CN111977630B - Metal-carbon hybrid material and preparation method thereof - Google Patents
Metal-carbon hybrid material and preparation method thereof Download PDFInfo
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- CN111977630B CN111977630B CN202010703996.8A CN202010703996A CN111977630B CN 111977630 B CN111977630 B CN 111977630B CN 202010703996 A CN202010703996 A CN 202010703996A CN 111977630 B CN111977630 B CN 111977630B
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention relates to a metal-carbon hybrid material and a preparation method thereof, wherein an amidoxime group is firstly introduced into a polyacrylonitrile grafted carbonaceous material to obtain an amidoxime modified carbonaceous material, the amidoxime modified carbonaceous material and a metal salt are dispersed in a hydrothermal kettle to carry out self-assembly reaction, and then are calcined in a reducing atmosphere to obtain the metal-carbon hybrid material, and in the preparation process, the size and the dispersion state of metal nano particles in the metal-carbon hybrid material are regulated and controlled by regulating the content of the amidoxime group in the amidoxime modified carbonaceous material and the molar ratio of the amidoxime group to metal ions in the metal salt; the prepared metal-carbon hybrid material consists of a carbonaceous substrate and metal nano-particles dispersed on the carbonaceous substrate, wherein the surface of the metal nano-particles is coated with a carbon layer, the metal nano-particles are in a monodispersed state, and are uniformly dispersed and uniform in size, and the average particle size is adjustable and controllable between 5nm and 20 nm. The metal nano particles in the metal-carbon hybrid material are highly dispersed and have small granularity.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material preparation, and relates to a metal-carbon hybrid material and a preparation method thereof.
Background
Carbon materials are widely found in nature, and have stable physicochemical properties and large specific surface area and pore volume. When the carbon material is used as a carrier, the intrinsic conductivity of the carbon material can be used as a continuous conductive framework to accelerate the transmission of electrons in the electrochemical process; meanwhile, the unique pore channel structure can be used as a mass transfer channel to accelerate the material transmission in the reaction process. In the current research work, the commonly used carbonaceous carriers mainly include carbon nanotubes, porous carbon, ordered mesoporous carbon, carbon spheres, graphene, and the like. The patent (CN104124022A) discloses a carbon nanotube-based nickel nanoparticle composite material and a preparation method thereof, the carbon nanotube-based magnetic nanoparticle composite material is prepared by adopting a solvothermal method, the preparation process of the method is carried out in a closed reaction kettle, the controllability is realized, the nucleation sites of metal-based nanoparticles are random due to the self-assembly process depending on surface electrostatic attraction, and the uniformly dispersed small-size metal-based nanoparticles are difficult to obtain. In addition, due to the agglomeration of the magnetic nanoparticles in the thermal reduction process, the size of the metal nanoparticles in the prepared carbon nanotube-based magnetic nanocomposite is about tens to hundreds of nanometers, and the large-size nanoparticles cannot expose enough active sites, so that the catalytic activity of the catalyst is inhibited; the patent (CN109286027A) discloses a preparation method of a Fe nanoparticle and carbon nanotube composite material, which adopts a solvothermal method to prepare Fe nanoparticles with large size (60-200 nm) and low dispersion degree. The reason why the size and the dispersion degree of the metal nanoparticles on the carbonaceous substrate are difficult to be effectively controlled by analyzing the technology is mainly that the carbonaceous material is not pretreated, the self-assembly process of the metal salt and the carbonaceous material in a hydrothermal system is mainly carried out through the electrostatic action, the nucleation sites are random, and the preliminarily obtained metal oxide nanoparticles possibly grow continuously on certain nucleation sites, so that the superfine metal nanoparticle/carbonaceous substrate hybrid material with uniform granularity and high dispersion degree cannot be prepared. In the current research, the metal/carbon hybrid material which has the advantages of superfine metal particle size, uniform size, controllable size and high dispersity is difficult to prepare. Therefore, there is a need to develop a method for uniformly supporting highly dispersed ultrafine metal nanoparticles with controllable size and kind on a carbonaceous substrate.
In addition, the amidoxime group has strong adsorption capacity on heavy metals, so that the carbon material modified by the amidoxime group has more applications in the environmental remediation fields of seawater uranium removal, heavy metal removal in soil and the like. The literature (ACS Sustainable Chemistry & Engineering 2019,7,10800-10807) grafts amidoxime groups onto porous carbon electrodes as electrochemical seawater uranium removal electrodes. The material has stronger chemical adsorption capacity to uranium ions, and shows good uranium removing capacity in a solution with low uranium ion concentration. The literature (Nature Communications 2019102440) grafts an amidoxime group on a porous carbon electrode, and the material shows good chemical adsorption capacity on metal ions such as Pb, Cd, Cu and the like as an electrode for electrochemically removing the metal ions in soil. However, in the above studies, in order to increase the adsorption amount of metal ions, amidoxime groups are often grafted on the surface of the carbon material as many as possible to increase the adsorption sites of the metal ions, so that the metal ions are distributed densely, and agglomeration is easily generated in the subsequent process of preparing metal simple substance particles by reducing the metal ions. In addition, in the process of recycling the adsorbed metal ions, an electrical reduction or thermal reduction method with more extensive condition control is often adopted, the sizes of the obtained metal particles are mostly micron-sized, or agglomeration is obviously generated, the dispersity is poor, and the catalytic performance is greatly influenced. In the current application research related to the amidoxime group functionalized carbon material, the carbon material is only used as a heavy metal ion adsorbent in the field of environmental remediation.
