CN111013624A - Nitrogen-doped porous carbon-coated metal nano composite catalyst and preparation method thereof - Google Patents

Nitrogen-doped porous carbon-coated metal nano composite catalyst and preparation method thereof Download PDF

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CN111013624A
CN111013624A CN201911294088.1A CN201911294088A CN111013624A CN 111013624 A CN111013624 A CN 111013624A CN 201911294088 A CN201911294088 A CN 201911294088A CN 111013624 A CN111013624 A CN 111013624A
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nitrogen
deionized water
temperature
porous carbon
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CN111013624B (en
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严亮
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Foshan Polytechnic
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J35/33—
    • B01J35/396—
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a nitrogen-doped porous carbon-coated metal nano composite catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: 1) adding fluoride into acidic solution for reaction, and then adding Mn+ 1AXnMagnetically stirring and reacting under the condition of water bath, washing and centrifuging a product by using deionized water, then sequentially ultrasonically washing and centrifuging by using an organic solvent and the deionized water, and freeze-drying the product to obtain a reactant 1; 2) weighing a certain amount of reactant 1, adding deionized water and an organic solvent, uniformly dispersing by ultrasonic, dissolving transition metal salt and urea in the deionized water, adding the dissolved transition metal salt and urea into the deionized water, and reacting by magnetic stirring under the condition of oil bath to obtain a reactant 2; 3) carrying out heat treatment on the reactant 2 and the nitrogen-containing compound in a high-temperature furnace to obtain a reactant 3; 4) the reactant 3 is reduced at high temperature under protective atmosphereAnd obtaining the nitrogen-doped porous carbon-coated metal nano composite catalyst. The invention solves the problems that the oxygen reduction catalyst prepared by the prior art is easy to agglomerate and the ORR activity is reduced because the active site is exposed less.

Description

Nitrogen-doped porous carbon-coated metal nano composite catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a nitrogen-doped porous carbon-coated metal nano composite catalyst and a preparation method thereof.
Background
A fuel cell is a power generation device that directly converts chemical energy of fuel into electrical energy in an electrochemical reaction without combustion. The power generation process is not limited by Carnot cycle, the energy conversion efficiency is high, the theoretical efficiency is as high as 85-90%, the actual efficiency is 40-60%, the environment is friendly, air pollutants such as sulfur oxides and nitrogen oxides are hardly discharged, the noise is low, the operation is simple and convenient, and the energy-saving power generation system is considered to be the preferred clean energy in the 21 st century. As an efficient and clean energy conversion technology, fuel cells must play an irreplaceable role in future non-fossil energy systems. The catalysts currently used in fuel cell cathodes are mainly noble Pt-based catalysts. Although it has a high oxygen reduction activity, the commercial application of fuel cell technology is limited by the natural scarcity of precious metals, the high cost of catalysts, and the electrochemical stability to be improved. Inexpensive high performance oxygen reduction catalysts are undoubtedly one of the key factors for large scale application of fuel cell technology. Therefore, the development of a high-activity and low-cost oxygen-reduced non-noble metal catalyst becomes an important step in the practical process of fuel cell technology.
Nitrogen-doped carbon-coated transition metal (M @ NC, M ═ Co, Fe, Ni, and the like) nanocatalysts have been proven to have activity to catalyze Oxygen Reduction Reactions (ORR) and have received extensive attention and research. However, the coated catalysts of this type reported in the literature have the following problems: 1) the agglomeration of metal particles in the high-temperature pyrolysis process causes the uneven dispersion of the metal particles, and the particle size is larger and ranges from dozens of nanometers to hundreds of nanometers; 2) the metal loading is low, generally less than 10%; 3) some metal particles are not completely coated, and the uneven dispersion and low metal loading of the metal particles affect the electronic effect of the metal core and the graphitized carbon layer and the active site density of the catalyst, thereby causing the reduction of the catalytic activity. In addition, because the metal is not completely coated, the metal particles are easily dissolved in an acidic medium, and the stability of the catalyst is reduced. Therefore, there is still a lot of work to be done to address the above problems.
Metal Organic Frameworks (MOFs), due to their good coordination environment and ordered framework structure, can be used as metal ion encapsulates. However, high temperature pyrolysis processes often result in structural collapse and agglomeration, resulting in uncontrolled subsequent growth of the metal particles, and thus their poor electrochemical activity.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a nitrogen-doped porous carbon-coated metal nanocomposite catalyst with high ORR activity.
Another object of the present invention is to provide a nitrogen-doped porous carbon-coated metal nanocomposite catalyst with high ORR activity.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of a nitrogen-doped porous carbon-coated metal nano composite catalyst is characterized by comprising the following steps of: 1) adding fluoride into acidic solution for reaction, and then adding Mn+1AXnMagnetically stirring and reacting under the condition of water bath, washing and centrifuging a product by using deionized water, then sequentially washing and centrifuging by using an organic solvent a and the deionized water in an ultrasonic mode, and freeze-drying the product to obtain a reactant 1, wherein M, A and X in the formula are respectively a transition metal element, a main group metal element and a main group nonmetal element, and n is 1,2 and 3; 2) adding the reactant 1 into deionized water and an organic solvent b in a protective atmosphere, ultrasonically dispersing uniformly, dissolving transition metal salt and urea in the deionized water, adding, and magnetically stirring for reaction under an oil bath condition to obtain a reactant 2; 3) carrying out heat treatment on the reactant 2 and a nitrogen-containing compound in a high-temperature furnace in a protective atmosphere to obtain a reactant 3; 4) and reducing the reactant 3 at high temperature in a protective atmosphere to obtain the nitrogen-doped porous carbon-coated metal nano composite catalyst.
Preferably, in step 1), the fluoride is selected from LiF, NaF, KF, MgF2、NiF2、CaF2、CrF3、AlF3、HF、NH4F、NH4HF2、Na3AlF6、K3AlF6One or two of them.
Preferably, in step 1), the acidic solution is one or two selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, hydrofluoric acid, and formic acid.
Preferably, in step 1), M is selected from Sc, Ti, V, Cr, Zr, Nb, Mo, Hf or Ta, A is selected from Al, Si or Ga, and X is selected from C or N.
Preferably, in step 1), the organic solvent a is one or two of methanol, ethanol, ethylene glycol, isopropanol, acetone, N-methylpyrrolidone and N-hexane.
