CN113173605B - Core-shell type metal sulfide composite material and preparation method and application thereof - Google Patents

Core-shell type metal sulfide composite material and preparation method and application thereof Download PDF

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CN113173605B
CN113173605B CN202110461935.XA CN202110461935A CN113173605B CN 113173605 B CN113173605 B CN 113173605B CN 202110461935 A CN202110461935 A CN 202110461935A CN 113173605 B CN113173605 B CN 113173605B
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杨勇
李思佳
朱芷霄
赵泽军
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Northwestern Polytechnical University
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Abstract

The invention belongs to the technical field of core-shell metal organic framework materials, and particularly relates to a core-shell metal sulfide composite material and a preparation method and application thereof, wherein the core-shell metal sulfide composite material is a hollow microsphere with a yolk structure, polyoxometallate provides transition metal oxoacid ions, various metal sources provide transition metal ions, and the transition metal ions and an m-benzenetricarboxylic acid organic ligand are subjected to coordination reaction to form a metal organic framework shell; meanwhile, a sulfur source and transition metal ions are reacted to form a 'core', and the hollow core-shell structure microsphere taking metal sulfide as the core is formed through etching and different diffusion speeds of the ions to the 'shell' and the ions to the 'shell'. The method obtains the gram-grade core-shell metal sulfide composite material by a one-step solvothermal method, has high efficiency, safety, high practicability and universality, is beneficial to industrial scale production, and has wide development prospect in the fields of nano reactors, catalysis, adsorption, energy storage and conversion.

Description

Core-shell type metal sulfide composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of core-shell metal organic framework materials, and particularly relates to a core-shell metal sulfide composite material and a preparation method and application thereof.
Background
The metal organic framework material is a long-range ordered crystal material with a porous structure, which is formed by taking metal ions or metal clusters as central sites and carrying out coordination with a series of organic ligands (such as isophthalic acid, terephthalic acid, dimethyl imidazole and the like). Due to the multi-selectivity of metal ions and the diversity and structure modifiability of organic ligands, a series of metal organic framework materials with specific structures and compositions are synthesized. Metal organic framework materials are widely used in the fields of catalysis, nano-reactors, energy storage and conversion, gas storage and separation, chemical sensing, drug delivery, etc. due to their diversified structural characteristics, high specific surface area, easy functionalization, adjustable pore canals and developed pores. Due to the fact that the types of the metal ions or the clusters and the organic ligands are various, the coordination strength between the components and the thermal stability of the framework are possibly greatly different, and endless potential is provided for synthesizing various functional specific materials. However, the metal-organic framework materials still have some disadvantages, mainly represented by the following three aspects: (1) although this material has many three-dimensional channels, it is easy to cause structural collapse when ligand molecules occupied in the channels are removed. (2) In the solvent, especially in the acid-base solvent, it is easy to be dissociated, and the moisture resistance is not good. (3) The thermal stability is not good, and most metal organic framework materials are easy to be structurally damaged at the temperature higher than 300 ℃.
The core-shell structure metal-organic framework material is a composite material formed by compounding MOFs serving as a core or a shell with another material. The core-shell structure material not only keeps the excellent characteristics of two single materials, but also can overcome the defects of the single material, shows good synergistic effect and can show excellent performance. Firstly, the stability difference between different materials can be utilized, the metal organic framework material with high strength and a porous structure is used as a shell layer, and the stability of the composite material can be greatly improved. And secondly, the performance of the non-porous material can be optimized, the gas adsorption performance can be enhanced by constructing a core-shell structure, and the recycling rate of the material can be improved. Although core-shell metal organic framework materials have great development potential in the chemical field due to unique physical and chemical properties, the current research is still in the initial stage. Therefore, it is necessary to search a general synthesis method to design and prepare a series of core-shell metal organic framework materials containing different metals and having stable structures.
