carbon black, drying the melamine and the carbon black for 20 hours at the temperature of 50 ℃ below zero and the vacuum degree of 10Pa, and calcining the melamine and the carbon black for 2 hours at the temperature of 550 ℃ in an air atmosphere after freeze drying; cooling to obtain the carbon nitride/carbon black composite material
B. Dispersing: weighing 6mg of carbon nitride/carbon black composite material in 10mL of a volume ratio of 1: 1, dispersing the mixture in a mixed solvent of ethanol and water by ultrasonic treatment for 1 hour to be uniform;
C. preparation: adding 0.0580g of nickel nitrate hexahydrate and 0.0025g of manganese nitrate into a mixed solution of 10mL of ethanol and water (the specific volume is 1: 1) at room temperature, then slowly dropwise adding the solution into the dispersion liquid obtained in the step B under the stirring action, then adding 300mg of urea, and finally heating the prepared solution to 100 ℃ for 18 hours;
D. and (3) drying: cooling and separating the reacted system, washing the precipitate with water and alcohol, and vacuum drying at 40 deg.c to constant weight to obtain carbon nitride modified NiMn double metal hydroxide/carbon black nanometer composite material (NiMn LDH/C)3N4/C) and the content of oxygen vacancies was 22%.
And (3) testing the electrocatalytic performance:
NiMn LDH/C obtained in example 23N4the/C is used as a catalyst for electrocatalytic reaction of methanol:
firstly, weighing a certain amount of NiMn LDH/C3N4the/C nano material is ultrasonically dispersed in deionized water to prepare a 3mg/L dispersion solution; secondly, preparing 0.1M KOH and 0.1M methanol solution by using deionized water; then, 6 mu L of 5mg/L dispersion solution is absorbed and dropped on the surface of the glassy carbon electrode and naturally cooled; finally, an electrochemical workstation is adopted to record the electrocatalysis process of the electrochemical workstation on methanol between 0.0-0.8V vs. Ag/AgCl, and the obtained NiMn LDH/C can be seen3N4the/C nano composite material has good electrocatalytic reaction on methanol. NiMn LDH/C in 0.1M KOH solution3N4The catalytic activity of the/C nano composite material to 0.1M methanol is 48 mA-cm-2
Under the same conditions, NiMn double metal hydroxide/carbon black nano composite material (NiMn LDH/C) is prepared for comparison, and the preparation procedure is as follows
A. Dispersing: weigh 6mg of carbon black in 10mL of 1: 1, in a mixed solvent of ethanol and water, and ultrasonically dispersing the mixture uniformly;
B. preparation: adding 0.0580g of nickel nitrate hexahydrate and 0.0025g of manganese nitrate hexahydrate into 10mL of mixed solution of ethanol and water (the specific volume is 1: 1) at room temperature, then slowly dropwise adding the solution into the dispersion liquid obtained in the step B under the action of stirring, adding 300mg of urea, and finally heating the prepared solution to 100 ℃ for 18 hours;
C. and (3) drying: and cooling and separating the reacted system, washing the precipitate with water and then alcohol, and drying in vacuum at 40 ℃ to constant weight to obtain the NiMn double metal hydroxide/carbon black nano composite material (NiMn LDH/C).
In 0.1M KOH solution, the catalytic activity of the NiMn LDH/C composite material to 0.1M methanol is only 2 mA-cm-2. In comparison, NiMn LDH/C3N4The electrocatalytic activity of the/C nano composite material is improved by 24 times.
Example 3
A preparation method of a carbon nitride modified methanol electrocatalyst comprises the following steps:
A. mixing: at room temperature, adding 100mg of dicyandiamide and 100mg of carbon nano tubes into 60mL of deionized water, performing ultrasonic treatment to uniformly disperse the dicyandiamide and the carbon nano tubes, drying the mixture for 15 hours at the temperature of minus 80 ℃ and the vacuum degree of 20Pa, and calcining the dried mixture for 2 hours at the temperature of 600 ℃ in an air atmosphere; cooling to obtain the carbon nitride/carbon nanotube composite material
B. Dispersing: weighing 8mg of carbon nitride/carbon nanotube composite material in 10mL of a mixture with the volume ratio of 1: 1, mixing the mixture of methanol and water in a mixed solvent of methanol and water, and performing ultrasonic treatment for 1 hour to obtain uniform mixture;
C. preparation: 0.0650g of nickel sulfate hexahydrate and 0.0035g of manganese sulfate monohydrate are added into 10mL of mixed solution of ethylene glycol and water (the specific volume is 1: 1) at room temperature, then the solution is slowly dripped into the dispersion liquid in the step B under the stirring action, 180mg of urea is added, and finally the prepared solution is heated to 80 ℃ and the reaction time is 24 hours;
D. and (3) drying: cooling and separating the reacted system, washing the precipitate with water and then alcohol, and vacuum drying at 60 deg.c to constant weight to obtain carbon nitride modified NiMn double metal hydroxide/carbon nanotube nano composite material (NiMn LDH/C)3N4/CNT) and the content of oxygen vacancies was 29%.