Preferably, in the step 2), the organic solvent b is one or two of methanol, ethanol, ethylene glycol, isopropanol, acetone, N-methylpyrrolidone and N-hexane.
Preferably, in the step 2), the transition metal salt is selected from one or more of iron salt, cobalt salt, nickel salt and copper salt; the ferric salt is selected from one or two of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric acetate, ferrous acetate and ferric acetylacetonate; the cobalt salt is selected from one or two of cobalt chloride, cobaltous chloride, cobalt sulfate, cobaltous sulfate, cobalt nitrate, cobaltous nitrate, cobalt acetate, cobaltous acetate and cobalt acetylacetonate; the nickel salt is selected from one or two of nickel chloride, nickel sulfate, nickel nitrate, nickel acetate and nickel acetylacetonate; the copper salt is selected from one or two of copper chloride, copper sulfate, copper nitrate, copper acetate and copper acetylacetonate.
Preferably, in step 3), the nitrogen-containing compound is one or more of cyanamide, urea, melamine, monomethyl imidazole, dimethyl imidazole, 2-amino terephthalic acid, N-dimethylformamide, 2-bipyridine, 2,3,6,7,10, 11-hexa-amino-triphenyl, dopamine, and polyacrylonitrile.
Preferably, in the step 1), the reaction temperature of the water bath condition is 30-100 ℃, more preferably 30-80 ℃, most preferably 35-60 ℃, the reaction time is 0.5-170 hours, more preferably 1-170 hours, and most preferably 5-170 hours.
Preferably, in the step 2), the oil bath reaction temperature is 30-200 ℃, more preferably 30-150 ℃, most preferably 60-100 ℃, the reaction time is 1-48 hours, more preferably 1-24 hours, and most preferably 5-20 hours.
Preferably, in the step 3), the temperature of the heating treatment is 100-800 ℃, more preferably 200-600 ℃, most preferably 250-500 ℃, the temperature rise rate is 0.5-10 ℃/min, more preferably the temperature rise rate is 1-8 ℃/min, most preferably the temperature rise rate is 2-5 ℃/min, the heat preservation time of the heating treatment is 0.1-8 hours, more preferably the heat preservation time is 0.5-4 hours, most preferably the heat preservation time is 1-3 hours.
Wherein the protective atmosphere is selected from one of nitrogen, hydrogen, argon or hydrogen/argon mixed gas.
Preferably, in the step 4), the temperature of the high-temperature reduction is 100-1000 ℃, more preferably 200-800 ℃, most preferably 300-700 ℃, the temperature rise rate of the high-temperature reduction is 0.5-10 ℃/min, more preferably the temperature rise rate of the high-temperature reduction is 1-8 ℃/min, most preferably the temperature rise rate of the high-temperature reduction is 2-5 ℃/min, the heat preservation time of the high-temperature reduction is 0.1-8 hours, more preferably the heat preservation time of the high-temperature reduction is 0.5-4 hours, most preferably the heat preservation time of the high-temperature reduction is 1-3 hours.
The invention also provides a nitrogen-doped porous carbon-coated metal nano composite catalyst which is characterized by comprising the nitrogen-doped porous carbon-coated metal nano composite catalyst prepared by the preparation method.
The invention has the beneficial effects that:
MXene is a novel two-dimensional crystal compound with a graphene-like structure and novel properties, has the chemical formula of Mn +1Xn (M is a transition metal element, X is carbon or nitrogen element, and n is 1,2,3), has the characteristics of high specific surface area and high conductivity of graphene, has the advantages of adjustable and controllable interlayer spacing and components, and has huge application potential in the fields of energy, catalysis, biomedicine, photoelectricity and the like. MXene is one of the new stars in the research field of functional materials in recent years due to unique electrical, optical and mechanical properties. Therefore, aiming at the problems of the MOF material in the sintering process, the MOF is grown in situ on the MXene nano-sheets, and then the MOF is further calcined to enable nano-particles to be uniformly nucleated, grown and anchored on the surfaces of the single-layer/few-layer MXene nano-sheets, so that the nitrogen-doped porous carbon coated metal nano/MXene composite catalyst (M @ NC/MXene) is obtained. The two-dimensional MXene nanosheets are used as conductive carriers of M @ NC, the conductivity of the catalyst is improved, the balance of carbon graphitization degree and specific surface area in the catalyst is coordinated, and the introduction of MXene is beneficial to rapid diffusion of O2 and effective exposure of catalytic active sites. The generated M @ NC/MXene catalyst not only shows excellent ORR activity, but also has excellent stability and poisoning resistance.
Compared with the existing preparation method of the nitrogen-doped porous carbon-coated metal nano catalyst, the method introduces MXene with high metal conductivity and excellent mechanical stability to stably and uniformly disperse M @ NC, so that the M @ NC and the MXene are combined to form a strong conductive chemical interface and a synergistic effect is generated between the M @ NC and the MXene, and therefore the M @ NC/MXene nano catalyst is designed and constructed, has three-way catalyst active sites and shows excellent catalytic activity, stability and poisoning resistance to ORR.
The M @ NC/MXene nano catalyst prepared by the specific preparation method has high catalytic activity on ORR, and solves the problem that the conventional nitrogen-doped porous carbon-coated metal material is easy to collapse and agglomerate at high temperature to cause low ORR activity. In addition, the preparation method of the M @ NC/MXene nano catalyst has the advantages of simple process, low cost and easiness in scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a scanning electron micrograph of reactant 1MXene prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the reactant 2Co-LDH/MXene prepared in example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of the reactant 3Co-MOF/MXene prepared in example 1 of the present invention.
FIG. 4 is a scanning electron micrograph of Co @ NC/MXene prepared according to example 1 of the present invention.
FIG. 5 is a scanning electron micrograph of Fe @ NC/MXene prepared according to example 5 of the present invention.
FIG. 6 is a scanning electron micrograph of Ni @ NC/MXene prepared according to EXAMPLE 9 of the present invention.
FIG. 7 is a scanning electron micrograph of Cu @ NC/MXene prepared in EXAMPLE 11 of the present invention.
FIG. 8 is a scanning electron microscope image of FeCo @ NC/MXene prepared in example 12 of the present invention.
Detailed Description
The invention provides a nitrogen-doped porous carbon-coated metal nano catalyst and a preparation method thereof, which can solve the problems that an oxygen reduction catalyst prepared by the prior art is easy to agglomerate and active sites are less exposed.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the following examples are all commercially available or self-made.