Disclosure of Invention
In order to solve the technical problems, the invention provides a core-shell metal sulfide composite material and a preparation method and application thereof. By varying the metal source (e.g., cobalt, nickel, copper, lead, iron, zinc, and manganese), a series of "yolk structured" hollow microspheres with different metal sulfide cores can be obtained. In the hollow microsphere, the shell is made of a metal organic framework material with certain rigidity, has certain pore distribution, and simultaneously ensures the structural stability and chemical stability of the whole material. The hollow microsphere material can be obtained by only one-step hydrothermal method, and the preparation of gram-grade powder can be realized by regulating and controlling different material ratios and solvent ratios, so that the hollow microsphere material has the potential of industrial production.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a core-shell type metal sulfide composite material, which has a structure of a hollow microsphere with a yolk structure, wherein polyoxometallate provides transition metal oxoacid ions, various metal sources provide transition metal ions, and the polyoxometallate and the metal sources are subjected to coordination reaction with an isophthalic acid organic ligand to form a metal organic framework shell; meanwhile, a sulfur source and transition metal ions are utilized to react to form a 'core', and a hollow core-shell structure microsphere taking metal sulfide as the core is formed through the etching action and different diffusion speeds of the ions to the 'shell' and the ions to the 'shell interior'; wherein, the metal ions and the organic ligand are subjected to coordination reaction to assemble into spheres, and the spheres are gradually hollowed through the etching action of metal sulfide nuclei; the carbon-based organic ligand can be used as a support frame and can be better coordinated with metal ions, so that metal elements are uniformly dispersed on the surface of the crust layer of the obtained core-shell composite material, the material has good structural strength, and meanwhile, the crust layer is endowed with certain rigidity.
The invention also provides a preparation method of the core-shell type metal sulfide composite material, which comprises the following steps:
dissolving polyoxometallate in deionized water to obtain a solution A; dissolving a metal source in a solvent I to obtain a solution B; dissolving an organic ligand m-benzene tricarboxylic acid in a solvent I to obtain a solution C; dissolving a surfactant and a dispersant polyvinylpyrrolidone in a solvent I to obtain a solution D; dissolving a stabilizer and a reducing agent hexamethylene tetramine in the solution II to obtain a solution E; dissolving a sulfur source in a solvent I to obtain a solution F; then adding a solvent I into a reaction kettle, then adding the solutions A, B, C, D, E and F into the reaction kettle, stirring for 2-10 h, and reacting for 1-12 h at 160-200 ℃; and obtaining a precipitate after the reaction is finished, and washing and drying the precipitate to obtain a powder sample of the core-shell type metal sulfide composite material. Preferably, the precipitate is centrifuged at 8000-10000 rpm for 2-5 min and then washed.
Preferably, the mass ratio of the polyoxometallate to the metal source is 0.5-1: 1, the metal sources include, but are not limited to, cobalt sources, nickel sources, copper sources, lead sources, iron sources, zinc sources, and manganese sources; the polyoxometallate includes, but is not limited to, phosphotungstic acid, ammonium molybdate, sodium tungstate, and phosphomolybdic acid.
Preferably, the mass ratio of the metal source to the m-benzenetricarboxylic acid is 9-16: 20.
preferably, the sulfur source includes, but is not limited to, thioacetamide, and the mass ratio of thioacetamide to metal source is 1:1.5 to 2.
Preferably, the mass ratio of the hexamethylene tetramine to the metal source is 1.5-4: 1; the mass ratio of the polyvinylpyrrolidone to the metal source is 2-8.2: 1.
preferably, the metal source providing the transition metal ion is cobalt acetylacetonate, nickel acetylacetonate, copper acetylacetonate, lead acetylacetonate, zinc acetylacetonate, manganese acetylacetonate, lead acetate, and zinc acetate.
Preferably, the solvent I is N, N-dimethylformamide; the solvent II is ethanol; the volume ratio of the solvent I to the solvent II is 1-7: 1.
preferably, the preparation method of the core-shell metal sulfide composite material further comprises the following steps:
after the obtained dry powder sample is subjected to high-temperature heat treatment, the organic ligand can be converted into a corresponding carbon matrix and successfully compounded with the converted metal particles, and the material subjected to vulcanization treatment can be converted into a corresponding double-sulfide core-shell metal organic framework material in situ; the shape of the powder sample is changed from an original smooth shell core-shell structure into a core-shell structure wrapped by external nano sheets;
the high-temperature heat treatment process is carried out in a tube furnace, and the carbonization treatment conditions are as follows: calcining for 2 hours at 800 ℃ under the argon atmosphere; the vulcanization treatment conditions are as follows: mixing the raw materials with sulfur powder according to the mass ratio of 1-2: 5, mixing, placing in an argon atmosphere, and calcining for 2 hours at 500-800 ℃.