Disclosure of Invention
The invention provides preparation and application of a metal-carbon hybrid material, and aims to overcome the technical problems of large size, nonuniform size and low dispersion degree of metal nano particles in the prior art, in particular to utilize the chemical adsorption capacity of an amidoxime group to metal ions, firstly take the amidoxime group as a nucleation site of metal oxide particles in a hydrothermal self-assembly process, realize anchoring of ultrafine metal oxide particles with uniform dispersion on a carbonaceous substrate by adjusting the modification amount of the amidoxime group on the carbonaceous substrate and the type and concentration of metal salts in the hydrothermal self-assembly process, and obtain the metal-carbon hybrid material by subsequent thermal reduction. During the self-assembly process, the size is regulated and controlled by the modification amount of the amidoxime group and the concentration of the metal salt: the amidoxime group is used as a nucleation site of the metal oxide nano-particles obtained by initial preparation, and the metal salt provides a metal source, so that the dispersion degree and the size of the metal nano-particles in the finally obtained metal nano-particle/carbonaceous substrate hybrid material can be regulated and controlled by adjusting the ratio of the modification amount of the amidoxime group to the adding amount of the metal salt. Specifically, for carbonaceous materials with the same modification amount of amidoxime groups, the amount concentration of metal salt substances is increased, namely the size of metal nanoparticles in the metal nanoparticle/carbonaceous substrate hybrid material is increased; for the carbonaceous material added with the same amount and concentration of the amidoxime group modification amount of the metal salt, if the amidoxime group modification amount on the carbonaceous material is higher, the size of the metal nano-particles in the obtained metal nano-particle/carbonaceous substrate hybrid material is smaller, and the dispersity is higher.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a metal-carbon hybrid material comprises the steps of firstly introducing an amidoxime group to a polyacrylonitrile grafted carbonaceous material to obtain an amidoxime modified carbonaceous material, then dispersing the amidoxime modified carbonaceous material and a metal salt in an organic solvent for self-assembly reaction, and calcining in a reducing atmosphere to obtain the metal-carbon hybrid material;
in the preparation process, the size and the dispersion state of metal nano particles in the metal-carbon hybrid material are regulated and controlled by regulating the content of an amidoxime group in the amidoxime-modified carbonaceous material and the molar ratio of the amidoxime group to metal ions in metal salt, specifically, when the content of the amidoxime group is fixed, the larger the molar ratio of the amidoxime group to the metal ions is, the smaller the size of the metal nano particles is, the higher the dispersion degree is, and vice versa; when the molar ratio of the amidoxime group to the metal ions is constant, the larger the content of the amidoxime group is, the smaller the size of the metal nanoparticles is, the higher the dispersity is, and vice versa.
The hydrothermal self-assembly method based on strong coordination of an amidoxime group to metal ions adopted by the invention specifically comprises the following steps: firstly, metal ions in a solution are chemically adsorbed on a carrier through coordination bonds, then the adsorbed metal ions are converted into metal oxide particles in situ in a hydrothermal process, and finally the metal oxide particles converted in situ are used as nucleation sites for subsequent growth of the particles. The invention mainly utilizes the strong coordination of the amidoxime group and the controllability of the modification amount (the content of the amidoxime group in the carbonaceous material), realizes the adsorption of metal ions and the in-situ conversion into metal oxide particles in the self-assembly process, and avoids the agglomeration of ultrafine nano particles in the preparation process for reducing the surface energy. Different from the common coordination adsorption mode based on carboxyl and hydroxyl, the amidoxime group can form a stable five-membered ring structure after being chelated with metal ions as a bidentate ligand, so that the amidoxime group has stronger coordination capacity and stripping resistance capacity for the metal ions. In addition, the ortho-position effect of adjacent amidoxime groups can jointly form coordination with metal ions, and the capability of chelating the metal ions is further enhanced. Therefore, in the processes of metal ion adsorption and in-situ conversion into oxide, the high selectivity chelation of the uniformly distributed amidoxime groups to the metal ions ensures the uniform dispersion of the metal ion adsorption and subsequent crystallization nucleation, and finally the surface-modified metal oxide particles are uniformly dispersed.
As a preferred technical scheme:
the preparation method of the metal-carbon hybrid material comprises the following specific steps:
(1) using carbon material with N2Plasma treatment (with N)2Plasma treatment is carried out for modifying active oxygen species on the surface of the carbon material so as to be beneficial to subsequent grafting of polyacrylonitrile on the surface), an organic solvent containing acrylonitrile is added, cyano groups can be introduced on the surface of the carbon material after heating reaction for a period of time, and suction filtration and washing are carried out to obtain the polyacrylonitrile grafted carbon material;
(2) dispersing a polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value, heating for reaction, and separating, washing and vacuum-drying a product after the reaction to obtain an amidoxime-modified carbonaceous material;
according to the invention, an amidoxime group is grafted on the surface of a carbonaceous material, and the amidoxime group is firstly used as an adsorption site of metal ions in the subsequent hydrothermal self-assembly process, so that the metal ions are crystallized and nucleated at fixed points on the surface of the amidoxime-modified carbonaceous material; the content (modification density) of the amidoxime groups on the surface of the carbonaceous material can be regulated by regulating the feed ratio of the hydroxylamine hydrochloride to the carbonaceous material, and finally the regulation of the nucleation sites of the metal oxide particles in the subsequent hydrothermal process is realized; other surface modification technologies (acidification and oxidation) adopt excessive auxiliary reagents to carry out excessive pretreatment on a carrier, so that the saturation of surface modification sites is caused, and the randomness of adsorption and nucleation sites is larger and obvious uncontrollable when a small amount of metal ion precursors are used in the subsequent liquid phase self-assembly process; the cyano conversion rate of the PAN can be improved by increasing the charge ratio and the reaction time of the hydroxylamine hydrochloride/PAN, namely, the modification amount of the surface amidoxime group is increased (the surface modification concentration is increased), otherwise, the modification amount of the surface amidoxime group is reduced (the surface modification concentration is reduced). Meanwhile, the specific surface area (fiber thickness) of the PAN fiber also influences the modification process of hydroxylamine hydrochloride, and when the charge ratio, the temperature and the reaction duration are the same, the larger the specific surface area of the PAN fiber is, the more reaction is easy to occur, so that the modification amount (cyano conversion rate) of the amidoxime group is higher;
wherein the calculation formula of the cyano conversion rate is as follows:
wherein W1For modified mass, W0For mass before modification, M1Molar mass of hydroxylamine (33), M0Is acrylonitrile monomer (C)3H3N) molar mass (53);
the modification amount (mol) of the amidoxime group can be calculated by the following formula:
wherein W1Mass after amidoximation modification, W0Mass before amidoximation modification, M1The molar mass of hydroxylamine (33).
