CN110272035B - Method for preparing carbon nanocages by catalyzing organic ligands with metal ions, carbon nanocages prepared by method and application of carbon nanocages - Google Patents
Method for preparing carbon nanocages by catalyzing organic ligands with metal ions, carbon nanocages prepared by method and application of carbon nanocages Download PDFInfo
- Publication number
- CN110272035B CN110272035B CN201910577442.5A CN201910577442A CN110272035B CN 110272035 B CN110272035 B CN 110272035B CN 201910577442 A CN201910577442 A CN 201910577442A CN 110272035 B CN110272035 B CN 110272035B
- Authority
- CN
- China
- Prior art keywords
- carbon
- salt
- metal
- temperature
- nanocage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/96—Carbon-based electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention relates to a method for preparing a carbon nanocage by catalyzing an organic ligand with metal ions, the carbon nanocage prepared by the method and application of the carbon nanocage. According to the method, an organic ligand aqueous solution and a metal salt aqueous solution are uniformly mixed in proportion and then react for 2-24 hours at normal temperature to obtain a metal organic framework precursor with a rhombic dodecahedron structure, the precursor is heated to 350-500 ℃ in an inert gas atmosphere and calcined at constant temperature for 1-2 hours, then the temperature is continuously increased to 800-900 ℃ and calcined at constant temperature for 1-4 hours, and after cooling, acid washing, water washing and drying are carried out to obtain the carbon nanocage. The size of the carbon nanocages obtained by the method is the smallest reported diameter at present, the size is about 10nm, in addition, the superfine carbon nanocage structure prepared by the method has rich pore structure, large specific surface area and excellent electrochemical performance, the preparation cost is low, the superfine carbon nanocage structure can be efficiently put into production and use, and the carbon nanocage has larger market competitiveness.
Description
Technical Field
The invention belongs to the technical field of preparation and application of nano materials, and particularly relates to a method for preparing a carbon nano cage by catalyzing an organic ligand by metal ions, the prepared carbon nano cage and application thereof.
Background
At present, carbon materials are widely used in the fields of energy and environment, for example: the battery material, the super-electricity material, the fiber material, the catalytic material and the like are closely related to the carbon material in future, and the development prospect is immeasurable. The reported carbon materials can be broadly classified into: one-dimensional tubular (carbon nanotubes), two-dimensional sheet (graphene), three-dimensional porous (carbon nanocages). Since the synthesis of carbon nanotubes by Kroto H.W and the like in 1985 and the synthesis of graphene by Andre Giem and the like in 2004, the application of carbon materials has been unprecedentedly developed, and researchers in various countries have intensively researched and explored carbon nanotubes and graphene materials, but researches on carbon nanocage materials are rarely reported. The carbon nano cage material is formed by a hollow cage-shaped structure formed by several to tens of carbon layers, has the size of less than 100nm generally, has rich pore structure, high specific surface area, acid and alkali corrosion resistance and excellent electric and heat conducting properties, can be widely applied to the fields of energy, environmental materials and the like, and has huge application prospect. According to the report of carbon industry in 2017, the carbon material is consumed in the automobile industry (2412.7 tons), the aerospace industry (5461.3 tons) and the leisure industry (3403.9 tons) in a huge way, and the use of the carbon material in various fields still keeps a higher growth trend. Therefore, the carbon nanocage material has very high research value as a novel carbon material.
At present, the preparation technology of the carbon nano cage is still very immature, and a plurality of technical problems need to be solved. The carbon nanocage can construct a specific micro-nano hollow cage-shaped structure only when a specific radian is required to be formed on the morphology, so that severe reaction conditions and precise reaction equipment are required in the preparation process of the material. The existing report shows that the technology for preparing the carbon nanocage material mainly comprises chemical vapor deposition, an arc discharge method, a hard template method, a plasma polymerization method, a laser graphite evaporation method and the like. The general mechanism of formation can be divided into two categories: one is to catalyze the organic matter through different metal nano-particles, the metal particles catalyze the carbon material to form a cavity under the high temperature condition, and a carbon nano-cage is formed along with further growth; another method is to form a carbon layer on the surface of the template by means of a specific spherical template, and then remove the template to obtain the carbon nanocages.