Example 1
The embodiment provides a first nitrogen-doped porous carbon-coated metal nano composite catalyst, which is prepared by the following steps:
1) dissolving 2g LiF in 40ml hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into solution a, reacting for 24 hr under magnetic stirring in water bath at 35 deg.C, washing with deionized water and centrifuging, ultrasonic treating with ethanol and deionized water sequentially and centrifuging, and freeze dryingDrying to obtain reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into deionized water and ethylene glycol, and performing ultrasonic dispersion uniformly to obtain a solution b; then, dissolving cobalt nitrate and urea in deionized water, slowly adding the solution b into the solution, reacting for 5 hours in an oil bath at 100 ℃ by magnetic stirring under the protection of nitrogen, and then sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and dimethyl imidazole on two sides of a quartz boat, wherein the dimethyl imidazole is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat to 280 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of nitrogen, preserving the temperature for 2 hours, and gasifying the dimethyl imidazole at high temperature and transmitting the gasified dimethyl imidazole to the side of the reactant 2 along with air flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 500 ℃ at the heating rate of 2 ℃/min in a hydrogen/argon mixed gas, and reacting for 2 hours at the temperature to obtain Ti3C2-MXene loaded nitrogen-doped porous carbon-coated cobalt nano catalyst (Co @ NC/Ti)3C2-MXene)。
From the changes of fig. 1 to fig. 4, the active sites of the nitrogen-doped porous carbon-coated metal nanocomposite catalyst prepared in the embodiment are more exposed and have substantially no agglomeration phenomenon.
Example 2
The present embodiment provides a second nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g NaF in 40ml of hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into the solution a, reacting for 48 hours under the condition of magnetic stirring in a water bath at 30 ℃, washing and centrifuging by using deionized water, then sequentially performing ultrasonic treatment and centrifugation by using ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the product obtained in the step 1) above,i.e. Ti3C2Adding MXene into deionized water and N-methylpyrrolidone, and performing ultrasonic dispersion uniformly to obtain a solution b; then, dissolving cobalt nitrate and urea in deionized water, slowly adding the solution b into the solution, reacting for 20 hours in an oil bath at 60 ℃ under the protection of nitrogen by magnetic stirring, and then sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and dimethyl imidazole on two sides of a quartz boat, wherein the dimethyl imidazole is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat to 500 ℃ from room temperature at the heating rate of 5 ℃/min under the protection of nitrogen, preserving the temperature for 1h, and gasifying the dimethyl imidazole at high temperature and transmitting the gasified dimethyl imidazole to the side of the reactant 2 along with air flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 700 ℃ at the heating rate of 5 ℃/min in a hydrogen/argon mixed gas, and preserving the heat for 1h at the temperature to obtain Ti3C2-MXene loaded nitrogen-doped porous carbon-coated cobalt nano catalyst (Co @ NC/Ti)3C2-MXene)。
Example 3
This example provides a third nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g of KF in 40ml of hydrochloric acid solution for reaction for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into solution a, reacting for 1 hr under magnetic stirring in water bath at 80 deg.C, washing with deionized water and centrifuging, ultrasonic treating with ethanol and deionized water sequentially and centrifuging, and freeze drying to obtain reactant 1, i.e. Ti3C2-MXene。
2) Weighing Ti obtained in the above step 1)3C2Adding MXene into deionized water and N-methylpyrrolidone, and performing ultrasonic dispersion uniformly to obtain a solution b; then, dissolving cobalt nitrate and urea in deionized water, slowly adding the solution into the solution b, reacting for 1 hour in an oil bath at 200 ℃ under the protection of nitrogen by magnetic stirring, and then sequentially washing, filtering and freezingDrying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and the methylimidazole on two sides of a quartz boat, wherein the methylimidazole is on the side of an air inlet, placing the quartz boat in a tube furnace, heating from room temperature to 100 ℃ at the heating rate of 0.5 ℃/min under the protection of nitrogen, keeping the temperature for 6 hours at the temperature, and gasifying the methylimidazole at high temperature and transmitting the gasified methylimidazole to the side of the reactant 1 along with air flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) into a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 100 ℃ at the heating rate of 0.5 ℃/min in a hydrogen/argon mixed gas, and reacting for 6 hours at the temperature to obtain Ti3C2-MXene loaded nitrogen-doped porous carbon-coated cobalt nano catalyst (Co @ NC/Ti)3C2-MXene)。
Example 4
This example provides a fourth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g of KF in 40ml of sulfuric acid solution for reaction for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into solution a, magnetically stirring and reacting for 0.5 h under the condition of 100 ℃ water bath, washing with deionized water and centrifuging, then ultrasonically treating with methanol and deionized water in sequence and centrifuging, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into deionized water and N-methylpyrrolidone, and performing ultrasonic dispersion uniformly to obtain a solution b; then, dissolving cobalt sulfate and urea in deionized water, slowly adding the solution b into the solution, reacting for 20 hours in an oil bath at 30 ℃ under the protection of nitrogen by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and dimethyl imidazole on two sides of a quartz boat, wherein the dimethyl imidazole is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat to 800 ℃ from room temperature at a heating rate of 10 ℃/min under the protection of nitrogen, keeping the temperature for 0.1h, and leading the dimethyl imidazole to be gasified at high temperature to be transmitted to the side of the reactant 2 along with air flow and react to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 1000 ℃ at the heating rate of 10 ℃/min in a hydrogen/argon mixed gas, and reacting at the temperature for 0.1h to obtain Ti3C2-MXene loaded nitrogen-doped porous carbon-coated cobalt nano catalyst (Co @ NC/Ti)3C2-MXene)。
Example 5
The present embodiment provides a fifth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) 2g of CaF2Dissolving the mixture in 40ml of nitric acid solution to react for half an hour to obtain solution a; then, 2g of Ti3AlC2Adding into solution a, reacting for 12 hours under the condition of 35 ℃ water bath and magnetic stirring, washing with deionized water and centrifuging, then sequentially carrying out ultrasonic treatment and centrifuging with ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into deionized water and N-methylpyrrolidone, and performing ultrasonic dispersion uniformly to obtain a solution b; and then dissolving ferric chloride and urea in deionized water, slowly adding the solution b into the solution, reacting for 10 hours in an oil bath at 80 ℃ under the protection of nitrogen by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and 2-aminoterephthalic acid on two sides of a quartz boat, wherein the 2-aminoterephthalic acid is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat from room temperature to 500 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen, and preserving the temperature for 3h, wherein the 2-aminoterephthalic acid is gasified at high temperature and is transmitted to the side of the reactant 2 along with air flow to carry out reaction, so as to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) into a tube furnace for high-temperature reduction, and heating from room temperature to room temperature at a heating rate of 5 ℃/min in a hydrogen/argon mixed gasAt 700 ℃ and reacted for 5h at this temperature to give Ti3C2-MXene loaded nitrogen doped porous carbon coated iron nano catalyst (Fe @ NC/Ti)3C2-MXene)。
As can be seen from fig. 5, the nitrogen-doped porous carbon-coated metal nanocomposite catalyst prepared in this example has more exposed active sites and substantially no agglomeration.