Finally, the concentration of metal oxide particle nucleation sites in the subsequent hydrothermal self-assembly process is regulated and controlled by regulating and controlling the modification amount (concentration) of the surface amidoxime groups, and the modification of monodisperse ultrafine nanoparticles on the surface of the carbon material is facilitated;
when sodium carbonate is used for adjusting the pH value, the reaction principle is as follows:
(3) dispersing a carbonacious material modified by amidoxime and metal salt in a hydrothermal kettle for self-assembly reaction, separating and washing a product after the reaction is finished, and finally calcining in a reducing atmosphere to obtain a metal-carbon hybrid material;
under the hydrothermal condition, an amidoxime group modified on a carbonaceous material is used as a bidentate ligand, lone-pair electrons on amino and hydroxyl of the amidoxime group can form a stable five-membered ring structure after being chelated with metal ions, the amidoxime group has strong coordination capacity on the metal ions, the ortho-position effect of adjacent amidoxime groups can form coordination with the metal ions together, the metal ions are further anchored on the surface of the carbonaceous material, and then the metal ions anchored on the surface of the carbonaceous material by the amidoxime group through coordination chelation are converted into metal oxides or metal nanoparticles in situ and serve as nucleation sites for continuous deposition and crystallization of the metal ions in a solution. When the concentration of the metal salt is higher, the more metal ions in the solution, and thus a large amount of metal ions may be continuously transformed, deposited and grown based on the nucleation sites, resulting in an increase in the size of the metal nanoparticles;
the amount of amidoxime modification (density) determines the number of grain nucleation sites at the initial stage of self-assembly (density); the concentration of the metal salt determines the amount of metal precursor, since the metal ions in solution will be converted, deposited and crystallized at the nucleation sites. In general, the modification of the amidoxime group mainly determines the degree of dispersion of the metal nanoparticles, and the concentration of the metal salt mainly determines the size of the metal nanoparticles. However, the ratio of the concentration of the metal salt to the modification amount of the amidoxime group determines the excess of the metal salt relative to the nucleation sites in the solution, the regulation effect is similar to the concentration of the metal salt, the higher the ratio of the concentration of the metal salt to the modification amount of the amidoxime group, the more metal ions are in the solution, and the larger the size of the metal nanoparticles is caused by the continuous growth of crystal grains on the nucleation sites.
A metal ion as described aboveIn the step (1), the carbonaceous material is a single-walled carbon nanotube, a multi-walled carbon nanotube (the single-walled carbon nanotube or the multi-walled carbon nanotube is prepared by a chemical vapor deposition method, a laser evaporation method, an arc discharge method or a template method), graphene (the graphene is prepared by a chemical vapor deposition method, a Hummers-like method or a physical stripping method), ordered mesoporous carbon (the ordered mesoporous carbon is prepared by a template method), porous carbon (the porous carbon is prepared by a template method or an etching method), a carbon sphere (the carbon sphere is prepared by a solvothermal method, a chemical vapor deposition method, a template method, a mechanical ball milling method or an emulsification method), a carbon fiber or melamine foam. For most carbonaceous materials not included herein, such as, but not limited to, carbon nanorods, various biomass carbon materials, various commercial carbon materials (e.g., Ketjen black), graphitic carbon nitride (g-C)3N4) The method has universality, and the metal nanoparticle/carbonaceous substrate hybrid material with metal nanoparticles loaded on a specific substrate can be obtained as long as the condition that the amidoxime group can be modified on the surface of the substrate is met;
the specific surface area of the carbonaceous material is 150-2500 m2(ii)/g; the specific surface area of the carbonaceous material determines the maximum surface modification amount of the amidoxime group, and the larger the specific surface area is, the higher the maximum modification amount of the amidoxime group is;
the plasma treatment time is 10-90 min, N2The pressure is 5-20 Pa, the power is 50-200W, the voltage is 500-1000V, and the current is 100-300 mA; plasma treatment time, N2When the pressure or the power is insufficient, the modified active oxygen species on the surface are less, which is not beneficial to the subsequent grafting of the surface polyacrylonitrile and the conversion of the cyano group to the amidoxime group;
in an organic solvent containing acrylonitrile, the volume fraction of the acrylonitrile is 30-70%, and the organic solvent is N-methyl pyrrolidone, N-dimethylformamide, ethylene glycol or glycerol; the organic solvent is used as a medium for reaction, and the following two conditions need to be met: 1) the performance of keeping stable in the reaction temperature range (considering physical properties such as freezing point, boiling point, pyrolysis temperature and the like); 2) does not react with the reactants and products;
N2plasma processThe concentration of the carbonaceous material after the daughter treatment in the organic solvent is 5-50 mg/mL;
the heating reaction is carried out for a period of time, namely heating to 20-80 ℃ for reaction for 5-10 h.
According to the preparation method of the metal-carbon hybrid material, in the step (2), the concentration of the polyacrylonitrile grafted carbon material in water is 0.1-10 mg/ml; the carbonaceous material is uniformly dispersed in the water for subsequent amidoxime modification, and the carbon material is uniformly dispersed in the water for uniformly modifying amidoxime groups on the surface of the carbonaceous material, so that the uniform distribution of nano-particles obtained by subsequent self-assembly is facilitated;
the mass ratio of the polyacrylonitrile grafted carbonaceous material to the hydroxylamine hydrochloride is 1: 0.001-0.5; this parameter determines the amount of substance of the precursor (hydroxylamine hydrochloride) that converts cyano groups to amidoxime groups, the more precursors, the more favorable the reaction, the higher the conversion of cyano groups (the higher the modification intensity);
the pH value regulator used for regulating the pH value is sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide or ammonia water, and the regulated pH value is 6-10; the pH of the amine oximation reaction is suitable to be 6-10, and the reaction products and the products are hydrolyzed when the acidity is too strong;
the heating reaction is carried out for a period of time, namely heating to 30-90 ℃ and reacting for 30-180 min; the reaction temperature determines the reaction rate, the reaction rate is too slow due to too low temperature, and reactants and products are pyrolyzed or hydrolyzed due to too high temperature, so that the optimal time range meeting the requirements is 30-90 ℃; the reaction time determines the progress of the reaction, and too short time causes a large amount of precursors not to be utilized and the conversion rate of the cyano group is too low; if the time is too long, the precursor is consumed early, chemical reaction does not occur in a large amount of subsequent time, and the large amount of subsequent time is meaningless, so that the time range of 30-180 min is the optimal time range for meeting the requirements;
the temperature of vacuum drying is 50-100 ℃.