The invention also provides application of the core-shell metal sulfide composite material in a nano reactor, catalysis, adsorption and energy storage and conversion.
Compared with the prior art, the invention has the following beneficial effects:
1. the method can obtain the core-shell metal organic framework hollow microspheres with a structure similar to yolk (also called yolk structure in the invention) by adjusting the proportion of the polyoxometallate to the filling amount of various metal sources, the proportion of the organic ligand to the metal sources, regulating and controlling the volume ratio of different solvents and introducing the surfactant and the stabilizer. The invention is realized by one-step solvent thermal reaction, the solution is required to be stirred before the reaction to ensure uniform mixing, and the core-shell structure material which is compounded with different metal sulfide cores and metal organic framework shells can be controllably obtained.
2. The synthesis process is simple and efficient, the practicability and the universality of the reaction are improved, the reaction materials are increased, the proportion of each component is finely adjusted, the powder with gram as a unit can be synthesized in one pot, and the industrial scale production is facilitated. Through the synergistic effect of the metal organic framework shell and the sulfide core, the thermal stability and the chemical stability of the hollow microsphere with the yolk structure are enhanced, the defect that most metal organic framework materials are easy to collapse in high temperature, acid-base solution and partial organic solvent is overcome, and good performances are shown in the fields of adsorption, catalytic carriers and energy sources.
3. The core-shell metal sulfide composite material obtained by the invention utilizes the periodic arrangement of metal ions and organic ligands to obtain a hollow microsphere with adjustable morphology and components, the nano microsphere can be used as a precursor, and can be converted into corresponding sulfide in situ through further calcination, so that the size of the nano particle is effectively limited, the nano particle is prevented from polymerizing at high temperature, and the close coupling of the nano particle and a carbon matrix is realized.
Drawings
FIG. 1 is a TEM image of the material obtained in example 1 of the present invention.
FIG. 2 is a TEM image of the material obtained in example 3 of the present invention.
FIG. 3 is a TEM image of the material obtained in example 4 of the present invention.
FIG. 4 is an XRD pattern of the material of example 3 after vulcanization treatment in example 10 of the present invention.
Figure 5 is an XRD pattern of the material of example 4 after sulfidation treatment in example 10 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following experimental methods and detection methods, unless otherwise specified, are conventional methods; the following reagents and starting materials are all commercially available unless otherwise specified.
Example 1
A preparation method of a core-shell type metal sulfide composite material comprises the following steps:
(1) Weighing 6.1mg of phosphotungstic acid, and dissolving in 61 mu L of deionized water to obtain a solution A;9mg of cobalt acetylacetonate is dissolved in 1mL of N, N-dimethylformamide to obtain a solution B; dissolving 15mg of m-benzenetricarboxylic acid in 0.25mL of N, N-dimethylformamide to obtain a solution C; dissolving 20mg of surfactant polyvinylpyrrolidone in 0.5mL of N, N-dimethylformamide to obtain a solution D; dissolving 20mg of hexamethylenetetramine serving as a stabilizer in 1mL of ethanol to obtain a solution E; dissolving 5mg thioacetamide in 0.25mL N, N-dimethylformamide to obtain a solution F; adding 5mL of N, N-dimethylformamide into a 25mL reaction kettle, then respectively adding the solutions A, B, C, D, E and F into the reaction kettle, and reacting for 12 hours at 180 ℃ to obtain black precipitates;
(2) Centrifuging the black precipitate at 10000rpm for 5min; then washing with ethanol, and drying in a vacuum drying oven at 40 ℃ for 10h to obtain 8mg of black cobalt sulfide core-shell composite material.
FIG. 1 is a TEM image of the product obtained in example 1. As is clear from FIG. 1, the material obtained by the method of example 1 was able to obtain uniform hollow microspheres having a diameter of about 500 nm.