Example 6
The present embodiment provides a sixth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g LiF in 40ml hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into the solution a, reacting for 36 hours under the condition of 35 ℃ water bath by magnetic stirring, washing and centrifuging by deionized water, then sequentially carrying out ultrasonic treatment and centrifugation by isopropanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into ethanol, and performing ultrasonic dispersion to obtain a solution b; then, dissolving ferric chloride and terephthalic acid in N, N-dimethylformamide, slowly adding into the solution b, reacting for 15 hours in an oil bath at 150 ℃ under the protection of nitrogen gas by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and melamine on two sides of a quartz boat, wherein the melamine is on the air inlet side, placing the quartz boat in a tube furnace, heating to 600 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of nitrogen, keeping the temperature for 1h at the temperature, and transmitting the high-temperature gasification of the melamine to the reactant 2 side along with air flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 800 ℃ at the heating rate of 8 ℃/min in a hydrogen/argon mixed gas, and reacting for 1h at the temperature to obtain Ti3C2-MXene loaded nitrogen doped porous carbon coated iron nano catalyst (Fe @ NC/Ti)3C2-MXene)。
Example 7
The present embodiment provides a seventh nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g LiF in 40ml hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into the solution a, reacting for 36 hours under the condition of magnetic stirring in a water bath at 30 ℃, washing and centrifuging by using deionized water, then sequentially performing ultrasonic treatment and centrifugation by using acetone and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing Ti obtained in the above step 1)3C2Adding MXene into deionized water and isopropanol, and performing ultrasonic dispersion uniformly to obtain a solution b; and then dissolving ferric chloride and urea in deionized water, slowly adding the solution b into the solution, reacting for 5 hours in an oil bath at 150 ℃ under the protection of nitrogen by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and terephthalic acid on two sides of a quartz boat, wherein the terephthalic acid is arranged on the gas inlet side, placing the quartz boat in a tube furnace, heating to 350 ℃ from room temperature at the heating rate of 1 ℃/min under the protection of nitrogen, keeping the temperature for 4 hours at the temperature, and transmitting the high-temperature gasification of the terephthalic acid to the reactant 2 side along with gas flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 800 ℃ at the heating rate of 1 ℃/min in nitrogen, and reacting for 4 hours at the temperature to obtain Ti3C2-MXene loaded nitrogen doped porous carbon coated iron nano catalyst (Fe @ NC/Ti)3C2-MXene)。
Example 8
This example provides an eighth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) 2g of NH4Dissolving F in 40ml of hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into solution a, magnetically stirring and reacting for 12 hours under the condition of water bath at 60 ℃, washing and centrifuging by using deionized water, sequentially performing ultrasonic treatment and centrifugation by using ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into deionized water and isopropanol, and performing ultrasonic dispersion uniformly to obtain a solution b; and then dissolving ferric chloride and urea in deionized water, slowly adding the solution b into the solution, reacting for 5 hours in an oil bath at 200 ℃ under the protection of nitrogen by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and terephthalic acid on two sides of a quartz boat, wherein the terephthalic acid is arranged on the gas inlet side, placing the quartz boat in a tube furnace, heating to 350 ℃ from room temperature at the heating rate of 4 ℃/min under the protection of nitrogen, keeping the temperature for 2h, and transmitting the high-temperature gasification of the terephthalic acid to the reactant 2 side along with gas flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) and dopamine on two sides of a quartz boat to react in a tube furnace at a high temperature, wherein the dopamine is arranged on the air inlet side, is heated to 350 ℃ from room temperature at the heating rate of 4 ℃/min in a hydrogen/argon mixed gas, and reacts for 2 hours at the temperature to obtain Ti3C2-MXene loaded nitrogen doped porous carbon coated iron nano catalyst (Fe @ NC/Ti)3C2-MXene)。
Example 9
The present embodiment provides a ninth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) 2g of NH4HF2Dissolving the mixture in 40ml of hydrochloric acid solution to react for half an hour to obtain solution a; then, 2g of Ti3AlC2Adding into the solution a, reacting for 24 hours under the condition of 35 ℃ water bath by magnetic stirring, washing and centrifuging by deionized water, then sequentially carrying out ultrasonic treatment and centrifugation by ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into deionized water and ethanol, and performing ultrasonic dispersion uniformly to obtain a solution b; and then, dissolving nickel acetylacetonate and urea in deionized water, slowly adding the solution b into the deionized water, reacting for 5 hours in an oil bath at 100 ℃ under the protection of nitrogen by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and 2,3,6,7,10, 11-hexaamino triphenyl on two sides of a quartz boat, wherein the 2,3,6,7,10, 11-hexaamino triphenyl is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, raising the temperature from room temperature to 800 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen, and preserving the temperature for 2h, 2,3,6,7,10, 11-hexaamino triphenyl at the temperature, so that high-temperature gasification of the reactant is transmitted to the side of the reactant 2 along with air flow and is reacted to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 600 ℃ at the heating rate of 5 ℃/min in a hydrogen/argon mixed gas, and reacting for 8 hours at the temperature to obtain Ti3C2-MXene loaded nitrogen doped porous carbon coated nickel nano catalyst (Ni @ NC/Ti)3C2-MXene)。
As can be seen from fig. 6, the nitrogen-doped porous carbon-coated metal nanocomposite catalyst prepared in this example has more exposed active sites and substantially no agglomeration.