And (3) testing the electrocatalytic performance:
NiMn LDH/C obtained in example 33N4the/CNT is used as a catalyst for electrocatalytic reaction of methanol:
firstly, weighing a certain amount of NiMn LDH/C3N4the/CNT nano material is ultrasonically dispersed in deionized water to prepare a 4mg/L dispersion solution; secondly, preparing 0.1M KOH and 0.1M methanol solution by using deionized water; then, 6 mu L of 4mg/L of dispersion solution is absorbed and dropped on the surface of the glassy carbon electrode and naturally cooled; finally, an electrochemical workstation is adopted to record the electrocatalysis process of the electrochemical workstation on methanol within the potential window of 0.0-0.8V vs. Ag/AgCl, and the obtained NiMn LDH/C can be seen3N4the/CNT nano composite material has good effect on methanolGood electrocatalytic reaction. NiMn LDH/C in 0.1M KOH solution3N4The catalytic activity of the/CNT nano composite material to 0.1M methanol is 52 mA-cm-2
Under the same condition, preparing NiMn double metal hydroxide/carbon nano tube nano composite material (NiMn LDH/C)3N4CNT) for comparison, the procedure for its preparation is as follows:
A. dispersing: weighing 8mg of the carbon nanotube composite material in 10mL of a mixture with the volume ratio of 1: 1, in a mixed solvent of methanol and water, and uniformly dispersing by ultrasonic;
B. preparation: 0.0650g of nickel sulfate hexahydrate and 0.0035g of manganese sulfate monohydrate are added into 10mL of mixed solution of ethylene glycol and water (the specific volume is 1: 1) at room temperature, then the solution is slowly dripped into the dispersion liquid in the step B under the stirring action, 180mg of urea is added, and finally the prepared solution is heated to 80 ℃ and the reaction time is 24 hours;
C. and (3) drying: cooling and separating the reacted system, washing the precipitate with water and alcohol, and vacuum drying at 60 deg.c to constant weight to obtain the NiMn double metal hydroxide/carbon nanotube nano composite material (NiMn LDH/C)3N4/CNT). NiMn LDH/C in 0.1M KOH solution3N4The catalytic activity of the/CNT on 0.1M methanol is only 3 mA-cm-2In comparison, NiMn LDH/C3N4The electrocatalytic activity of the/CNT nano composite material is improved by 17 times.
Example 4
A preparation method of a carbon nitride modified methanol electrocatalyst comprises the following steps:
A. mixing: at room temperature, 70mg of urea and 100mg of graphene are added into 40mL of deionized water and are dispersed uniformly by ultrasonic treatment, and the mixture is dried for 40 hours at the temperature of minus 55 ℃ and the vacuum degree of 15 Pa; calcining at 550 ℃ for 2h in an air atmosphere after freeze drying; cooling to obtain the carbon nitride/graphene composite material
B. Dispersing: weighing 5mg of carbon nitride/graphene composite material in a volume ratio of 10mL to 1: 1, dispersing the mixture in a mixed solvent of ethylene glycol and water by ultrasonic waves;
C. preparation: adding 0.0540g of nickel chloride hexahydrate and 0.0060g of manganese acetate tetrahydrate into 10mL of mixed solution of ethylene glycol and water (the specific volume is 1: 1) at room temperature, then slowly dropwise adding the solution into the dispersion liquid obtained in the step B under the action of stirring, adding 130mg of urea, and finally heating the prepared solution to 120 ℃ for 10 hours;
D. and (3) drying: cooling and separating the reacted system, washing the precipitate with water and then with alcohol, and drying the precipitate in vacuum at 60 ℃ to constant weight, namely the NiMn double-metal hydroxide/graphene nano composite material (NiMn LDH/C) modified by carbon nitride and containing oxygen vacancies3N4/G) and the content of oxygen vacancies was 12%.