According to the preparation method of the metal-carbon hybrid material, in the step (3), the mass ratio of the amidoxime-modified carbonaceous material to the metal salt is 1: 0.01-0.6; the concentration of the carbonacious material modified by the amidoxime in water is 0.1-10 mg/ml, the mass ratio of the carbonacious material modified by the amidoxime to the metal salt is 1: 0.01-0.6, and the following results are obtained: the concentration of the metal salt is 0.001-6 mg/ml;
the metal salt is MnCl2·4H2O、MnSO4·4H2O、FeCl3·6H2O、Fe(NO3)3·9H2O、CoCl2·6H2O、Co(NO3)2·6H2O、Co(Ac)2·4H2O、NiCl2·6H2O、Ni(NO3)2·6H2O、Ni(Ac)2·4H2O、CuCl2·2H2O、CuSO4·5H2O、Cu(NO3)2·2.5H2O、Cu(Ac)2·H2O、Zn(NO3)2·6H2O、Zn(Ac)2·2H2O、ZnSO4·7H2O、TiCl4、SnCl2、SnCl4Or BiCl3(ii) a In the self-assembly process based on the amidoxime group, metal salt is used as an important precursor to provide metal ions for a reaction system, so that the selection of the type of the metal salt (such as iron salt, manganese salt and the like) determines the type of the zero-valent metal nanoparticles in the final product (corresponding to the iron nanoparticles, the manganese nanoparticles and the like in the prior art); for the metal salt not included in the present invention, the metal/carbon hybrid material with controllable size and dispersity can be prepared by the method provided by the present invention as long as "the amidoxime group has chemical adsorption to the metal ion in the metal salt" is satisfied during the self-assembly process.
According to the preparation method of the metal-carbon hybrid material, in the step (3), the concentration of the amidoxime-modified carbonaceous material in water is 0.1-10 mg/ml;
dispersing under the stirring condition, wherein the stirring speed is 100-1000 rpm;
the temperature of the self-assembly reaction is 120-200 ℃, and the time is 30-180 min;
the reducing atmosphere is H2Mixed gas of/Ar or H2/N2Mixed gas of H2Mass fraction in reducing atmosphere1-50%;
the calcination is to heat the mixture to 600-1000 ℃ at a heating rate of 1-10 ℃/min and then to preserve the temperature for 60-300 min.
The invention also provides a metal-carbon hybrid material prepared by the preparation method of the metal-carbon hybrid material, which consists of a carbonaceous substrate and metal nano particles dispersed on the carbonaceous substrate, wherein the surface of the metal nano particles is coated with a carbon layer, the metal nano particles are in a monodisperse state, are uniformly dispersed and have uniform size, and the average particle size is adjustable and controllable between 5nm and 20 nm. The metal particle species and the carbonaceous substrate species can be regulated. Different metal nanoparticles can be loaded on different carbonaceous substrates by adjusting the types of the metal salt and the carbonaceous substrates; the average particle size of the nanoparticles can be adjusted by adjusting the modification amount of the amidoxime group and the concentration of the metal salt, and the adjustable range is 5-20 nm. The particle size is controlled by the modification amount of the amidoxime group and the concentration of the metal salt. The dispersion is uniform or good as long as no agglomeration occurs between the particles.
The invention is not limited to the preparation of the metal nanoparticle/carbonaceous substrate hybrid material with the adjustable range of the average particle size of the metal nanoparticles being 5-20 nm, and all preparation process data are not completely optimized, so that the metal/carbonaceous substrate hybrid material with the average particle size of the metal nanoparticles being less than 5nm can be prepared by optimizing the precursor proportion in the preparation process. In addition, the upper limit of the average particle size of the nanoparticles to 20nm in the present invention is based on the consideration that as many active sites as possible are exposed. Similarly, if the actual production efficiency or different application requirements are considered, the metal nanoparticle/carbonaceous substrate hybrid material with the average metal nanoparticle diameter larger than 20nm can be prepared by adjusting the proportion of the amidoxime group and the metal salt.
The principle of the invention is as follows:
because an amidoxime group has stronger chemical adsorption capacity to metal ions, amidoxime modified carbon materials are currently more applied to the field of environmental remediation and are used for adsorbing heavy metal ions in water; when the metal/carbon hybrid material is prepared by self-assembly through electrostatic force, the nucleation sites of the metal nanoparticles are random, and agglomeration or continuous growth of crystal grains on the random nucleation sites is likely to occur.
The amidoxime group in the amidoxime-modified carbonaceous material is used as a structure-directing group, and the amidoxime group has strong chemical adsorption capacity to metal ions, so that the amidoxime group can be used as a nucleation site of metal oxide nanoparticles in hydrothermal self-assembly reaction. On one hand, the metal oxide particles are nucleated at the site modified by the amidoxime group, and the dispersion degree of the amidoxime determines the dispersion degree of the metal oxide particles and the finally obtained metal nano-particles, so that the agglomeration of the particles in the thermal reduction process can be effectively avoided. On the other hand, the metal oxide nanocrystals are uniformly crystallized and nucleated on the amidoxime group modification sites, so that the randomness of crystallization and nucleation in the electrostatic self-assembly process is avoided, the continuous growth of the metal oxide nanocrystals on random sites is avoided, and the characteristics of small granularity and uniformity are ensured; therefore, the method of the present invention facilitates the preparation of a metal/carbon hybrid material in which metal nanoparticles are highly dispersed, small in size, and uniform.
In addition, in the invention, carbon on the carbonaceous material can diffuse in the high-temperature calcination process of the product after the self-assembly reaction, so that the metal nano particles used in the metal/carbon hybrid material are coated with a carbon layer, and the specific coating structure can avoid the direct contact of a medium and the metal nano particles in the catalysis process, namely effectively avoid the corrosion of the metal nano particles and the secondary pollution caused by the leakage of metal ions. In addition, a highly graphitized carbonaceous material (the graphitization degree has a large relationship with the preparation mode of the carbonaceous material, generally relates to factors such as the calcining temperature, the introduction of a catalyst for assisting pyrolysis and the like, the higher the temperature is, the more favorable the conversion of the carbon material from amorphous state to graphitization is, and the addition of the catalyst (such as transition metal, phosphoric acid and the like) is, the higher the graphitization degree of the carbon material is, the more favorable the graphitization degree of the carbon material is) is adopted as a continuous conductive substrate, so that the electron transmission is facilitated. The carbon material has a unique pore channel structure which can be used as a mass transfer channel, shortens a mass transfer path and has higher mass transfer capacity.