Example 10
The present embodiment provides a tenth nitrogen-doped porous carbon-coated metal nanocatalyst, which is prepared by the following steps:
1) dissolving 2g NaF in 40ml of sulfuric acid solution to react for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into the solution a, reacting for 24 hours under the condition of 35 ℃ water bath by magnetic stirring, washing and centrifuging by deionized water, then sequentially carrying out ultrasonic treatment and centrifugation by ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Addition of MXene to deionizationUltrasonically dispersing the mixture in water and ethanol uniformly to obtain a solution b; and then, dissolving nickel nitrate, zinc nitrate and urea in deionized water, slowly adding the solution b into the solution, reacting for 6 hours in an oil bath at 80 ℃ under the protection of nitrogen by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and the methylimidazole on two sides of a quartz boat, wherein the methylimidazole is on the side of an air inlet, placing the quartz boat in a tube furnace, heating from room temperature to 300 ℃ at the heating rate of 0.5 ℃/min under the protection of nitrogen, keeping the temperature for 6 hours at the temperature, and gasifying the methylimidazole at high temperature and transmitting the gasified methylimidazole to the side of the reactant 2 along with air flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) into a tube furnace, heating the reactant from room temperature to 430 ℃ at the heating rate of 3 ℃/min in a hydrogen/argon mixed gas, and reacting for 8h at the temperature to obtain Ti3C2-MXene loaded nitrogen doped porous carbon coated nickel nano catalyst (Ni @ NC/Ti)3C2-MXene)。
Example 11
The present embodiment provides an eleventh nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g NaF in 40ml of hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into the solution a, reacting for 24 hours under the condition of 35 ℃ water bath by magnetic stirring, washing and centrifuging by deionized water, then sequentially carrying out ultrasonic treatment and centrifugation by ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into deionized water and ethanol, and performing ultrasonic dispersion uniformly to obtain a solution b; and then, dissolving copper acetate and trimesic acid in deionized water, slowly adding the solution b into the solution, reacting for 5 hours in an oil bath at 100 ℃ under the protection of nitrogen by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and 2,2' -bipyridine on two sides of a quartz boat, wherein the 2,2' -bipyridine is arranged on the side of an air inlet, placing the quartz boat in a tubular furnace, heating from room temperature to 280 ℃ at the heating rate of 2 ℃/min under the protection of nitrogen, and preserving the temperature for 2h, and the high-temperature gasification of the 2,2' -bipyridine is carried out along with the air flow to the side of the reactant 2 to react to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) into a tube furnace, heating the reactant from room temperature to 550 ℃ at the heating rate of 3 ℃/min in a hydrogen/argon mixed gas, and reacting for 3 hours at the temperature to obtain Ti3C2-MXene loaded nitrogen-doped porous carbon-coated copper nano catalyst (Cu @ NC/Ti)3C2-MXene)。
As can be seen from fig. 7, the nitrogen-doped porous carbon-coated metal nanocomposite catalyst prepared in this example has more exposed active sites and substantially no agglomeration.
Example 12
The present embodiment provides a twelfth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g NaF in 40ml of hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into solution a, reacting for 8 hours under magnetic stirring in a water bath at 35 ℃, washing with deionized water and centrifuging, then sequentially carrying out ultrasonic treatment and centrifugation with ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into deionized water and isopropanol, and performing ultrasonic dispersion uniformly to obtain a solution b; then, dissolving cobalt nitrate and ferric chloride in deionized water, slowly adding the solution b into the solution, reacting for 12 hours in an oil bath at 100 ℃ under the protection of nitrogen by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2 and dimethyl imidazole on two sides of a quartz boat, wherein the dimethyl imidazole is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat to 280 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of nitrogen, keeping the temperature for 2h, and gasifying the dimethyl imidazole at high temperature and transmitting the gasified dimethyl imidazole to the side of the reactant 2 along with air flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 450 ℃ at the heating rate of 3 ℃/min in a hydrogen/argon mixed gas, and reacting for 2 hours at the temperature to obtain Ti3C2-MXene loaded nitrogen-doped porous carbon-coated iron-cobalt nano catalyst (FeCo @ NC/Ti)3C2-MXene)。
As can be seen from fig. 8, the nitrogen-doped porous carbon-coated metal nanocomposite catalyst prepared in this example has more exposed active sites and substantially no agglomeration.
Example 13
This example provides a thirteenth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g of KF in 40ml of hydrochloric acid solution for reaction for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into the solution a, reacting for 16 hours under the condition of 35 ℃ water bath by magnetic stirring, washing and centrifuging by deionized water, then sequentially carrying out ultrasonic treatment and centrifugation by ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into deionized water and isopropanol, and performing ultrasonic dispersion uniformly to obtain a solution b; then, dissolving cobalt nitrate and nickel chloride in deionized water, slowly adding the solution b into the solution, reacting for 5 hours in an oil bath at 100 ℃ under the protection of nitrogen by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and dimethyl imidazole on two sides of a quartz boat, wherein the dimethyl imidazole is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat to 280 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of nitrogen, preserving the temperature for 8 hours, and gasifying the dimethyl imidazole at high temperature and transmitting the gasified dimethyl imidazole to the side of the reactant 2 along with air flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 500 ℃ at the heating rate of 5 ℃/min in a hydrogen/argon mixed gas, and reacting for 4 hours at the temperature to obtain Ti3C2-MXene loaded nitrogen-doped porous carbon-coated cobalt nickel nano catalyst (CoNi @ NC/Ti)3C2-MXene)。
Example 14
The present embodiment provides a fourteenth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g of KF in 40ml of hydrochloric acid solution for reaction for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into the solution a, reacting for 24 hours under the condition of magnetic stirring in water bath at 40 ℃, washing and centrifuging by using deionized water, then sequentially performing ultrasonic treatment and centrifugation by using ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into deionized water and ethanol, and performing ultrasonic dispersion uniformly to obtain a solution b; and then, dissolving ferric chloride and nickel chloride in deionized water, slowly adding into the solution b, reacting for 48 hours in an oil bath at 100 ℃ under the protection of nitrogen by magnetic stirring, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and dimethyl imidazole on two sides of a quartz boat, wherein the dimethyl imidazole is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat to 300 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of nitrogen, preserving the temperature for 5 hours, and gasifying the dimethyl imidazole at high temperature and transmitting the gasified dimethyl imidazole to the side of the reactant 2 along with air flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 650 ℃ at the heating rate of 2 ℃/min in a hydrogen/argon mixed gas, and reacting for 6 hours at the temperature to obtain Ti3C2-MXene loaded nitrogen doped porous carbon coatingIron-nickel nano catalyst (FeNi @ NC/Ti)3C2-MXene)。