The carbon nanocage material is preliminarily explored by a hokken professor team of Nanjing university, benzene is used as a carbon source on the basis of MgO as a template through an in-situ method, and the carbon nanocages with the diameter of about 20nm are obtained through different high-temperature treatments, wherein the specific experimental process comprises the following steps: firstly, putting basic magnesium carbonate or magnesium carbonate into a tubular furnace, gradually raising the reaction temperature to 700-900 ℃ under the protection of continuous inert gas, continuously introducing a solution containing benzene into the tubular furnace, introducing carbon source gas into a reaction zone of the tubular furnace through inert gas flow, wrapping a carbon layer on the surface of magnesium oxide nanoparticles generated in situ, and performing acid cleaning treatment on the obtained powder to obtain a required carbon cage material (Xie K, Qin XT, Wang XZ, Hu Z. carbon nanotubes as Supercapacitor materials adv Mater 2012,24(7), 347-; in addition, patent CN 200410024700.0 reports that a metal carbonyl compound is uniformly mixed with a low-carbon organic liquid, the mixture is sprayed from the top of a main reactor by using a heating main reactor through an electronic peristaltic pump, a solid carbon nanocage coated with metal ions is obtained in a collector, and then the solid carbon nanocage is dissolved in an acidic solution, and a black product is dried to obtain a hollow carbon nanocage material. In addition, patent CN 1810635a provides a method for preparing carbon nanocages using metal ions as catalysts: introducing a mixed gas of inert gas and acetylene into carbonyl iron liquid, introducing a catalyst gas carrying metal ions into the top of a main reactor, reacting in a high-temperature zone, continuously obtaining a composite product with uniformly distributed iron-containing catalyst particles in a collector at the bottom of the main reactor, then carrying out heat treatment on a precursor, and finally carrying out acid treatment to remove residual catalyst to obtain the carbon nanocage material. Compared with the complex synthesis technologies, the professor pandurage of southern ocean university of singapore firstly uses specific Organic matters and Metal ions to carry out primary compounding at normal temperature by using a Metal Organic Framework as a template to obtain an Organic matter precursor with regular morphology, and then carries out simple carbonization treatment to prepare a large amount of carbon nano cage-shaped Materials, the synthesis method is simple and efficient, and the carbon nano cage-shaped Materials show excellent electrochemical performance when applied to battery Materials and super-electric Materials (Zhang H, Nai J, Yu L, Lou X W, Metal-Organic-Framework-Based Materials for Material for Renewable Energy and Environmental applications, Joule 2017,1(1), 77-107). However, the size of the carbon nanocages obtained in these methods is generally on the micrometer scale, and there is a large gap from the ideal nanometer size.
In summary, according to the methods for preparing carbon nanocages reported in the prior art, it is not difficult to find that expensive equipment is generally adopted for preparing carbon nanocages, the preparation conditions are severe, the efficiency is low, and the large-scale production of carbon nanocage materials is difficult. Secondly, the raw materials adopted by most methods contain high toxicity, such as highly toxic organic substances (hydrazine compounds and ether compounds) and heavy metal-containing compounds, and harmful substances, such as chlorides and fluorides, can be generated in the preparation process. Finally, in the aspect of practical application, the carbon nanocage materials prepared at present are different in appearance and size specifications, the sizes of most of the materials are still in the micron level, the chemical activity of the carbon material is limited to a great extent, and meanwhile, the specific surface area of the material is greatly influenced, so that the method for searching the carbon nanocage material which is simple, convenient, effective, economical, practical, green and environment-friendly and can produce high-performance carbon nanocage materials in a large scale has important significance.
Disclosure of Invention
In view of the above problems and defects existing in the prior art, the present invention aims to provide a method for preparing carbon nanocages by using metal ions to catalyze organic ligands, carbon nanocages prepared by the method, and applications of the carbon nanocages.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:
a method for preparing carbon nanocages by catalyzing organic ligands with metal ions specifically comprises the following steps:
(1) dissolving organic ligand in distilled water according to a ratio, and uniformly stirring to form a solution A, wherein: the organic ligand is any one or more of imidazole, methylimidazole, 2-methylimidazole, benzimidazole, phthalic acid, isophthalic acid, benzimidazole formic acid, pyridine and bipyridine;
(2) dissolving metal salt in distilled water according to a ratio, and uniformly stirring to form a solution B, wherein the metal salt is any two or more of zirconium salt, copper salt, iron salt, zinc salt, nickel salt, cobalt salt and molybdenum salt;
(3) slowly adding the solution B into the solution A, reacting for 2-24 hours at normal temperature, and after the reaction is finished, centrifuging and washing a product to obtain a metal organic framework precursor with a rhombic dodecahedron structure;
(4) and (2) placing the metal organic framework precursor in a high-temperature furnace, heating to 350-500 ℃ under the inert gas atmosphere, calcining for 1-2 h at constant temperature, then continuing to heat to 800-900 ℃ and calcining for 1-4 h at constant temperature, naturally cooling to room temperature, and drying the obtained product after acid washing and water washing in sequence to obtain the carbon nano cage-shaped powder.
Further, according to the technical scheme, the ratio of the organic ligand in the step (1) to the distilled water is (3-6) by mass: (40-100) parts by volume; wherein: the mass portion and the volume portion are as follows: mL was used as a reference.
Preferably, in the above technical scheme, the organic ligand is preferably 2-methylimidazole.