Has the advantages that:
(1) according to the metal-carbon hybrid material, amidoxime is used as a structure guiding group, so that the agglomeration of particles in the thermal reduction process is effectively avoided, and the highly dispersed metal nano-particle/carbon-based hybrid material with small granularity is prepared;
(2) according to the metal-carbon hybrid material, the metal nano particles are coated with the carbon layer in the high-temperature calcination process, so that secondary pollution caused by corrosion of the metal nano particles and leakage of metal ions is effectively avoided;
(3) according to the metal-carbon hybrid material, the small-size nano particles obtained by the method can obviously increase the material/solvent interface, and the utilization rate of the metal nano particles can be improved;
(4) the metal-carbon hybrid material takes the highly graphitized carbonaceous material with rich pore channel structures as a continuous conductive substrate, thereby being beneficial to the transmission of ions and electrons.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a metal-carbon hybrid material comprises the following steps:
(1) using carbon material (single-wall carbon nano tube) with N2Performing plasma treatment for 20min, then dispersing in an organic solvent (NMP) containing acrylonitrile, heating to 30 ℃ for reaction for 5h, performing suction filtration and washing to obtain a polyacrylonitrile grafted carbonaceous material; wherein N is in plasma treatment2The pressure was 5Pa, the power was 80W, the voltage was 700V, the current was 150mA, the concentration of the plasma-treated carbonaceous material in an organic solvent (NMP) was 10mg/ml, and the volume fraction of acrylonitrile in the organic solvent was 40%.
(2) Dispersing the polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value to 7 by using sodium carbonate, heating to react (the temperature is 90 ℃ and the time is 60min), and separating, washing and vacuum drying a product (the temperature is 60 ℃) after the reaction to obtain the amidoxime modified carbonaceous material; wherein the concentration of the carbonaceous material in water is 1.33 mg/ml; the mass ratio of the carbonaceous material to the hydroxylamine hydrochloride is 1: 0.03.
(3) Mixing the obtained amidoxime-modified carbonaceous material with metal salt (MnCl)2·4H2O) dispersing in water under the stirring condition (the rotating speed of magnetic stirring is 220rpm), carrying out self-assembly in a hydrothermal kettle (the temperature is 180 ℃ and the time is 60min), and separating and washing a product after the reaction is finished, wherein the concentration of the amidoxime modified carbonaceous material in NMP is 0.67 mg/ml; the mass ratio of the amidoxime-modified carbonaceous material to the metal salt is 1: 0.03;
(4) calcining the washed product in a reducing atmosphere, wherein the temperature rise rate of the calcination is 5 ℃/min, the pyrolysis temperature is 950 ℃, and the heat preservation time is 120 min; the reducing atmosphere is H2Mixed gas of/Ar; h2The mass fraction in the reducing atmosphere is 25 percent; obtaining the metal-carbon hybrid material.
In the prepared metal-carbon hybrid material, the average particle size of metal nanoparticles is 8 nm;
example 2
A preparation method of a metal-carbon hybrid material comprises the following steps:
(1) using N as carbon material (ordered mesoporous carbon)2Performing plasma treatment for 90min, then dispersing in an organic solvent (EG) containing acrylonitrile, heating to 40 ℃ for reaction for 7h, performing suction filtration and washing to obtain a polyacrylonitrile grafted carbonaceous material; wherein N is in plasma treatment2The pressure was 7Pa, the power was 100W, the voltage was 900V, the current was 300mA, the concentration of the plasma-treated carbonaceous material in an organic solvent (NMP) was 20mg/ml, and the volume fraction of acrylonitrile in the organic solvent was 60%.
(2) Dispersing the polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value to 8 by using potassium hydroxide, heating to react (the temperature is 70 ℃ and the time is 180min), and separating, washing and vacuum drying a product (the temperature is 70 ℃) after the reaction to obtain the amidoxime modified carbonaceous material; wherein the concentration of the carbonaceous material in water is 2 mg/ml; the mass ratio of the carbonaceous material to the hydroxylamine hydrochloride is 1: 0.05.
(3) Mixing the obtained amidoxime-modified carbonaceous material with a metal salt (Ni (NO)3)2·6H2O) dispersing in water under the stirring condition (the rotating speed of magnetic stirring is 320rpm), carrying out self-assembly in a hydrothermal kettle (the temperature is 160 ℃, the time is 50min), and separating and washing a product after the reaction is finished, wherein the concentration of the amidoxime modified carbonaceous material in the water is 3 mg/ml; the mass ratio of the amidoxime-modified carbonaceous material to the metal salt is 1: 0.05;
(4) calcining the washed product in a reducing atmosphere, wherein the temperature rise rate of the calcination is 10 ℃/min, the pyrolysis temperature is 800 ℃, and the heat preservation time is 100 min; the reducing atmosphere is H2A mixed gas of/Ar; h2The mass fraction in the reducing atmosphere is 12 percent; obtaining the metal-carbon hybrid material.
In the prepared metal-carbon hybrid material, the average particle size of the metal nanoparticles is 10 nm.
Example 3
A preparation method of a metal-carbon hybrid material comprises the following steps:
(1) using N as carbon material (graphene)2Performing plasma treatment for 40min, dispersing in an organic solvent (NMP) containing acrylonitrile, heating to 50 ℃ for reaction for 10h, performing suction filtration and washing to obtain a polyacrylonitrile grafted carbonaceous material; wherein N is in plasma treatment2The pressure was 10Pa, the power was 120W, the voltage was 700V, the current was 150mA, the concentration of the plasma-treated carbonaceous material in an organic solvent (NMP) was 10mg/ml, and the volume fraction of acrylonitrile in the organic solvent was 30%.
(2) Dispersing a polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value to 9 by using potassium carbonate, heating to react (the temperature is 80 ℃ and the time is 70min), and separating, washing and vacuum drying a product after the reaction (the temperature is 80 ℃) to obtain an amidoxime modified carbonaceous material; wherein the concentration of the carbonaceous material in water is 4 mg/ml; the mass ratio of the carbonaceous material to the hydroxylamine hydrochloride is 1: 0.008.