Example 15
The present embodiment provides a fifteenth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g LiF in 40ml hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g V2Adding AlC into the solution a, reacting for 120 hours under the condition of 35 ℃ water bath by magnetic stirring, cleaning and centrifuging by using deionized water, then sequentially ultrasonically cleaning and centrifuging by using ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely V2C-MXene。
2) Weighing V obtained in the step 1)2C-MXene is added into deionized water and ethylene glycol to be uniformly dispersed by ultrasonic to obtain a solution b; then, dissolving cobalt nitrate in deionized water, slowly adding the solution b into the solution, reacting for 5 hours in an oil bath at 100 ℃ by magnetic stirring under the protection of nitrogen, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and dimethyl imidazole on two sides of a quartz boat, wherein the dimethyl imidazole is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat to 280 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of nitrogen, preserving the temperature for 2 hours, and gasifying the dimethyl imidazole at high temperature and transmitting the gasified dimethyl imidazole to the side of the reactant 2 along with air flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 450 ℃ at the heating rate of 2 ℃/min in a hydrogen/argon mixed gas, and reacting for 2h at the temperature to obtain V2C-MXene loaded nitrogen-doped porous carbon-coated cobalt nano catalyst (Co @ NC/V)2C-MXene)。
Example 16
The present embodiment provides a sixteenth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g NaF in 40ml of hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g of Mo2Ga2Adding C into the solution a, reacting for 170 hours under the condition of magnetic stirring in a water bath at 55 ℃, washing and centrifuging by using deionized water, then sequentially performing ultrasonic treatment and centrifugation by using ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Mo2C-MXene。
2) Weighing Mo obtained in the step 1)2C-MXene is added into deionized water and ethylene glycol to be uniformly dispersed by ultrasonic to obtain a solution b; and then dissolving ferric chloride in deionized water, slowly adding the solution b into the solution, reacting for 5 hours in an oil bath at 100 ℃ by magnetic stirring under the protection of nitrogen, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and 2-aminoterephthalic acid on two sides of a quartz boat, wherein the 2-aminoterephthalic acid is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat from room temperature to 500 ℃ at the heating rate of 2 ℃/min under the protection of nitrogen, and preserving the temperature for 2h, wherein the 2-aminoterephthalic acid is gasified at high temperature and is transmitted to the side of the reactant 2 along with air flow to carry out reaction, and a reactant 3 is obtained.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 600 ℃ at the heating rate of 2 ℃/min in a hydrogen/argon mixed gas, and reacting for 2h at the temperature to obtain Mo2C-MXene loaded nitrogen-doped porous carbon-coated iron nano catalyst (Fe @ NC/Mo)2C-MXene)。
Example 17
The present embodiment provides a seventeenth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) adding 2g of Na3AlF6Dissolving the mixture in 40ml of hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g of Ti2Adding AlN into the solution a, magnetically stirring and reacting for 5 hours under the condition of water bath at 40 ℃, washing and centrifuging by using deionized water, then ultrasonically centrifuging by using ethanol and deionized water in sequence, and freeze-drying to obtain a reactant 1, namely Ti2N-MXene。
2) Weighing the Ti obtained in the step 1)2Adding N-MXene into deionized water and N-methylUniformly dispersing the pyrrolidone in the pyrrolidone by ultrasonic waves to obtain a solution b; then, dissolving cobalt nitrate in deionized water, slowly adding the solution b into the solution, reacting for 5 hours in an oil bath at 100 ℃ by magnetic stirring under the protection of nitrogen, and sequentially carrying out washing, filtering and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and dimethyl imidazole on two sides of a quartz boat, wherein the dimethyl imidazole is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat to 300 ℃ from room temperature at the heating rate of 3 ℃/min under the protection of nitrogen, preserving the temperature for 2h, and gasifying the dimethyl imidazole at high temperature and transferring the dimethyl imidazole to the side of the reactant 2 along with air flow to perform reaction to obtain a reactant 3.
4) Placing the reactant 3 obtained in the step 3) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 440 ℃ at the heating rate of 2 ℃/min in a hydrogen/argon mixed gas, and reacting for 2 hours at the temperature to obtain Ti2N-MXene loaded nitrogen-doped porous carbon-coated cobalt nano catalyst (Co @ NC/Ti)2N-MXene)。
Example 18
The present embodiment provides an eighteenth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) 2g of a mixture of KF, LiF and NaF (KF: LiF: NaF mass ratio of 0.59:0.29:0.12) and 2g of Ti4AlN3The mixture is evenly mixed and placed in a quartz boat, the temperature is increased from room temperature to 550 ℃ at the heating rate of 10 ℃/min under the protection of argon, and the temperature is kept for 1h at the temperature, thus obtaining a reactant 1.
2) Dissolving 1g of reactant 1 in 40ml of sulfuric acid solution for reaction for 1 hour, washing with deionized water and centrifuging, then sequentially performing ultrasonic treatment and centrifugation with ethanol and deionized water, and freeze-drying to obtain a reactant 2, namely Ti4N3-MXene。
3) Weighing the Ti obtained in the step 2)4N3Adding MXene into deionized water and N-methylpyrrolidone, and performing ultrasonic dispersion uniformly to obtain a solution a; then, dissolving nickel chloride in deionized water, slowly adding the solution into the solution a, and performing magnetic force at 100 ℃ in an oil bath under the protection of nitrogenThe reaction was stirred for 5 hours, and then washed, filtered and freeze-dried in this order to obtain reaction product 3.
4) Placing the reactant 3 obtained by the treatment of the step 3) and 2,3,6,7,10, 11-hexaamino triphenyl on two sides of a quartz boat, wherein the 2,3,6,7,10, 11-hexaamino triphenyl is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, raising the temperature from room temperature to 800 ℃ at the heating rate of 3 ℃/min under the protection of nitrogen, and preserving the temperature for 2h at the temperature, wherein the high-temperature gasification of the 2,3,6,7,10, 11-hexaamino triphenyl is transmitted to the side of the reactant 3 along with the air flow and reacts to obtain a reactant 4.