Further, according to the technical scheme, the ratio of the metal salt in the step (2) to the distilled water is (1-3) by mass: (40-100) parts by volume; wherein: the mass portion and the volume portion are as follows: mL was used as a reference.
Further, in the above technical solution, the metal salt in step (2) is any one or a mixture of more of sulfate, nitrate, acetate, halide, phosphate, carbonate, oxalate, and the like.
Preferably, in the above technical solution, the metal salt in step (2) preferably consists of cobalt salt and nickel salt, and the molar ratio of the cobalt salt to the nickel salt is 1: 1-6: 1.
specifically, in the above technical scheme, the normal temperature refers to a natural room temperature condition in four seasons, no additional cooling or heating treatment is performed, and the normal temperature is generally controlled to be 10-30 ℃, preferably 15-25 ℃.
Further, according to the above technical scheme, in the step (4), when the calcination treatment is performed, the heating rate is 1-10 ℃/min, preferably 5 ℃/min.
Further, according to the technical scheme, the pickling treatment time in the step (4) is 4-24 hours.
Further, in the above technical solution, the acid washing solvent in the step (4) is dilute hydrochloric acid or dilute sulfuric acid with low concentration, and the concentration of the acid washing solvent is 0.1-1.0M, and more preferably 0.5M.
The second purpose of the invention is to provide the carbon nanocage material prepared by the method.
The third purpose of the invention is to provide the application of the carbon nanocage material prepared by the method as an electrode catalyst in a zinc-air battery.
An air electrode comprising an air electrode catalyst, an electrolyte for the air electrode, and a conductive material, wherein: the air electrode catalyst is the carbon nanocage material prepared by the method.
A zinc-air battery comprises the air electrode.
Compared with the prior art, the method for preparing the carbon nanocages by catalyzing the organic ligands by the metal ions, the prepared carbon nanocages and the application thereof have the following beneficial effects:
(1) the invention does not need expensive production equipment, and the carbon nanocages can be directly prepared by common chemical synthesis and heat treatment;
(2) the size of the carbon nanocages obtained by the method is the smallest reported diameter at present, and the size is about 10 nm;
(3) the synthesis process is simple, and the process flow can be divided into two steps: hydrothermal and high-temperature pyrolysis at normal temperature;
(4) in the whole preparation process, no high-toxicity chemical reagent and product are involved, and the production requirement of environmental protection is met.
(5) The superfine carbon nanocage structure prepared by the method has the advantages of rich pore structure, large specific surface area, excellent electrochemical performance, low preparation cost, high efficiency in production and use and high market competitiveness.
Drawings
Fig. 1 is a flow chart of a preparation process for preparing a carbon nanocage material by using metal ions to catalyze an organic ligand in example 1 of the present invention.
Fig. 2(a) and (b) are SEM photographs of the metal organic framework precursor prepared in example 1 of the present invention and a carbon nano ridge powder sample obtained after high temperature treatment, respectively.
FIG. 3 is a TEM photograph of a carbon nanowridge powder sample obtained after high temperature treatment in example 1 of the present invention.
FIG. 4 is a XRD test result chart of carbon nanocage materials obtained by different high temperature heat treatments in examples 1 to 3 of the present invention.
Fig. 5(a) and (b) are graphs showing the results of specific surface area (BET) and particle size analysis tests of the carbon nanocage materials obtained in example 1 and comparative example 1, respectively.
Fig. 6 is a diagram showing a zinc-air cell lighting small bulb in application example 1 of the present invention.
Fig. 7 is a graph showing the cycle stability test of the zinc-air battery according to application example 1 of the present invention and comparative application example 1.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
The carbon nanocage material with uniform appearance can be obtained by a simple preparation method, firstly, the organic framework precursor containing metal ions is prepared by a normal-temperature aqueous solution system, secondly, the carbon nanocage is generated by high-temperature pyrolysis and catalysis in a tubular furnace, and no harmful substance is involved in the whole experimental process. The material has unique cage-shaped appearance, rich pore structure and higher specific surface area, and can be directly applied to materials such as super capacitors, lithium ion batteries, electrolytic water catalysts and the like. Or the composite material is compounded with other materials in the preparation process to obtain a unique core-shell structure material, and the inner material is protected by the outer-layer carbon nanocages, so that the stability and the electron transmission efficiency of the material can be effectively improved. For example, the lithium sulfur compound can be used as a carrier of a lithium sulfur battery, and the volume expansion of sulfur can be inhibited, and the dissolution of the lithium sulfur compound can be simultaneously alleviated, so that the lithium sulfur compound has higher capacity and cycling stability. The material has a plurality of unique advantages in structure and has great application potential.