(3) Mixing the obtained amidoxime-modified carbonaceous material with a metal salt (CoCl)2·6H2O) dispersing in a solvent (DMF) under the stirring condition (the rotating speed of magnetic stirring is 420rpm), carrying out self-assembly in a hydrothermal kettle (the temperature is 120 ℃ and the time is 30min), and separating and washing a product after the reaction is finished, wherein the concentration of the amidoxime modified carbonaceous material in the DMF is 2 mg/ml; the mass ratio of the amidoxime-modified carbonaceous material to the metal salt is 1: 0.02;
(4) calcining the washed product in a reducing atmosphere, wherein the temperature rising rate of the calcination is 8 ℃/min, the pyrolysis temperature is 700 ℃, and the heat preservation time is 110 min; the reducing atmosphere is H2Mixed gas of/Ar; h2The mass fraction in the reducing atmosphere is 10 percent; obtaining the metal-carbon hybrid material.
In the prepared metal-carbon hybrid material, the average particle size of the metal nanoparticles is 15 nm.
Example 4
A preparation method of a metal-carbon hybrid material comprises the following steps:
(1) using carbon material (porous carbon) with N2Treating with plasma for 50min, dispersing in organic solvent (DMF) containing acrylonitrile, heating to 80 deg.C, reacting for 5h, filtering, and washing to obtain polyacrylonitrile grafted carbonaceous material; wherein N is in plasma treatment2The pressure was 15Pa, the power was 120W, the voltage was 1000V, the current was 200mA, the concentration of the plasma-treated carbonaceous material in an organic solvent (NMP) was 30mg/ml, and the volume fraction of acrylonitrile in the organic solvent was 60%.
(2) Dispersing the polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value to 9 by using sodium hydroxide, heating to react (the temperature is 60 ℃ and the time is 90min), and separating, washing and vacuum drying a product (the temperature is 100 ℃) after the reaction to obtain the amidoxime modified carbonaceous material; wherein the concentration of the carbonaceous material in water is 0.3 mg/ml; the mass ratio of the carbonaceous material to the hydroxylamine hydrochloride is 1: 0.016.
(3) Mixing the obtained amidoxime-modified carbonaceous material with a metal salt (CuCl)2·2H2O) dispersing in solvent water under the stirring condition (the rotating speed of magnetic stirring is 520rpm), carrying out self-assembly in a hydrothermal kettle (the temperature is 120 ℃, and the time is 180min), and separating and washing a product after the reaction is finished, wherein the concentration of the amidoxime modified carbonaceous material in DMF is 0.1 mg/ml; the mass ratio of the amidoxime-modified carbonaceous material to the metal salt is 1: 0.016;
(4) calcining the washed product in a reducing atmosphere, wherein the temperature rise rate of the calcination is 5 ℃/min, the pyrolysis temperature is 600 ℃, and the heat preservation time is 90 min; the reducing atmosphere is H2Mixed gas of/Ar; h2The mass fraction in the reducing atmosphere is 50 percent; obtaining the metal-carbon hybrid material.
In the prepared metal-carbon hybrid material, the average particle size of the metal nanoparticles is 6 nm.
Example 5
A preparation method of a metal-carbon hybrid material comprises the following steps:
(1) using N as carbon material (carbon spheres)2Treating with plasma for 60min, dispersing in organic solvent (GL) containing acrylonitrile, heating to 60 deg.C, reacting for 8h, filtering, and washing to obtain polyacrylonitrile grafted carbonaceous material; wherein N is in plasma treatment2The pressure was 20Pa, the power was 50W, the voltage was 1000V, the current was 200mA, the concentration of the plasma-treated carbonaceous material in an organic solvent (NMP) was 30mg/ml, and the volume fraction of acrylonitrile in the organic solvent was 60%.
(2) Dispersing the polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value to 9 by using sodium carbonate, heating to react (the temperature is 60 ℃ and the time is 90min), and separating, washing and vacuum drying a product (the temperature is 60 ℃) after the reaction to obtain the amidoxime modified carbonaceous material; wherein the concentration of the carbonaceous material in water is 0.2 mg/ml; the mass ratio of the carbonaceous material to the hydroxylamine hydrochloride is 1: 0.1.
(3) Mixing the prepared amidoxime-modified carbonaceous material with a metal salt (Zn (Ac)2·2H2O) dispersing in water under the stirring condition (the rotating speed of magnetic stirring is 520rpm), carrying out self-assembly in a hydrothermal kettle (the temperature is 170 ℃, the time is 150min), and separating and washing a product after the reaction is finished, wherein the concentration of the amidoxime modified carbonaceous material in the water is 1 mg/ml; the mass ratio of the amidoxime-modified carbonaceous material to the metal salt is 1: 0.1;
(4) calcining the washed product in a reducing atmosphere, wherein the temperature rise rate of the calcination is 5 ℃/min, the pyrolysis temperature is 500 ℃, and the heat preservation time is 180 min; the reducing atmosphere is H2Mixed gas of/Ar; h2The mass fraction in the reducing atmosphere is 45 percent; obtaining the metal-carbon hybrid material.
In the prepared metal-carbon hybrid material, the average particle size of the metal nanoparticles is 20 nm.
Example 6
A preparation method of a metal-carbon hybrid material comprises the following steps:
(1) using N as carbon material (carbon spheres)2Treating with plasma for 60min, dispersing in organic solvent (EG) containing acrylonitrile, heating to 40 deg.C, reacting for 8h, filtering, and washing to obtain polyacrylonitrile grafted carbonaceous material; wherein N is in plasma treatment2The pressure was 10Pa, the power was 100W, the voltage was 900V, the current was 100mA, the concentration of the plasma-treated carbonaceous material in an organic solvent (NMP) was 40mg/ml, and the volume fraction of acrylonitrile in the organic solvent was 40%.
(2) Dispersing the polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value to 6 by using sodium carbonate, heating to react (the temperature is 50 ℃ and the time is 100min), and separating, washing and vacuum drying a product (the temperature is 50 ℃) after the reaction to obtain the amidoxime modified carbonaceous material; wherein the concentration of the carbonaceous material in water is 0.1 mg/ml; the mass ratio of the carbonaceous material to the hydroxylamine hydrochloride is 1: 0.016.