5) Placing the reactant 4 obtained in the step 4) into a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 550 ℃ at the heating rate of 5 ℃/min in a hydrogen/argon mixed gas, and reacting for 2 hours at the temperature to obtain Ti2N-MXene loaded nitrogen-doped porous carbon-coated nickel nano catalyst (Ni @ NC/Ti)4N3-MXene)。
Example 19
The present embodiment provides a nineteenth nitrogen-doped porous carbon-coated metal nanocomposite catalyst, which is prepared by the following steps:
1) dissolving 2g LiF in 40ml hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g V2Adding AlC into the solution a, reacting for 120 hours under the condition of 35 ℃ water bath by magnetic stirring, cleaning and centrifuging by using deionized water, then sequentially ultrasonically cleaning and centrifuging by using ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely V2C-MXene。
2) Heating the reactant 1 obtained by the treatment in the step 1) from room temperature to 600 ℃ at a heating rate of 5 ℃/min in an ammonia atmosphere, preserving heat for 2 hours at the temperature, and reacting the reactant 1 with ammonia to obtain a reactant 2, namely V2N-MXene。
3) Weighing V obtained in the step 2)2Adding N-MXene into deionized water and N-methylpyrrolidone, and performing ultrasonic dispersion uniformly to obtain a solution b; then, dissolving cobalt nitrate and ferric chloride in deionized water, slowly adding into the solution b, magnetically stirring and reacting for 5 hours at 100 ℃ in an oil bath under the protection of nitrogen, and sequentially performing washing, filtering and freeze-drying treatmentTo obtain a reactant 3.
4) Placing the reactant 3 obtained by the treatment in the step 3) and dimethyl imidazole on two sides of a quartz boat, wherein the dimethyl imidazole is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat to 280 ℃ from room temperature at the heating rate of 3 ℃/min under the protection of nitrogen, preserving the temperature for 2h, and gasifying the dimethyl imidazole at high temperature and transmitting the gasified dimethyl imidazole to the side of the reactant 3 along with air flow to perform reaction to obtain a reactant 4.
5) Placing the reactant 4 obtained in the step 4) in a tubular furnace for high-temperature reduction, heating the reactant from room temperature to 500 ℃ at the heating rate of 3 ℃/min in a hydrogen/argon mixed gas, and reacting for 2h at the temperature to obtain V2N-MXene loaded nitrogen-doped porous carbon-coated iron-cobalt nano catalyst (FeCo @ NC/V)2N-MXene)。
Comparative example 1
This example provides a comparative example, which was prepared as follows:
1) dissolving 2g LiF in 40ml hydrochloric acid solution to react for half an hour to obtain a solution a; then, 2g of Ti3AlC2Adding into the solution a, reacting for 24 hours under the condition of 35 ℃ water bath by magnetic stirring, washing and centrifuging by deionized water, then sequentially carrying out ultrasonic treatment and centrifugation by ethanol and deionized water, and freeze-drying to obtain a reactant 1, namely Ti3C2-MXene。
2) Weighing the Ti obtained in the step 1)3C2Adding MXene into deionized water and ethylene glycol, and performing ultrasonic dispersion uniformly to obtain a solution b; then, dissolving cobalt nitrate and urea in deionized water, slowly adding the solution b, reacting for 5 hours in oxygen or air under the condition of 100 ℃ oil bath by magnetic stirring, and sequentially carrying out washing filtration and freeze drying treatment to obtain a reactant 2.
3) Placing the reactant 2 obtained by the treatment in the step 2) and dimethyl imidazole on two sides of a quartz boat, wherein the dimethyl imidazole is arranged on the side of an air inlet, placing the quartz boat in a tube furnace, heating the quartz boat to 280 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of nitrogen, preserving the temperature for 2 hours, and gasifying the dimethyl imidazole at high temperature and transmitting the gasified dimethyl imidazole to the side of the reactant 2 along with air flow to perform reaction to obtain a reactant 3.
4) And (3) placing the reactant 3 obtained in the step 3) into a tubular furnace for high-temperature reduction, heating to 500 ℃ from room temperature at a heating rate of 3 ℃/min in a hydrogen/argon mixed gas, and reacting for 2h at the temperature.
Ti could not be obtained by the method of comparative example3C2-MXene loaded nitrogen doped porous carbon coated metal nano catalyst.
It will be appreciated by those skilled in the art from the foregoing description of construction and principles that the invention is not limited to the specific embodiments described above, and that modifications and substitutions based on the teachings of the art may be made without departing from the scope of the invention as defined by the appended claims and their equivalents. The details not described in the detailed description are prior art or common general knowledge.

Claims (10)

1. A preparation method of a nitrogen-doped porous carbon-coated metal nano composite catalyst is characterized by comprising the following steps of:
1) adding fluoride into acidic solution for reaction, and then adding Mn+1AXnMagnetically stirring and reacting under the condition of water bath, washing and centrifuging a product by using deionized water, then sequentially ultrasonically washing and centrifuging by using an organic solvent a and the deionized water, and freeze-drying the product to obtain a reactant 1; mn+1AXnWherein M, A and X are transition metal elements, main group metal elements and main group nonmetal elements, respectively, and n is 1,2, 3;
2) in a protective atmosphere, adding the reactant 1 into deionized water and an organic solvent b, ultrasonically dispersing uniformly, dissolving transition metal salt and urea into the deionized water, adding the dissolved transition metal salt and urea into the deionized water, and magnetically stirring for reaction under an oil bath condition to obtain a reactant 2;
3) carrying out heat treatment on the reactant 2 and a nitrogen-containing compound in a high-temperature furnace in a protective atmosphere to obtain a reactant 3;
4) and reducing the reactant 3 at high temperature in a protective atmosphere to obtain the nitrogen-doped porous carbon-coated metal nano composite catalyst.
2. The method according to claim 1, wherein said fluoride is selected from the group consisting of LiF, NaF, KF, MgF2、NiF2、CaF2、CrF3、AlF3、HF、NH4F、NH4HF2、Na3AlF6、K3AlF6One kind of (1).
3. The method according to claim 1, wherein the acidic solution is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, hypochlorous acid, phosphoric acid, acetic acid, citric acid, hydrofluoric acid, formic acid, oxalic acid; the organic solvent a is one or two selected from methanol, ethanol, ethylene glycol, isopropanol, diethyl ether, acetone, N-methyl pyrrolidone, ethyl acetate, dichloromethane, N-hexane and chloroform;
the organic solvent b is one or two of methanol, ethanol, glycol, isopropanol, diethyl ether, acetone, N-methylpyrrolidone, ethyl acetate, dichloromethane, normal hexane and chloroform;
the transition metal salt is selected from one or more of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric acetate, ferrous acetate, ferric acetylacetonate, cobalt chloride, cobaltous chloride, cobalt sulfate, cobaltous sulfate, cobalt nitrate, cobaltous nitrate, cobalt acetate, cobalt acetylacetonate, nickel chloride, nickel sulfate, nickel nitrate, nickel acetate, nickel acetylacetonate, copper chloride, copper sulfate, copper nitrate, copper acetate and copper acetylacetonate.