Example 1
As shown in fig. 1, the method for preparing carbon nanocages by using metal ions to catalyze organic ligands of this embodiment specifically includes the following steps: first 3.7g of 2-methylimidazole were dissolved in 80mL of aqueous solution and magnetically stirred for 30min to form a homogeneous solution A, while 1.23g of cobalt nitrate (Co (NO) (Co)3)2·6H2O) and 0.34g of nickel nitrate (Ni (NO)3)2·6H2O) was dissolved in 80mL of aqueous solution and magnetically stirred for 30min to form a homogeneous solution B. And slowly pouring the solution B into the solution A, reacting for 12 hours at room temperature to generate purple precipitates, obtaining the precipitates at 8000rpm/min by a high-speed centrifuge, and repeatedly washing and drying the products by using distilled water to obtain the metal organic framework precursor with the shape regular size of about 500 nm. Putting the pretreated powder (metal organic frame precursor) in a porcelain boat, placing in a high temperature furnace, heating to 400 deg.C, calcining at constant temperature for 2h, heating to 900 deg.C, calcining at constant temperature for 2h at a heating rate of 5 deg.C/min, and performing N calcination2And (5) protecting under an atmosphere. Naturally cooling to room temperature, reacting the obtained product in 0.5M HCl solution for 12h, repeatedly cleaning with distilled water, and drying in a drying oven for 12h to obtain carbon nano cage-shaped powder with the size of about 10 nm.
SEM photographs of the metal-organic framework precursor prepared by the above method and the carbon nanowhisker powder sample obtained after the high temperature treatment in this example are shown in fig. 2(a) and (b), respectively. As can be seen from FIG. 2, 2-methylimidazole reacts with metal ions through a normal-temperature hydrothermal reaction to obtain a precursor material with a regular morphology and a rhombic dodecahedron structure, and as shown in FIG. (a), the surface of the material is smooth and the size of the material is uniform. And (c) performing heat treatment at different temperatures to obtain the carbonized material shown in the figure (b), wherein the original appearance of the material disappears, the carbonized material becomes more irregular, and the surface of the material contains rough and spherical particles which are uniformly aggregated together.
The material is observed to contain a large number of carbon nano cage structures through a high-power transmission electron microscope, as shown in fig. 3, the size of the material is about 10nm, the material only comprises a plurality of carbon layers, and certain connection exists between the carbon cage layers.
The reaction mechanism of the above method of this example is as follows:
2-methylimidazole is an important organic raw material for constructing a metal organic framework (ZIF-67) and plays a role in providing a carbon source. The organic ligand and the metal cobalt ions form a specific rhombic dodecahedron structure, and with the addition of nickel nitrate, the cobalt and nickel metal ions are uniformly dispersed in the obtained metal organic framework. Through the specific high-temperature heat treatment, metal ions play a catalytic role in the amorphous carbon, and the amorphous carbon is promoted to be converted to an ordered direction. Due to the synergistic effect of the cobalt and nickel bimetallic ions, different ions can be mutually influenced, along with the rise of the heat treatment temperature, the metal ions which are originally uniformly dispersed in the organic framework body are changed in position and gradually aggregated to form tiny metal particles, the original vacancies form vacancies, and along with the rise of the temperature, cavities are finally formed, so that the carbon nano cage-shaped structure required by people is obtained. For existing metal nano particles, diluted hydrochloric acid can be used for acid treatment, but the metal nano particles cannot be completely washed away, however, for most energy materials, the performance of the material can be effectively improved due to the existence of metal ions, and the activity of the material can be optimized due to the retention of some metal particles.
Example 2
The method for preparing carbon nanocages by using metal ions to catalyze organic ligands in the embodiment basically has the same steps as the embodiment, and only differs from the following steps: the heat treatment steps of the metal-organic framework precursor in this embodiment are: heating to 400 ℃ for constant-temperature calcination for 2h, then continuously heating to 800 ℃ for constant-temperature calcination for 2h, and the rest conditions are completely the same.
Example 3
The method for preparing carbon nanocages by using metal ions to catalyze organic ligands in the embodiment basically has the same steps as the embodiment, and only differs from the following steps: the high-temperature treatment steps of the metal organic framework precursor are as follows: heating to 400 ℃ for constant-temperature calcination for 2h, then continuously heating to 1000 ℃ for constant-temperature calcination for 2h, and the rest conditions are completely the same.
XRD tests were performed on the carbon nanocage materials obtained in examples 1 to 3 by different high temperature heat treatments, and the results are shown in FIG. 4. Further analyzing the chemical composition of the material, finding that the position of a stronger characteristic peak in the XRD relative to a standard card containing nickel and cobalt shows that the material contains a certain amount of cobalt and nickel metal elements and the crystallization performance of the metal is good. With the temperature rise, the characteristic peak of carbon appears at the position of 26.5 degrees and corresponds to a (200) crystal face, which indicates that the material contains carbon element, indicates that the carbon material is transformed from an amorphous state to a crystalline state, and can obtain the carbon nanocage material with regular morphology under the appropriate temperature condition.