Example 2
A preparation method of a core-shell type metal sulfide composite material comprises the following steps:
(1) Weighing 122mg of phosphotungstic acid, and dissolving in 1220 mu L of deionized water to obtain a solution A; dissolving 180mg of cobalt acetylacetonate in 10mL of N, N-dimethylformamide to obtain a solution B; dissolving 300mg of m-benzene tricarboxylic acid in 10mL of N, N-dimethylformamide to obtain a solution C; dissolving 400mg of surfactant polyvinylpyrrolidone in 10mL of N, N-dimethylformamide to obtain a solution D; dissolving 400mg of stabilizer hexamethylene tetramine in 12mL of ethanol to obtain a solution E; dissolving 100mg of thioacetamide in 10mL of N, N-dimethylformamide to obtain a solution F; adding 10mL of N, N-dimethylformamide into a 100mL reaction kettle, then respectively adding the solutions A, B, C, D, E and F into the reaction kettle, and reacting for 9 hours at 180 ℃ to obtain black precipitates;
(2) Then carrying out centrifugal treatment, wherein the centrifugal rotating speed is 10000rpm, and the time is 2min; then, after washing with ethanol, the core-shell composite was dried in a vacuum oven at 40 ℃ for 10 hours to obtain 187mg of a black cobalt sulfide core-shell composite.
Example 3
A preparation method of a core-shell type metal sulfide composite material comprises the following steps:
(1) Weighing 415mg of phosphotungstic acid, and dissolving in 4.15mL of deionized water to obtain a solution A; dissolving 600mg of cobalt acetylacetonate in 30mL of N, N-dimethylformamide to obtain a solution B; dissolving 1020mg of m-benzene tricarboxylic acid in 30mL of N, N-dimethylformamide to obtain a solution C; 1360mg of surfactant polyvinylpyrrolidone is dissolved in 30mL of N, N-dimethylformamide to obtain a solution D; 1360mg of stabilizer hexamethylene tetramine is dissolved in 41mL of ethanol to obtain a solution E; dissolving 340mg of thioacetamide in 30mL of N, N-dimethylformamide to obtain a solution F; 50mL of N, N-dimethylformamide is added into a 300mL reaction kettle, and then the solutions A, B, C, D, E and F are respectively added into the reaction kettle and react for 9 hours at 180 ℃ to obtain black precipitates;
(2) Then carrying out centrifugal treatment, wherein the centrifugal rotating speed is 9000rpm, and the time is 3min; then washing with ethanol, and drying in a vacuum drying oven at 40 ℃ for 10h to obtain 1g of black cobalt sulfide core-shell composite material.
FIG. 2 is a TEM image of the core-shell metal sulfide composite obtained in example 3, and it is understood that the method can form hollow spheres having a uniform yolk structure and a diameter of about 500 nm.
Example 4
A preparation method of a core-shell type metal sulfide composite material comprises the following steps:
(1) Weighing 61mg of phosphotungstic acid, and dissolving in 1.22mL of deionized water to obtain a solution A;80mg of nickel acetylacetonate is dissolved in 8mL of N, N-dimethylformamide to obtain a solution B; dissolving 150mg of m-benzene tricarboxylic acid in 8mL of N, N-dimethylformamide to obtain a solution C; dissolving 500mg of surfactant polyvinylpyrrolidone in 8mL of N, N-dimethylformamide to obtain a solution D; dissolving 200mg of hexamethylenetetramine serving as a stabilizer in 16mL of ethanol to obtain a solution E; 50mg of thioacetamide is dissolved in 8mL of N, N-dimethylformamide to obtain a solution F; adding 16mL of ethanol into a 100mL reaction kettle, then respectively adding the solutions A, B, C, D, E and F into the reaction kettle, and reacting for 9 hours at 180 ℃ to obtain black precipitates;
(2) Then carrying out centrifugal treatment, wherein the centrifugal rotating speed is 8000rpm, and the time is 4min; then washing with ethanol, and drying in a vacuum drying oven at 40 ℃ for 10h to obtain 90mg of black core-shell composite material.
FIG. 3 is a TEM image of the core-shell type metal sulfide composite obtained in example 4, and the pellet diameter of the yolk structure is about 200nm, compared with the pellet of example 1.