4. The method according to claim 1, wherein M is selected from Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, and Ta, A is selected from Al, Si, and Ga, and X is selected from C and N.
5. The method according to claim 1, wherein in the step 1), the reaction temperature of the water bath condition is 30 to 100 ℃ and the reaction time is 0.5 to 170 hours.
6. The production method according to claim 1, wherein in the step 2), the oil bath condition is performed at a reaction temperature of 30 to 200 ℃ for 1 to 48 hours.
7. The method of claim 1, wherein the protective atmosphere is selected from one of nitrogen, hydrogen, argon, or a hydrogen/argon mixture.
8. The method according to claim 1, wherein the nitrogen-containing compound is one or more selected from the group consisting of cyanamide, urea, melamine, monomethyl imidazole, dimethyl imidazole, 2-aminoterephthalic acid, N-dimethylformamide, 2-bipyridine, 2,3,6,7,10, 11-hexa-amino-triphenyl, dopamine, polyacrylonitrile, ethylenediamine, acetonitrile, and pyrrole.
9. The preparation method according to claim 1, wherein in the step 3), the temperature of the heating treatment is 100 to 800 ℃, the temperature rise rate is 0.5 to 10 ℃/min, and the heat preservation time of the heating treatment is 0.1 to 8 hours;
in the step 4), the temperature of the high-temperature reduction is 100-1000 ℃, the heating rate of the high-temperature reduction is 0.5-10 ℃/min, and the heat preservation time of the high-temperature reduction is 0.1-8 hours.
10. A nitrogen-doped porous carbon-coated metal nanocomposite catalyst, characterized by comprising the nitrogen-doped porous carbon-coated metal nanocomposite catalyst obtained by the preparation method according to any one of claims 1 to 9.
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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN111477883A (en) * 2020-05-11 2020-07-31 叶际宽 MOFs-derived porous carbon-coated NiFe nano-alloy oxygen evolution catalyst and preparation method thereof
CN111978555A (en) * 2020-07-20 2020-11-24 华南理工大学 Ternary metal organic framework sterilization material and preparation method and application thereof
CN112366328A (en) * 2020-11-09 2021-02-12 重庆大学 Preparation method of partially ordered two-dimensional superlattice platinum alloy catalyst layer
CN112371150A (en) * 2020-10-26 2021-02-19 厦门大学 Nickel-aluminum bimetal nitrogen-carbon doped catalyst, preparation method thereof and application thereof in catalyzing levulinic acid hydrogenation to prepare gamma-valerolactone
CN112563515A (en) * 2020-12-11 2021-03-26 苏州大学张家港工业技术研究院 Iron-nitrogen co-doped carbon and MXene compound and preparation method and application thereof
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CN115000426A (en) * 2022-06-22 2022-09-02 郑州轻工业大学 Two-dimensional titanium carbide loaded two-component high-efficiency zinc-air battery catalyst and preparation method and application thereof
CN115090334A (en) * 2022-07-06 2022-09-23 扬州工业职业技术学院 MOF-derived porous carbon-based nano composite light degradation material
CN115259088A (en) * 2022-07-03 2022-11-01 复旦大学 Photothermal driven solid hydride MgH2Composite hydrogen storage material and preparation method thereof
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CN116742024A (en) * 2023-08-10 2023-09-12 金川集团股份有限公司 Nitrogen-doped induced carbon-coated bi-crystal Ni catalyst, and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160211529A1 (en) * 2013-09-19 2016-07-21 Council Of Scientific & Industrial Research N-doped porous carbon electrocatalyst and process for preparation thereof
CN108660473A (en) * 2018-05-17 2018-10-16 大连理工大学 A kind of electrolytic seawater catalyst for preparing hydrogen and its synthetic method based on MXene Yu transition metal carbide composite nanostructure
CN109304476A (en) * 2017-07-28 2019-02-05 中国石油化工股份有限公司 Carbon coating transition metal nanocomposite and its preparation method and application
CN110034306A (en) * 2019-03-13 2019-07-19 上海交通大学 The preparation method and application of the composite material of the porous carbon coating cobalt nano-particle of N doping
CN110474062A (en) * 2019-08-02 2019-11-19 北京化工大学常州先进材料研究院 A kind of preparation and application of efficient MXene titanium carbide cell catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160211529A1 (en) * 2013-09-19 2016-07-21 Council Of Scientific & Industrial Research N-doped porous carbon electrocatalyst and process for preparation thereof
CN109304476A (en) * 2017-07-28 2019-02-05 中国石油化工股份有限公司 Carbon coating transition metal nanocomposite and its preparation method and application
CN108660473A (en) * 2018-05-17 2018-10-16 大连理工大学 A kind of electrolytic seawater catalyst for preparing hydrogen and its synthetic method based on MXene Yu transition metal carbide composite nanostructure
CN110034306A (en) * 2019-03-13 2019-07-19 上海交通大学 The preparation method and application of the composite material of the porous carbon coating cobalt nano-particle of N doping
CN110474062A (en) * 2019-08-02 2019-11-19 北京化工大学常州先进材料研究院 A kind of preparation and application of efficient MXene titanium carbide cell catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIYI CHEN ET AL.: ""Sublimation-Vapor Phase Pseudomorphic Transformation of Template-Directed MOFs for Efficient Oxygen Evolution Reaction"", 《ADVANCED FUNCTIONAL MATERIALS》 *
TENG LIU ET AL.: ""Self-Sacrificial Template-Directed Vapor-Phase Growth of MOF Assemblies and Surface Vulcanization for Efficient Water Splitting"", 《ADVANCED MATERIALS》 *

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CN111468163A (en) * 2020-05-12 2020-07-31 大连理工大学 Two-dimensional iron monatomic catalyst, preparation thereof and application thereof in reduction production of ethylene by 1, 2-dichloroethane
CN111468163B (en) * 2020-05-12 2022-11-18 大连理工大学 Two-dimensional iron monatomic catalyst, preparation thereof and application thereof in production of ethylene by reducing 1,2-dichloroethane
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