Example 4
The method for preparing the carbon nanocages by using the metal ions to catalyze the organic ligands specifically comprises the following steps: first 3g of methylimidazole were dissolved in 40mL of aqueous solution and magnetically stirred for 30min to form a homogeneous solution A, while 0.5g of cobalt chloride (CoCl) was added2·6H2O) and 0.5g of nickel chloride (NiCl)2·6H2O) was dissolved in 40mL of aqueous solution and magnetically stirred for 30min to form a homogeneous solution B. And slowly pouring the solution B into the solution A, reacting for 2 hours at room temperature to generate purple precipitates, obtaining the precipitates at 8000rpm/min by a high-speed centrifuge, and repeatedly washing and drying the products by using distilled water to obtain the metal organic framework precursor with the shape regular size of about 500 nm. Putting the pretreated powder (metal organic framework precursor) in a porcelain boat, placing in a high-temperature furnace, heating to 350 deg.C, calcining at constant temperature for 2h, heating to 900 deg.C, calcining at constant temperature for 1h at a heating rate of 5 deg.C/min, and performing N2And (5) protecting under an atmosphere. Naturally cooling to room temperature, reacting the obtained product in 0.5M HCl solution for 4h, repeatedly cleaning with distilled water, and drying in a drying oven for 12h to obtain carbon nano cage-shaped powder with the size of about 10 nm.
Example 5
The preparation of carbon nano-particles by using metal ions to catalyze organic ligands in the embodimentThe method of the cage specifically comprises the following steps: first 6g of benzimidazolecarboxylic acid was dissolved in 100mL of aqueous solution and magnetically stirred for 30min to form a homogeneous solution A, while 2.52g of copper sulfate (CoSO)4·5H2O) and 0.48g Zinc sulfate (Zn (SO)4)2·7H2O) was dissolved in 100mL of aqueous solution and magnetically stirred for 30min to form a homogeneous solution B. And slowly pouring the solution B into the solution A, reacting for 24 hours at room temperature to generate purple precipitates, obtaining the precipitates at 8000rpm/min by a high-speed centrifuge, and repeatedly washing and drying the products by using distilled water to obtain the metal organic framework precursor with the shape regular size of about 500 nm. Putting the pretreated powder (metal organic framework precursor) in a porcelain boat, placing in a high-temperature furnace, heating to 500 deg.C, calcining at constant temperature for 1h, heating to 800 deg.C, calcining at constant temperature for 4h at heating rate of 5 deg.C/min, and performing N calcination2And (5) protecting under an atmosphere. Naturally cooling to room temperature, reacting the obtained product in 0.5M dilute sulfuric acid solution for 24h, repeatedly cleaning with distilled water, and drying in a drying oven for 12h to obtain carbon nano cage-shaped powder with the size of about 10 nm.
Comparative example 1
The procedure of the preparation method of the carbon nanocage of this comparative example was substantially the same as that of example 1 except that: the high-temperature treatment steps of the metal organic framework precursor are as follows: directly heating to 900 ℃ and calcining for 2h at constant temperature, wherein the rest conditions are completely the same.
The carbon nanocage materials obtained in example 1 and comparative example 1 were subjected to specific surface area (BET) and particle size analysis tests, respectively, and the test results are shown in fig. 5(a), (b), respectively. As can be seen from FIG. 5, it was found that the sample obtained by heating to 400 ℃ for 2 hours and then heating to 900 ℃ for 2 hours had a higher specific surface area than the sample obtained by directly heating to 900 ℃ for 2 hours, and that the specific surface area of the material obtained by heating to 400 ℃ was as high as 2069m2(ii) in terms of/g. Meanwhile, the material obtained after heat preservation at 400 ℃ has abundant microporous structures in pore size distribution, the pore size is concentrated below 10nm and exactly corresponds to the diameter of a carbon nanocage of about 10nm, and for a sample without heat preservation, the pore size contains a large number of mesoporous structures, which indicates that the temperature is a control poreThe carbon material containing a large amount of nano cage structures can be obtained by controlling a temperature raising program.
Application example 1
The carbon nanocage material prepared in the embodiment 1 of the invention is applied to an air electrode catalyst in a zinc-air battery.