(3) Mixing the obtained amidoxime-modified carbonaceous material with metal salt (FeCl)3·6H2O) is dispersed in water under stirring (rotation speed of magnetic stirring is 100rpm) and self-assembly is carried out in a hydrothermal kettle (temperature is 150 ℃ C., time is 180 mi)n), separating and washing a product after the reaction is finished, wherein the concentration of the amidoxime-modified carbonaceous material in water is 0.2 mg/ml; the mass ratio of the amidoxime-modified carbonaceous material to the metal salt is 1: 0.012;
(4) calcining the washed product in a reducing atmosphere, wherein the temperature rise rate of the calcination is 1 ℃/min, the pyrolysis temperature is 1000 ℃, and the heat preservation time is 200 min; the reducing atmosphere is H2/N2Mixing the gas; h2The mass fraction in the reducing atmosphere is 30 percent; obtaining the metal-carbon hybrid material.
In the prepared metal-carbon hybrid material, the average particle size of the metal nanoparticles is 6 nm.
Example 7
A preparation method of a metal-carbon hybrid material comprises the following steps:
(1) using carbon material (single-wall carbon nano tube) with N2Treating with plasma for 50min, dispersing in organic solvent (GL) containing acrylonitrile, heating to 20 deg.C, reacting for 9h, filtering, and washing to obtain polyacrylonitrile grafted carbonaceous material; wherein N is in plasma treatment2The pressure was 10Pa, the power was 50W, the voltage was 500V, the current was 300mA, the concentration of the plasma-treated carbonaceous material in an organic solvent (NMP) was 20mg/ml, and the volume fraction of acrylonitrile in the organic solvent was 50%.
(2) Dispersing a polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value to 10 by using potassium carbonate, heating to react (the temperature is 30 ℃ and the time is 180min), and separating, washing and vacuum drying a product (the temperature is 90 ℃) after the reaction to obtain an amidoxime modified carbonaceous material; wherein the concentration of the carbonaceous material in water is 10 mg/ml; the mass ratio of the carbonaceous material to the hydroxylamine hydrochloride is 1: 0.5.
(3) Mixing the obtained amidoxime-modified carbonaceous material with a metal salt (BiCl)3) Dispersing the mixture in water under the stirring condition (the rotating speed of magnetic stirring is 1000rpm), carrying out self-assembly in a hydrothermal kettle (the temperature is 200 ℃, the time is 30min), and separating and washing a product after the reaction is finished, wherein the concentration of the amidoxime modified carbonaceous material in the water is 0.2 mg/ml; aminoxime-modifiedThe mass ratio of the carbonaceous material to the metal salt is 1: 0.1;
(4) calcining the washed product in a reducing atmosphere, wherein the temperature rising rate of the calcination is 4 ℃/min, the pyrolysis temperature is 750 ℃, and the heat preservation time is 60 min; the reducing atmosphere is H2/N2Mixing the gas; h2The mass fraction in the reducing atmosphere is 15 percent; obtaining the metal-carbon hybrid material.
In the prepared metal-carbon hybrid material, the average particle size of the metal nanoparticles is 5 nm.
Example 8
A preparation method of a metal-carbon hybrid material comprises the following steps:
(1) using carbon material (multi-wall carbon nano tube) with N2Treating with plasma for 80min, dispersing in organic solvent (DMF) containing acrylonitrile, heating to 20 deg.C, reacting for 5h, filtering, and washing to obtain polyacrylonitrile grafted carbonaceous material; wherein N is in plasma treatment2The pressure was 20Pa, the power was 50W, the voltage was 500V, the current was 100mA, the concentration of the plasma-treated carbonaceous material in an organic solvent (NMP) was 5mg/ml, and the volume fraction of acrylonitrile in the organic solvent was 30%.
(2) Dispersing the polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value to 8 by using ammonia water, heating to react (the temperature is 70 ℃ and the time is 30min), separating, washing and drying a product in vacuum (the temperature is 100 ℃) after the reaction to obtain the amidoxime modified carbonaceous material; wherein the concentration of the carbonaceous material in water is 0.5 mg/ml; the mass ratio of the carbonaceous material to the hydroxylamine hydrochloride was 1: 0.077.
(3) Mixing the obtained amidoxime-modified carbonaceous material with a metal salt (TiCl)4) Dispersing the mixture in solvent water under the stirring condition (the rotating speed of magnetic stirring is 580rpm), carrying out self-assembly in a hydrothermal kettle (the temperature is 120 ℃, the time is 150min), and separating and washing a product after the reaction is finished, wherein the concentration of the amidoxime modified carbonaceous material in the water is 10 mg/ml; the mass ratio of the amidoxime-modified carbonaceous material to the metal salt is 1: 0.077;
(4) calcining the washed product in a reducing atmosphere,the heating rate of calcination is 8 ℃/min, the pyrolysis temperature is 850 ℃, and the heat preservation time is 300 min; the reducing atmosphere is H2/N2Mixing the gas; h2The mass fraction in the reducing atmosphere is 10 percent; obtaining the metal-carbon hybrid material.
In the prepared metal-carbon hybrid material, the average particle size of the metal nanoparticles is 14 nm.
Example 9
A preparation method of a metal-carbon hybrid material comprises the following steps:
(1) using carbon material (multi-wall carbon nano tube) with N2Treating with plasma for 30min, dispersing in organic solvent (DMF) containing acrylonitrile, heating to 40 deg.C, reacting for 8h, filtering, and washing to obtain polyacrylonitrile grafted carbonaceous material; wherein N is in plasma treatment2The pressure was 5Pa, the power was 150W, the voltage was 600V, the current was 100mA, the concentration of the plasma-treated carbonaceous material in an organic solvent (NMP) was 40mg/ml, and the volume fraction of acrylonitrile in the organic solvent was 70%.
(2) Dispersing the polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value to 6 by using ammonia water, heating to react (the temperature is 70 ℃ and the time is 30min), separating, washing and drying a product in vacuum (the temperature is 100 ℃) after the reaction to obtain the amidoxime modified carbonaceous material; wherein the concentration of the carbonaceous material in water is 0.5 mg/ml; the mass ratio of the carbonaceous material to the hydroxylamine hydrochloride was 1: 0.077.