Example 5
A preparation method of a core-shell type metal sulfide composite material comprises the following steps:
(1) Weighing 6.0mg of phosphomolybdic acid, and dissolving in 61 mu L of deionized water to obtain a solution A;10mg of copper acetylacetonate was dissolved in 1mL of N, N-dimethylformamide to obtain a solution B; dissolving 15mg of organic ligand m-benzene tricarboxylic acid in 0.25mL of N, N-dimethylformamide to obtain a solution C; dissolving 20mg of surfactant polyvinylpyrrolidone in 0.5mL of N, N-dimethylformamide to obtain a solution D; dissolving 20mg of hexamethylenetetramine serving as a stabilizer in 1mL of ethanol to obtain a solution E; dissolving 5mg thioacetamide in 0.25mL of N, N-dimethylformamide to obtain a solution F; adding 5mL of N, N-dimethylformamide into a 25mL reaction kettle, then respectively adding the solutions A, B, C, D, E and F into the reaction kettle, and reacting at 180 ℃ for 12h to obtain black precipitate;
(2) Then carrying out centrifugal treatment, wherein the centrifugal rotation speed is 10000rpm, and the time is 4min; then washing with ethanol, and drying in a vacuum drying oven at 40 ℃ for 10h to obtain 10mg of black core-shell composite material.
Example 6
A preparation method of a core-shell type metal sulfide composite material comprises the following steps:
(1) Weighing 6.0mg of ammonium molybdate and dissolving in 61 mu L of deionized water to obtain a solution A; dissolving 12mg of lead acetylacetonate in 1mL of N, N-dimethylformamide to obtain a solution B; dissolving 15mg of m-benzenetricarboxylic acid in 0.25mL of N, N-dimethylformamide to obtain a solution C; dissolving 20mg of surfactant polyvinylpyrrolidone in 0.5mL of N, N-dimethylformamide to obtain a solution D; dissolving 48mg of hexamethylenetetramine serving as a stabilizer in 7mL of ethanol to obtain a solution E; dissolving 6mg thioacetamide in 0.25mL of N, N-dimethylformamide to obtain a solution F; adding 5mL of N, N-dimethylformamide into a 25mL reaction kettle, then respectively adding the solutions A, B, C, D, E and F into the reaction kettle, and reacting at 180 ℃ for 12h to obtain black precipitate;
(2) Then carrying out centrifugal treatment, wherein the centrifugal rotation speed is 10000rpm, and the time is 4min; then washing with ethanol, and drying in a vacuum drying oven at 40 ℃ for 10h to obtain 8mg of black lead sulfide core-shell composite material.
Example 7
A preparation method of a core-shell type metal sulfide composite material comprises the following steps:
(1) Weighing 6.1mg of sodium tungstate, and dissolving in 61 mu L of deionized water to obtain a solution A;6.1mg of lead acetate is dissolved in 1mL of N, N-dimethylformamide to obtain a solution B; dissolving 10mg of m-benzenetricarboxylic acid in 0.25mL of N, N-dimethylformamide to obtain a solution C; dissolving 50.02mg of surfactant polyvinylpyrrolidone in 0.5mL of N, and obtaining solution D by N-dimethylformamide; dissolving 9.15mg of hexamethylenetetramine serving as a stabilizer in 1mL of ethanol to obtain a solution E; dissolving 4.07mg thioacetamide in 0.25mL N, N-dimethylformamide to obtain a solution F; adding 5mL of N, N-dimethylformamide into a 25mL reaction kettle, then respectively adding the solutions A, B, C, D, E and F into the reaction kettle, and reacting for 12 hours at 180 ℃ to obtain black precipitates;
(2) Then carrying out centrifugal treatment, wherein the centrifugal rotation speed is 10000rpm, and the time is 4min; then washing with ethanol, and drying in a vacuum drying oven at 40 ℃ for 10h to obtain 8mg of black lead sulfide core-shell composite material.
Example 8
A preparation method of a core-shell type metal sulfide composite material comprises the following steps:
(1) Weighing 6.1mg of phosphotungstic acid, and dissolving in 61 mu L of deionized water to obtain a solution A; dissolving 9mg of zinc acetylacetonate in 1mL of N, N-dimethylformamide to obtain a solution B; dissolving 20mg of m-benzene tricarboxylic acid in 0.25mL of N, N-dimethylformamide to obtain a solution C; dissolving 30mg of surfactant polyvinylpyrrolidone in 0.5mL of N, N-dimethylformamide to obtain a solution D; dissolving 30mg of stabilizer hexamethylene tetramine in 1mL of ethanol to obtain a solution E; dissolving 5mg thioacetamide in 0.25mL of N, N-dimethylformamide to obtain a solution F; adding 5mL of N, N-dimethylformamide into a 25mL reaction kettle, then respectively adding the solutions A, B, C, D, E and F into the reaction kettle, and reacting at 180 ℃ for 12h to obtain gray precipitate;
(2) Then carrying out centrifugal treatment, wherein the centrifugal rotation speed is 10000rpm, and the time is 4min; then washed by ethanol and dried in a vacuum drying oven at 40 ℃ for 10h to obtain 7mg of gray core-shell composite material.
Example 9
A preparation method of a core-shell type metal sulfide composite material comprises the following steps:
(1) Weighing 6.1mg of phosphotungstic acid, and dissolving in 61 mu L of deionized water to obtain a solution A;10mg of manganese acetylacetonate is dissolved in 1mL of N, N-dimethylformamide to obtain a solution B; dissolving 15mg of m-benzenetricarboxylic acid in 0.25mL of N, N-dimethylformamide to obtain a solution C; dissolving 20mg of surfactant polyvinylpyrrolidone in 0.5mL of N, N-dimethylformamide to obtain a solution D; dissolving 20mg of stabilizer hexamethylene tetramine in 1mL of ethanol to obtain a solution E; dissolving 5mg thioacetamide in 0.25mL N, N-dimethylformamide to obtain a solution F; adding 5mL of N, N-dimethylformamide into a 25mL reaction kettle, then respectively adding the solutions A, B, C, D, E and F into the reaction kettle, and reacting at 180 ℃ for 12h to obtain yellow precipitate;
(2) Then carrying out centrifugal treatment, wherein the centrifugal rotation speed is 10000rpm, and the time is 4min; then, after washing with ethanol, the mixture was dried in a vacuum oven at 40 ℃ for 10 hours to obtain 10mg of a yellow core-shell composite material.
Example 10
A method for preparing a core-shell metal sulfide composite material, which is different from the method of example 3,
after the obtained dry powder sample is subjected to high-temperature heat treatment, the organic ligand can be converted into a corresponding carbon matrix and successfully compounded with the converted metal particles, and the material subjected to vulcanization treatment can be converted into a corresponding double-sulfide core-shell metal organic framework material in situ; the shape of a powder sample is changed from an original hollow sphere to a core-shell structure wrapped by external nanosheets.
The high-temperature heat treatment process is carried out in a tube furnace, and the treatment conditions are as follows: calcining for 2 hours at 800 ℃ under the argon atmosphere; the vulcanization treatment conditions are as follows: mixing the raw materials with sulfur powder according to a mass ratio of 1:5, mixing, placing in an argon atmosphere, and calcining for 2h at 500 ℃.
Fig. 4 is an XRD spectrum of the material obtained from the cobalt sulfide core-shell type metal sulfide composite material obtained in example 3 after high temperature sulfidation by the method of example 10, which has obvious crystallinity, and is a bimetallic tungsten sulfide composite material of tungsten sulfide and cobalt sulfide by comparison.
FIG. 5 is a nickel-tungsten sulfide composite obtained by subjecting the material obtained in example 4 to the high-temperature sulfidation method of example 10. Obvious diffraction peaks appear after vulcanization, and further shows that the core-shell metal organic framework can be synthesized into the bimetallic sulfide composite material by an in-situ conversion method.
It should be noted that, when the present invention relates to a numerical range, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all changes and modifications that fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. The core-shell metal sulfide composite material is characterized in that the core-shell metal sulfide composite material is a hollow microsphere with a yolk structure, wherein polyoxometallate provides transition metal oxoacid ions and a metal source provides transition metal ions, and the transition metal ions and an organic ligand of m-benzenetricarboxylic acid are subjected to coordination reaction to form a metal organic framework shell; meanwhile, a sulfur source and transition metal ions are utilized to react to form a 'core', and hollow microspheres taking metal sulfide as the core are formed through etching and different diffusion speeds of the ions to the 'shell' and the ions to the 'shell' respectively;
the core-shell metal sulfide composite material is prepared according to the following method:
dissolving polyoxometallate in deionized water to obtain a solution A; dissolving a metal source in a solvent I to obtain a solution B; dissolving m-benzene tricarboxylic acid in a solvent I to obtain a solution C; dissolving polyvinylpyrrolidone in a solvent I to obtain a solution D; dissolving hexamethylenetetramine in the solution II to obtain a solution E; dissolving a sulfur source in a solvent I to obtain a solution F; then adding a solvent I into a reaction kettle, then adding the solutions A, B, C, D, E and F into the reaction kettle, stirring for 2-10 h, and reacting for 1-12 h at 160-200 ℃; and obtaining a precipitate after the reaction is finished, and washing and drying the precipitate to obtain a powder sample of the core-shell type metal sulfide composite material.
2. The method of claim 1, comprising the steps of:
dissolving polyoxometallate in deionized water to obtain a solution A; dissolving a metal source in a solvent I to obtain a solution B; dissolving m-benzene tricarboxylic acid in a solvent I to obtain a solution C; dissolving polyvinylpyrrolidone in a solvent I to obtain a solution D; dissolving hexamethylenetetramine in the solution II to obtain a solution E; dissolving a sulfur source in a solvent I to obtain a solution F; then adding a solvent I into a reaction kettle, then adding the solution A, B, C, D, E and F into the reaction kettle, stirring for 2-10 h, and reacting for 1-12 h at 160-200 ℃; and obtaining a precipitate after the reaction is finished, and washing and drying the precipitate to obtain a powder sample of the core-shell type metal sulfide composite material.
3. The method for preparing the core-shell metal sulfide composite material according to claim 2, wherein the mass ratio of the polyoxometallate to the metal source is 0.5-1: 1, the metal sources include, but are not limited to, cobalt sources, nickel sources, copper sources, lead sources, iron sources, zinc sources, and manganese sources; the polyoxometallates include, but are not limited to, phosphotungstic acid, ammonium molybdate, sodium tungstate and phosphomolybdic acid.
4. The method for preparing the core-shell metal sulfide composite material according to claim 3, wherein the mass ratio of the metal source to the isophthalic acid is 9 to 16:20.
5. the method of claim 4, wherein the sulfur source includes, but is not limited to, thioacetamide, and the mass ratio of thioacetamide to metal source is 1:1.5 to 2.
6. The method for preparing the core-shell metal sulfide composite material as claimed in claim 3, wherein the mass ratio of hexamethylenetetramine to the metal source is 1.5-4: 1; the mass ratio of the polyvinylpyrrolidone to the metal source is 2-8.2: 1.
7. the method of claim 3, wherein the metal source providing the transition metal ions is cobalt acetylacetonate, nickel acetylacetonate, copper acetylacetonate, lead acetylacetonate, iron acetylacetonate, zinc acetylacetonate, manganese acetylacetonate, lead acetate, or zinc acetate.
8. The method of claim 2, wherein the solvent I is N, N-dimethylformamide; the solvent II is ethanol; the volume ratio of the solvent I to the solvent II is 1-7: 1.
9. the method of claim 2, further comprising:
after the obtained dry powder sample is subjected to high-temperature heat treatment, the organic ligand can be converted into a corresponding carbon matrix and successfully compounded with the converted metal particles, and the material subjected to vulcanization treatment can be converted into a corresponding double-sulfide core-shell metal organic framework material in situ; the shape of the powder sample is changed from an original smooth shell core-shell structure into a core-shell structure wrapped by external nano sheets;
the high-temperature heat treatment process is carried out in a tube furnace, and the carbonization treatment conditions are as follows: calcining for 2 hours at 800 ℃ under the argon atmosphere; the vulcanization treatment conditions are as follows: mixing the raw materials with sulfur powder according to the mass ratio of 1-2: 5, mixing, placing in an argon atmosphere, and calcining for 2 hours at 500-800 ℃.
10. Use of the core-shell metal sulfide composite of claim 1 in nanoreactors, catalysis, adsorption, and energy storage and conversion.
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