The zinc-air battery belongs to a metal-air battery. One electrode (called air electrode) of the zinc-air battery absorbs oxygen in the air in the discharging process, and the oxygen is subjected to oxygen reduction reaction under the action of a catalyst and is reduced into OH-While the metallic zinc is oxidized to Zn at the other electrode (called zinc electrode)2+. During charging, OH in the electrolyte-Will be oxidized into O under the action of catalyst2(oxygen evolution reaction), and Zn2+Is reduced to metallic zinc at the zinc electrode. The reaction equation of the alkaline zinc-air battery during discharging is as follows:
cathode: o is2+2H2O+4e-→4OH-
Anode: 2Zn → 2Zn2++4e-
The reaction equation during charging is:
cathode: 2Zn2++4e-→2Zn
Anode: 4OH- → O2+2H2O+4e-。
The preparation process of the zinc-air battery of the application example is as follows: 5mg of the catalyst was dispersed in a mixed solution of 800. mu.L of ethanol and 150. mu.L of distilled water, 50. mu.L of Nafion additive was added, and ultrasonic treatment was performed for 30min to obtain a uniform mixed solution. 200 mul of the solution was applied uniformly to a carbon cloth (D ═ 1cm circle) using a pipette, and then dried at 60 ℃ to assemble a zinc-air cell with 6mol/L KOH and 0.2mol/L ZnCl2The stability of the assembled cell was tested in a blue test cabinet using a zinc plate as the negative electrode as the electrolyte at a test temperature of 25 ℃. The catalyst respectively adopts the carbon nano cage-shaped powder and the platinum carbon obtained in the embodiment 1; the stability test results are shown in fig. 7.
The traditional air electrode catalytic material mainly uses noble metals, but is high in price and limited in reserve and difficult to produce on a large scale, so that the prepared carbon nano cage material is adopted as the catalytic material to replace the noble metal material, as can be seen from figure 7, the carbon nano cage material prepared by the invention has very good catalytic performance, can light a small bulb, and meanwhile, tests on the stability of an assembled battery show that the stability of the assembled battery is superior to that of a noble metal platinum carbon material, the assembled battery has excellent cycle stability within 200h, performance attenuation does not occur, and the platinum carbon material has serious performance attenuation, so that the carbon nano cage material has very wide prospect in practicability.
Therefore, the carbon nano cage-shaped material with uniform size can be obtained by adopting the heat treatment process of firstly low temperature and then high temperature, has higher specific surface area and abundant micropore structures, can provide a large number of active sites due to the high specific surface area in the process of participating in chemical reaction, simultaneously remains partial metal particles, can reduce the chemical energy barrier of the reaction in the reaction, and is favorable for accelerating the reaction. In the migration of ions and electrolyte, the abundant pore structure plays an important role, the transmission path of the electrolyte and materials is shortened, and the reaction efficiency is improved. The special nano cage structure is beneficial to increasing the stability of the material, and the active material embedded in the nano cage is protected by the carbon cage, so that the corrosion of the external environment to the internal material is greatly avoided, and the service life of the material under severe conditions can be prolonged.
In conclusion, the carbon nanocage material prepared by the method for preparing the carbon nanocage by catalyzing the organic ligand by the metal ions has the advantages of high specific surface area, extremely small size, excellent conductivity and rich pore structure, and has good application prospects in battery materials, super-electricity materials, fiber materials and catalytic materials.
Claims (8)
1. A method for preparing carbon nanocages by using metal ions to catalyze organic ligands is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) dissolving organic ligand in distilled water according to a ratio, and uniformly stirring to form a solution A, wherein: the organic ligand is any one or more of imidazole, methylimidazole, 2-methylimidazole, benzimidazole, phthalic acid, isophthalic acid, benzimidazole formic acid, pyridine and bipyridine; the ratio of the organic ligand to the distilled water is (3-6) by mass: (40-100) parts by volume; wherein: the mass portion and the volume portion are as follows: mL is taken as a benchmark;
(2) dissolving metal salt in distilled water according to a ratio, and uniformly stirring to form a solution B, wherein the metal salt is any of zirconium salt, copper salt, iron salt, zinc salt, nickel salt, cobalt salt and molybdenum salt; the metal salt and the distilled water are mixed in a ratio of (1-3) parts by mass: (40-100) parts by volume; wherein: the mass portion and the volume portion are as follows: mL is taken as a benchmark;
(3) slowly adding the solution B into the solution A, reacting for 2-24 hours at normal temperature, and after the reaction is finished, centrifuging and washing a product to obtain a metal organic framework precursor with a rhombic dodecahedron structure;
(4) and (2) placing the metal organic framework precursor in a high-temperature furnace, heating to 350-500 ℃ under the inert gas atmosphere, calcining for 1-2 h at constant temperature, then continuing to heat to 800-900 ℃ and calcining for 1-4 h at constant temperature, naturally cooling to room temperature, and drying the obtained product after acid washing and water washing in sequence to obtain the carbon nano cage-shaped powder.
2. The method of claim 1, wherein the metal ions catalyze the organic ligands to prepare carbon nanocages, and the method comprises the following steps: the metal salt in the step (2) is any one or a mixture of a plurality of sulfate, nitrate, acetate, halide, phosphate, carbonate and oxalate.
3. The method of claim 1, wherein the metal ions catalyze the organic ligands to prepare carbon nanocages, and the method comprises the following steps: the metal salt in the step (2) consists of cobalt salt and nickel salt, and the molar ratio of the cobalt salt to the nickel salt is 1: 1-6: 1.