(3) Mixing the obtained amidoxime-modified carbonaceous material with metal salt (SnCl)2) Dispersing the mixture in solvent water under the stirring condition (the rotating speed of magnetic stirring is 580rpm), carrying out self-assembly in a hydrothermal kettle (the temperature is 120 ℃, the time is 150min), and separating and washing a product after the reaction is finished, wherein the concentration of the amidoxime modified carbonaceous material in the water is 0.2 mg/ml; the mass ratio of the amidoxime-modified carbonaceous material to the metal salt is 1: 0.077;
(4) calcining the washed product in a reducing atmosphere, wherein the temperature rising rate of the calcination is 8 ℃/min, the pyrolysis temperature is 850 ℃, and the heat preservation time is 300 min; the reducing atmosphere is H2/N2MixingA gas; h2The mass fraction in the reducing atmosphere is 1 percent; obtaining the metal-carbon hybrid material.
In the prepared metal-carbon hybrid material, the average particle size of the metal nanoparticles is 9 nm.
Claims (5)
1. A preparation method of a metal-carbon hybrid material is characterized in that an amidoxime group is firstly introduced to a polyacrylonitrile grafted carbonaceous material to obtain an amidoxime modified carbonaceous material, the amidoxime modified carbonaceous material and a metal salt are dispersed in a hydrothermal kettle to carry out self-assembly reaction, and then the mixture is calcined in a reducing atmosphere to obtain the metal-carbon hybrid material;
the method comprises the following specific steps:
(1) using carbon material with N2After plasma treatment, adding an organic solvent containing acrylonitrile, heating for reaction for a period of time, and then carrying out suction filtration and washing to obtain a polyacrylonitrile grafted carbonaceous material;
(2) dispersing the polyacrylonitrile grafted carbonaceous material in water, adding hydroxylamine hydrochloride, adjusting the pH value, heating for reaction for a period of time, and then separating, washing and vacuum drying to obtain an amidoxime modified carbonaceous material;
(3) dispersing a carbonacious material modified by amidoxime and metal salt in an organic solvent for self-assembly reaction, separating and washing after the reaction is finished, and calcining in a reducing atmosphere to obtain a metal-carbon hybrid material;
in the preparation process, the size and the dispersion state of metal nano particles in the metal-carbon hybrid material are regulated and controlled by regulating the content of an amidoxime group in the amidoxime-modified carbonaceous material and the molar ratio of the amidoxime group to metal ions in metal salt, specifically, when the content of the amidoxime group is fixed, the larger the molar ratio of the amidoxime group to the metal ions is, the smaller the size of the metal nano particles is, the higher the dispersion degree is, and vice versa; when the molar ratio of the amidoxime group to the metal ions is constant, the larger the content of the amidoxime group is, the smaller the size of the metal nanoparticles is, the higher the dispersity is, and otherwise, the opposite is true;
the metal-carbon hybrid material consists of a carbonaceous substrate and metal nano particles dispersed on the carbonaceous substrate, wherein the surface of the metal nano particles is coated with a carbon layer, the metal nano particles are in a monodispersed state, are uniformly dispersed and uniform in size, and the average particle size is adjustable and controllable between 5nm and 20 nm.
2. The method for preparing a metal-carbon hybrid material according to claim 1, wherein in the step (1), the carbonaceous material is single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, ordered mesoporous carbon, porous carbon, carbon spheres or carbon fibers;
the specific surface area of the carbonaceous material is 150-2500 m2/g；
The plasma treatment time is 10-90 min, N2The pressure is 5-20 Pa, the power is 50-200W, the voltage is 500-1000V, and the current is 100-300 mA;
in an organic solvent containing acrylonitrile, the volume fraction of the acrylonitrile is 30-70%, and the organic solvent is N-methyl pyrrolidone, N-dimethylformamide, ethylene glycol or glycerol;
N2the concentration of the carbonaceous material after the plasma treatment in the organic solvent is 5-50 mg/mL;
the heating reaction is carried out for a period of time, namely heating to 20-80 ℃ and reacting for 5-10 h.
3. The preparation method of the metal-carbon hybrid material according to claim 1, wherein in the step (2), the concentration of the polyacrylonitrile-grafted carbonaceous material in water is 0.1-10 mg/ml;
the mass ratio of the polyacrylonitrile grafted carbonaceous material to the hydroxylamine hydrochloride is 1: 0.001-0.5;
the pH value regulator used for regulating the pH value is sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide or ammonia water, and the regulated pH value is 6-10;
the heating reaction is carried out for a period of time, namely heating to 30-90 ℃ and reacting for 30-180 min;
the temperature of vacuum drying is 50-100 ℃.
4. The preparation method of the metal-carbon hybrid material according to claim 1, wherein in the step (3), the mass ratio of the amidoxime-modified carbonaceous material to the metal salt is 1: 0.01-0.6;
the metal salt is MnCl2·4H2O、MnSO4·4H2O、FeCl3·6H2O、Fe(NO3)3·9H2O、CoCl2·6H2O、Co(NO3)2·6H2O、Co(Ac)2·4H2O、NiCl2·6H2O、Ni(NO3)2·6H2O、Ni(Ac)2·4H2O、CuCl2·2H2O、CuSO4·5H2O、Cu(NO3)2·2.5H2O、Cu(Ac)2·H2O、Zn(NO3)2·6H2O、Zn(Ac)2·2H2O、ZnSO4·7H2O、TiCl4、SnCl2、SnCl4Or BiCl3。
5. The method for preparing the metal-carbon hybrid material according to claim 1, wherein in the step (3), the concentration of the amidoxime-modified carbonaceous material in the organic solvent is 0.1-10 mg/ml;
dispersing under the stirring condition, wherein the stirring speed is 100-1000 rpm;
the temperature of the self-assembly reaction is 120-200 ℃, and the time is 30-180 min;
the reducing atmosphere is H2Mixed gas of/Ar or H2/N2Mixed gas of H2The mass fraction in the reducing atmosphere is 1-50%;
the calcination is to heat the mixture to 600-1000 ℃ at a heating rate of 1-10 ℃/min and then to preserve the temperature for 60-300 min.
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