And (3) testing the electrocatalytic performance:
the NiMn LDH/C obtained in example 4 was used3N4The catalyst is used for electrocatalytic reaction of methanol:
firstly, weighing a certain amount of NiMn LDH/C3N4the/G nano material is ultrasonically dispersed in deionized water to prepare a 4mg/L dispersion solution; secondly, preparing 0.1M KOH and 0.1M methanol solution by using deionized water; then, 6 mu L of 4mg/L of dispersion solution is absorbed and dropped on the surface of the glassy carbon electrode and naturally cooled; finally, an electrochemical workstation is adopted to record the electrocatalysis process of the electrochemical workstation on methanol between 0.0-0.8V vs. Ag/AgCl, and the obtained NiMn LDH/C can be seen3N4the/G nano composite material has good electrocatalytic reaction on methanol. NiMn LDH/C in 0.1M KOH solution3N4The catalytic activity of the/G nano composite material to 0.1M methanol is 38 mA-cm-2
Preparing the NiMn double metal hydroxide/graphene nanocomposite material (NiMn LDH/C) under the same condition3N4For comparison,/G) was prepared as follows:
A. dispersing: weighing 5mg of graphene in 10mL of a volume ratio of 1: 1, dispersing the mixture in a mixed solvent of ethylene glycol and water by ultrasonic waves;
B. preparation: adding 0.0540g of nickel chloride hexahydrate and 0.0060g of manganese acetate tetrahydrate into 10mL of mixed solution of glycol and water (the specific volume is 1: 1) at room temperature, then slowly dropwise adding the solution into the dispersion liquid in the step B under the action of stirring, adding 130mg of urea, and finally heating the prepared solution to 120 ℃ for reaction for 10 hours;
C. and (3) drying: cooling and separating the reacted system, washing the precipitate with water and then alcohol, and vacuum drying at 60 ℃ to constant weight, namely the NiMn double metal hydroxide/graphene nano composite material (NiMn LDH/C)3N4/G).
In 0.1M KOH solution, the catalytic activity of the NiMn LDH/G nano composite material to 0.1M methanol is only 3 mA-cm-2While under the same conditions, NiMn LDH/C3N4The electrocatalytic activity of the/G nano composite material is improved by 13 times.

Claims (6)

1. A method for preparing a carbon nitride modified methanol electrocatalyst, comprising the steps of:
A. dispersing a carbon material and a nitrogen-containing compound in water, uniformly stirring, freeze-drying, and calcining the obtained mixture to obtain a carbon nitride/carbon material;
B. dispersing carbon nitride/carbon material in a mixed solvent to form a uniformly dispersed dispersion liquid;
C. dropwise adding the nickel-manganese mixed solution into the dispersion liquid prepared in the step B under the stirring state, then adding urea, and carrying out hydrothermal reaction to obtain a carbon nitride modified NiMn double metal hydroxide/carbon nano composite material;
in the step A, the calcining temperature ranges from 400 ℃ to 700 ℃, and the calcining time is 0.5-2 h;
in the step B, the dosage ratio of the carbon nitride/carbon material to the mixed solvent is 0.2-2 mg/ml;
the preparation method of the nickel-manganese mixed solution in the step C comprises the following steps: dissolving nickel salt and manganese salt in a mixed solvent of water and alcohol; the ratio of the total mass of the nickel salt and the manganese salt to the dosage of the mixed solvent is 1-10 mg/mL; the molar ratio of the nickel salt to the manganese salt is 2:1-25: 1;
the volume ratio of the nickel-manganese mixed solution in the step C to the dispersion liquid in the step B is 0.1: 1-10: 1;
the hydrothermal reaction in the step C refers to: reacting for 4-48 hours at 70-180 ℃;
the content of oxygen vacancy of the prepared carbon nitride modified methanol electrocatalyst is 5-40%.
2. The method according to claim 1, wherein the carbon material in step a comprises one or more of carbon black, graphene or carbon nanotubes; the nitrogen-containing compound is one or more of urea, dicyandiamide or melamine.
3. The production method according to claim 1 or 2, characterized in that the mass ratio of the carbon material and the nitrogen-containing compound in step a is in the range of 2: 1-1: 3, or less.
4. The production method according to claim 1, wherein the mixed solvent in step B is a mixed solvent of water and alcohol.
5. The process according to claim 1 or 2, wherein the ratio of the amount of urea used to the total mass of the nickel salt and the manganese salt in step C is 1: 1-100: 1.
6. Use of a carbon nitride-modified methanol electrocatalyst prepared by the preparation method according to any one of claims 1 to 5 in methanol electrocatalysis.
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