4. the method of claim 1, wherein the metal ions catalyze the organic ligands to prepare carbon nanocages, and the method comprises the following steps: and (4) pickling for 4-24 hours.
5. The carbon nanocage material prepared by the method for preparing the carbon nanocage by catalyzing the organic ligand with the metal ion as claimed in any one of claims 1 to 4.
6. The carbon nanocage material prepared by the method of any one of claims 1 to 4 is applied to a zinc-air battery as an electrode catalyst.
7. An air electrode, characterized by: comprising an air electrode catalyst, an electrolyte for an air electrode, and a conductive material, wherein: the air electrode catalyst is a carbon nanocage material prepared by the method of any one of claims 1 to 4.
8. A zinc-air battery characterized in that the battery comprises the air electrode of claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910577442.5A CN110272035B (en) | 2019-06-28 | 2019-06-28 | Method for preparing carbon nanocages by catalyzing organic ligands with metal ions, carbon nanocages prepared by method and application of carbon nanocages |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910577442.5A CN110272035B (en) | 2019-06-28 | 2019-06-28 | Method for preparing carbon nanocages by catalyzing organic ligands with metal ions, carbon nanocages prepared by method and application of carbon nanocages |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110272035A CN110272035A (en) | 2019-09-24 |
| CN110272035B true CN110272035B (en) | 2021-07-13 |
Family
ID=67963857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910577442.5A Active CN110272035B (en) | 2019-06-28 | 2019-06-28 | Method for preparing carbon nanocages by catalyzing organic ligands with metal ions, carbon nanocages prepared by method and application of carbon nanocages |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110272035B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113823773B (en) * | 2020-06-19 | 2023-07-28 | 国家纳米科学中心 | Size-controllable carbon cage material and preparation method and application thereof |
| CN112678802B (en) * | 2020-08-13 | 2023-01-24 | 北京化工大学 | Preparation method of cobalt-nitrogen co-doped carbon nanocage |
| KR20230095966A (en) * | 2020-10-02 | 2023-06-29 | 디킨슨 코포레이션 | Scalable synthesis of perimorphic materials |
| CN113013427A (en) * | 2021-02-26 | 2021-06-22 | 华南理工大学 | High-performance electrocatalyst carrier derived based on Metal Organic Framework (MOF) material and preparation method thereof |
| CN115703633A (en) * | 2021-08-12 | 2023-02-17 | 西南大学 | Micron-sized embroidered spherical porous carbon material and preparation method and application thereof |
| CN113816375B (en) * | 2021-10-20 | 2023-03-21 | 温州大学 | P-containing tripyridine ligand derived carbon material and application thereof |
| CN114457349B (en) * | 2022-01-30 | 2023-08-08 | 中国华能集团清洁能源技术研究院有限公司 | Carbon-coated nickel-molybdenum-cobalt hydrogen evolution electrode and preparation method and application thereof |
| CN114566654A (en) * | 2022-03-01 | 2022-05-31 | 安徽理工大学 | ZIF-derived Fe/Co-N-C electrocatalyst in shape of rich-edge round cake, preparation method and application thereof |
| CN114797797B (en) * | 2022-03-11 | 2023-04-28 | 湖北工业大学 | Preparation method of hollow carbon nano-cage hydrogel adsorption material with anion recognition function |
| CN116396225B (en) * | 2023-06-02 | 2023-10-20 | 吉林省卓材新研科技有限公司 | Metal organic frame material for zinc-air battery, ligand and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105110315A (en) * | 2015-07-28 | 2015-12-02 | 大连理工大学 | Method for synthesis of double-casing layer carbon nanometer hollow polyhedron by metal-organic framework as template |
| KR20160001279A (en) * | 2014-06-27 | 2016-01-06 | 연세대학교 산학협력단 | Hollow porous carbon particles and their synthetic method |
| CN106495128A (en) * | 2016-11-09 | 2017-03-15 | 江苏理工学院 | A kind of single dispersing N doping hollow carbon nanometer polyhedral and preparation method thereof |
| CN107459029A (en) * | 2017-07-07 | 2017-12-12 | 武汉理工大学 | A kind of nitrogen/metal atom doped hollow polyhedral nano-sized carbon shell material and preparation method |
| CN108183224A (en) * | 2017-12-30 | 2018-06-19 | 武汉理工大学 | Porous nucleocapsid carbon/selenium composite material of a kind of original position nitrating and its preparation method and application |
| CN108963278A (en) * | 2018-07-03 | 2018-12-07 | 河南师范大学 | A kind of preparation method for having the function of hollow polyhedral nanocages microstructure and adulterating carbon material supported alloy double elctro-catalyst |
| CN109908938A (en) * | 2019-03-26 | 2019-06-21 | 南京航空航天大学 | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904596A (en) * | 2017-03-06 | 2017-06-30 | 武汉理工大学 | The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application |
-
2019
- 2019-06-28 CN CN201910577442.5A patent/CN110272035B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160001279A (en) * | 2014-06-27 | 2016-01-06 | 연세대학교 산학협력단 | Hollow porous carbon particles and their synthetic method |
| CN105110315A (en) * | 2015-07-28 | 2015-12-02 | 大连理工大学 | Method for synthesis of double-casing layer carbon nanometer hollow polyhedron by metal-organic framework as template |
| CN106495128A (en) * | 2016-11-09 | 2017-03-15 | 江苏理工学院 | A kind of single dispersing N doping hollow carbon nanometer polyhedral and preparation method thereof |
| CN107459029A (en) * | 2017-07-07 | 2017-12-12 | 武汉理工大学 | A kind of nitrogen/metal atom doped hollow polyhedral nano-sized carbon shell material and preparation method |
| CN108183224A (en) * | 2017-12-30 | 2018-06-19 | 武汉理工大学 | Porous nucleocapsid carbon/selenium composite material of a kind of original position nitrating and its preparation method and application |
| CN108963278A (en) * | 2018-07-03 | 2018-12-07 | 河南师范大学 | A kind of preparation method for having the function of hollow polyhedral nanocages microstructure and adulterating carbon material supported alloy double elctro-catalyst |
| CN109908938A (en) * | 2019-03-26 | 2019-06-21 | 南京航空航天大学 | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT |
Non-Patent Citations (2)
| Title |
|---|
| Core-shell carbon materials derived from metal-organic frameworks as an efficient oxygen bifunctional electrocatalyst;Zhijuan Wang et al;《Nano Energy》;20161011;第30卷;4.9节 * |
| High energy density supercapacitors composed of nickel cobalt oxide nanosheets on nanoporous carbon nanoarchitectures;Christine Young et al;《Journal of Materials Chemistry A》;20170330;第5卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110272035A (en) | 2019-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110272035B (en) | Method for preparing carbon nanocages by catalyzing organic ligands with metal ions, carbon nanocages prepared by method and application of carbon nanocages | |
| Li et al. | MOF‐derived metal oxide composites for advanced electrochemical energy storage | |
| Li et al. | Metal‐organic framework‐derived carbons for battery applications | |
| Huang et al. | Application of polyoxometalate derivatives in rechargeable batteries | |
| CN106549163B (en) | A kind of preparation method and applications of cobalt, nitrogen co-doped ultrathin nanometer carbon plate | |
| CN108767260B (en) | Carbon-coated FeP hollow nano-electrode material and preparation method and application thereof | |
| Zhou et al. | Recent progress in Co–based metal–organic framework derivatives for advanced batteries | |
| CN109244427B (en) | Preparation method of carbon-coated zinc sulfide loaded graphene as potassium ion battery cathode | |
| CN102842710A (en) | Preparation method of Co3O4/graphene nanocomposite material | |
| CN104835654A (en) | 3D nitrogen-doped graphene/molybdenum disulfide compound and preparation method thereof | |
| Qiu et al. | Tunable MOFs derivatives for stable and fast sulfur electrodes in Li-S batteries | |
| Li et al. | Recent progress of nanostructured metal chalcogenides and their carbon-based hybrids for advanced potassium battery anodes | |
| Jiao et al. | Non-precious transition metal single-atom catalysts for the oxygen reduction reaction: progress and prospects | |
| CN103840176B (en) | Three-dimensional grapheme based combined electrode of a kind of area load Au nano particle and its preparation method and application | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN112481653A (en) | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof | |
| CN108807943B (en) | CeO with hollow structure2@ C core-shell nano composite material and preparation method and application thereof | |
| Wang et al. | Progress of transition metal sulfides used as the lithium-ion battery anodes | |
| Zhou et al. | Progress of NiO‐Based Anodes for High‐Performance Li‐Ion Batteries | |
| Liu et al. | Optimizing oxygen vacancies can improve the lithium storage properties in NiO porous nanosheet anodes | |
| CN110492076B (en) | Preparation method of two-dimensional porous hexagonal metal oxide nanosheet composite material and application of composite material in potassium ion battery | |
| Mei et al. | Enabling the fabrication of advanced NiCo/Bi alkaline battery via MOF-hydrolyzing derived cathode and anode | |
| Xie et al. | A review on metal–organic framework-derived anode materials for potassium-ion batteries | |
| Hu et al. | Ternary layered double hydroxide cathode materials for electrochemical energy storage: a review and perspective | |
| Zhang et al. | Graphene oxide-wrapped cobalt-doped oxygen-deficient titanium dioxide hollow spheres clusters as efficient sulfur immobilizers for lithium-sulfur batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |