CN111916737B - Preparation method and application of porous carbon with one-dimensional core-shell structure - Google Patents
Preparation method and application of porous carbon with one-dimensional core-shell structure Download PDFInfo
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- CN111916737B CN111916737B CN202010802031.4A CN202010802031A CN111916737B CN 111916737 B CN111916737 B CN 111916737B CN 202010802031 A CN202010802031 A CN 202010802031A CN 111916737 B CN111916737 B CN 111916737B
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Abstract
The invention discloses a preparation method of a one-dimensional core-shell structure porous carbon, which comprises the following steps: dissolving 2-methylimidazole powder in methanol, adding Co-MOF-74 powder to form a uniform suspension A, and stirring at room temperature; dissolving zinc nitrate hexahydrate in methanol to form a solution B; slowly adding the solution B into the suspension A, continuously stirring at room temperature, centrifuging the product, washing with ethanol, and drying in an oven to obtain a Co-MOF-74@ ZIF-8 one-dimensional core-shell structure; and carrying out nitric acid pickling on the Co-MOF-74@ ZIF-8 one-dimensional core-shell structure after annealing under the protection of argon to obtain a product. The one-dimensional core-shell structure porous carbon prepared by the method can be widely applied to the fields of electrochemical energy storage, separation and purification, drug sustained release and the like.
Description
Technical Field
The invention relates to the technical field of synthesis of micro-nano composite materials, in particular to a preparation method and application of porous carbon with a one-dimensional core-shell structure, which is obtained by taking Metal Organic Frameworks (MOFs) as precursors and combining argon annealing treatment.
Background
Metal Organic Frameworks (MOFs) are a novel class of porous crystalline materials, and are formed by matching organic ligands and inorganic metal ions (metal clusters). As a class of branches of coordination polymers, the major advantage of MOFs, which have become an area of rapid development and have attracted the attention of researchers in the last two decades, is that their structures can be designed according to the application of researchers, varying from ligand to ligand and metal center. The key structural features of MOFs are their porosity and high specific surface area. The catalyst has excellent performance in the fields of catalysis, energy storage and conversion, gas adsorption and separation and the like. As a multifunctional material, the material for synthesizing the MOFs can enable the raw material with lower cost to have low frame density and high thermal stability, and the advantages enable the MOFs to become a candidate material of an energy material. The one-dimensional core-shell structure porous carbon prepared by the invention fully exerts the advantages of two MOF material derived porous carbons, has the conductivity of graphitized carbon and the high specific surface area of the porous carbon, and contributes to higher specific capacity. The method further enriches the types of MOF structural materials, expands the application field of MOFs materials, provides more alternative electrode active materials for high-efficiency electrochemical energy storage application, and has great practical utilization value.
Disclosure of Invention
The invention aims to: provides a preparation method of a porous carbon with a one-dimensional core-shell structure, and aims to develop an electrode material applied to a high-performance sodium-ion battery. The material has simple preparation method, low cost and wide application prospect.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of porous carbon with a one-dimensional core-shell structure comprises the following steps:
(1) Dissolving 2-methylimidazole powder in methanol, adding Co-MOF-74 powder to form a uniform suspension A, and stirring at room temperature;
(2) Dissolving zinc nitrate hexahydrate in methanol to form a solution B;
(3) Slowly adding the solution B into the suspension A, continuously stirring at room temperature, centrifuging the product, washing with ethanol, and drying in an oven to obtain a Co-MOF-74@ ZIF-8 one-dimensional core-shell structure;
(4) Annealing the Co-MOF-74@ ZIF-8 one-dimensional core-shell structure under the protection of argon to obtain a one-dimensional core-shell structure porous carbon material;
(5) And (3) placing the one-dimensional core-shell structure porous carbon material in a nitric acid solution, stirring and reacting in a water bath, then centrifugally separating a product, washing with ethanol, and drying in an oven to obtain the pure one-dimensional core-shell structure porous carbon.
Preferably, in the step (1), the concentration of 2-methylimidazole in the suspension A is 1.49mol L -1 The concentration of Co-MOF-74 was 6.66g L -1 The room temperature is 25 ℃;
preferably, in step (2), the concentration of solution B is 0.55mol L -1 ；
Preferably, in the step (3), the room temperature is 25 ℃, and the stirring time is 30min; the temperature of the oven is 75-85 ℃;
preferably, in the step (4), the annealing temperature is 900 ℃, and the holding time is 2 hours;
preferably, in the step (5), the volume ratio of the concentrated nitric acid to the water in the nitric acid solution is 1;
preferably, in the step (5), the water bath temperature is 75-85 ℃, and the water bath time is 23-25h;
preferably, in step (5), the temperature of the oven is 75-85 ℃.
Furthermore, the prepared one-dimensional core-shell structure porous carbon can be used as a negative electrode material of a high-performance sodium ion battery.
Compared with the prior art, the invention has the beneficial technical effects that:
1. the one-dimensional core-shell structure porous carbon prepared by the invention has different properties of two MOFs, graphitized carbon with high conductivity is arranged inside the derived carbon material, the porous carbon with high specific surface area is arranged outside the derived carbon material, and nitrogen is doped on the surface of the one-dimensional material, so that the performance requirements of large specific surface area, high conductivity and the like required by high-efficiency energy storage can be met, and the electrochemical performance of the porous carbon is further improved.
2. Provides an available way for the controllable preparation of the MOF @ MOF core-shell structure, enriches the types of MOF structural materials, expands the application of the MOF materials, and provides more optional electrode active materials for the application of high-efficiency electrochemical energy storage.
3. The surface of the one-dimensional material is convex, and nucleation growth on the surface is generally difficult, but the preparation method of the invention solves the problem, and the preparation method is simple and easy to operate, safe and pollution-free, and low in cost.
Drawings
FIG. 1 is a FESEM image of Co-MOF-74 prepared in example 1.
FIG. 2 is a FESEM and TEM image of the one-dimensional core-shell structure of Co-MOF-74@ ZIF-8 prepared in example 2.
Fig. 3 is a FESEM image and a TEM image of the one-dimensional core-shell structure porous carbon prepared in example 2.
FIG. 4 is an XRD pattern of Co-MOF-74 prepared in example 1 and an XRD pattern of Co-MOF-74@ ZIF-8 one-dimensional core-shell structure prepared in example 2.
Fig. 5 is an electrochemical performance diagram of the one-dimensional core-shell structure porous carbon prepared in example 3.
Detailed Description
For the convenience of understanding of those skilled in the art, the present invention will be described with reference to the accompanying drawings and examples.
Example 1 preparation of Co-MOF-74 powder
(1) 0.4g of 2, 5-dihydroxyterephthalic acid was added to 90ml of deionized water to form a solution A; 1.0g of cobalt acetate tetrahydrate is dissolved in 10ml of deionized water to form a solution B; slowly adding the solution B into the solution A after the solution A is continuously stirred and heated to boiling, and continuously stirring and reacting for 40min under the state;
(2) And (3) centrifugally separating the product, washing the product with ethanol, and drying the product in an oven at 80 ℃ to obtain Co-MOF-74 powder.
FIG. 1 is a FESEM image of Co-MOF-74 prepared in this example, showing that the nanorods are uniformly distributed and have a smooth surface.
Example 2 preparation of porous carbon with Co-MOF-74@ ZIF-8 one-dimensional core-shell structure and one-dimensional core-shell structure
(1) Dissolving 1.84g of 2-methylimidazole in 15ml of methanol, adding 0.1g of Co-MOF-74 powder to form a uniform suspension A, and stirring at room temperature; 0.83g of zinc nitrate hexahydrate is dissolved in 5ml of methanol to form a solution B; slowly adding the solution B into the suspension A, continuously stirring at room temperature, and stirring for reaction for 30min;
(2) Centrifugally separating the product, washing the product with ethanol, and drying the product in an oven at 80 ℃ to obtain a Co-MOF-74@ ZIF-8 one-dimensional core-shell structure;
(3) And (2) annealing the Co-MOF-74@ ZIF-8 one-dimensional core-shell structure powder with argon at 900 ℃, pickling in a nitric acid solution, stirring for 24 hours at 80 ℃, centrifugally separating the product, washing for 3 times with ethanol, and then drying the product in an oven at 80 ℃ to obtain the one-dimensional core-shell structure porous carbon.
FIG. 2 is a FESEM and TEM image of the one-dimensional core-shell structure of Co-MOF-74@ ZIF-8 prepared in this example. Fig. 3 is FESEM and TEM images of the one-dimensional core-shell structure porous carbon prepared in this example. It can be found that a layer of uniform particles is successfully loaded on the surface of the original nano rod, and a plurality of holes are formed after annealing. FIG. 4 is an XRD pattern of a one-dimensional core-shell structure of Co-MOF-74@ ZIF-8 prepared in this example, and the corresponding 2 θ corresponds to the peak of the nanorod Co-MOF-74, respectively, and also corresponds to the position of the standard peak of ZIF-8 reported in the literature, which indicates that the one-dimensional core-shell structure material is successfully prepared.
Example 3 Performance testing of one-dimensional core-shell porous carbon
(1) Uniformly mixing and dissolving the one-dimensional core-shell structure porous carbon, the conductive carbon black and the PVDF in a mass ratio of (8);
(2) Slicing the dried copper foil current collector to prepare a working electrode, taking glass fiber as a diaphragm and electrolyte as binary electrolyte, assembling the working electrode and the electrolyte into a 2032 button cell in a glove box filled with argon, wherein the test voltage range is 0.01V-3V vs Na + /Na。
FIG. 5 is a performance diagram of electrochemical storage of sodium ions in porous sodium with one-dimensional core-shell structure prepared in example 3. The sodium electrical property of the porous carbon with the one-dimensional core-shell structure is excellent.
The above examples are typical examples of the present invention, and are not intended to limit the present invention, for example, the reaction concentration, the reaction time, the temperature of the water bath, the annealing temperature, etc. can be further adjusted. Accordingly, it is intended that all such modifications and variations within the spirit and scope of the invention be limited only by the claims and their equivalents.
Claims (8)
1. A preparation method of porous carbon with a one-dimensional core-shell structure is characterized by comprising the following steps: the method comprises the following steps:
(1) Dissolving 2-methylimidazole powder in methanol, adding Co-MOF-74 powder to form a uniform suspension A, and stirring at room temperature, wherein the Co-MOF-74 powder is in a nanorod shape;
(2) Dissolving zinc nitrate hexahydrate in methanol to form a solution B;
(3) Slowly adding the solution B into the suspension A, continuously stirring at room temperature, centrifugally separating the product, washing with ethanol, and drying in an oven to obtain a Co-MOF-74@ ZIF-8 one-dimensional core-shell structure;
(4) Annealing the Co-MOF-74@ ZIF-8 one-dimensional core-shell structure under the protection of argon to obtain the one-dimensional core-shell structure porous carbon material, wherein the annealing temperature is 900 ℃, and the heat preservation time is 2 hours;
(5) And (3) placing the one-dimensional core-shell structure porous carbon material in a nitric acid solution, stirring and reacting in a water bath, then centrifugally separating a product, washing with ethanol, and drying in an oven to obtain the pure one-dimensional core-shell structure porous carbon.
2. The method for preparing one-dimensional core-shell porous carbon according to claim 1, wherein in the step (1), the concentration of 2-methylimidazole in the suspension A is 1.49mol L -1 The concentration of Co-MOF-74 was 6.66g L -1 The room temperature was 25 ℃.
3. The preparation method of porous carbon with one-dimensional core-shell structure according to claim 1, wherein in the step (2), the concentration of the solution B is 0.55mol L -1 。
4. The preparation method of the one-dimensional core-shell porous carbon according to claim 1, wherein in the step (3), the room temperature is 25 ℃, and the stirring time is 30min; the temperature of the oven is 75-85 ℃.
5. The preparation method of one-dimensional core-shell structure porous carbon according to claim 1, wherein in the step (5), the volume ratio of concentrated nitric acid to water in the nitric acid solution is 1.
6. The preparation method of the one-dimensional core-shell porous carbon according to claim 1, wherein in the step (5), the water bath temperature is 75-85 ℃ and the water bath time is 23-25h.
7. The method for preparing one-dimensional core-shell porous carbon according to claim 1, wherein in the step (5), the temperature of the oven is 75-85 ℃.
8. Application of the porous carbon with one-dimensional core-shell structure prepared by the preparation method according to any one of claims 1 to 7, which is characterized by being used as a negative electrode material of a sodium ion battery.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668548A (en) * | 2016-03-29 | 2016-06-15 | 北京化工大学 | New method for customizing high-dispersion co-doping porous carbon with core-shell structure |
| CN109638304A (en) * | 2018-12-29 | 2019-04-16 | 江苏大学 | A kind of preparation method and purposes of M-MOF-74/ graphene composite cathode material |
| CN110739463A (en) * | 2019-10-24 | 2020-01-31 | 南京邮电大学 | Preparation method and application of bimetal organic framework composite materials |
| CN111082050A (en) * | 2019-12-20 | 2020-04-28 | 兰州大学 | Lithium ion battery cathode material and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2578593A1 (en) * | 2011-10-04 | 2013-04-10 | Fundació Privada Institut Català de Nanotecnologia | Method for the preparation of metal organic frameworks |
| KR101669169B1 (en) * | 2014-12-19 | 2016-10-26 | 한국생산기술연구원 | Composites of carbon materials and covalent-organic frameworks, a preparation method thereof and a use thereof |
| CN105037444A (en) * | 2015-06-19 | 2015-11-11 | 哈尔滨工业大学 | Synthetic method of metal organic frameworks Co-MOF-74 |
| EP3413326B1 (en) * | 2016-02-04 | 2020-09-23 | Tpr Co., Ltd. | Electrode material comprising core-shell composite, method for producing same, catalyst, electrode, secondary battery, and electric double-layer capacitor |
| CN107399729A (en) * | 2017-06-28 | 2017-11-28 | 中山大学 | A kind of bimetallic MOFs nitrogenous graphitized carbon material |
| CN110090621A (en) * | 2019-05-16 | 2019-08-06 | 南京林业大学 | Derivative porous carbon materials of a kind of metal organic framework and the preparation method and application thereof |
| CN110212194B (en) * | 2019-06-12 | 2021-01-08 | 合肥工业大学 | Preparation method and application of one-dimensional MOF @ ZIF core-shell structure |
| CN110364712A (en) * | 2019-07-15 | 2019-10-22 | 合肥工业大学 | A kind of preparation method and applications of porous carbon@N doping porous carbon core-shell structure |
-
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- 2020-08-11 CN CN202010802031.4A patent/CN111916737B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668548A (en) * | 2016-03-29 | 2016-06-15 | 北京化工大学 | New method for customizing high-dispersion co-doping porous carbon with core-shell structure |
| CN109638304A (en) * | 2018-12-29 | 2019-04-16 | 江苏大学 | A kind of preparation method and purposes of M-MOF-74/ graphene composite cathode material |
| CN110739463A (en) * | 2019-10-24 | 2020-01-31 | 南京邮电大学 | Preparation method and application of bimetal organic framework composite materials |
| CN111082050A (en) * | 2019-12-20 | 2020-04-28 | 兰州大学 | Lithium ion battery cathode material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Expanding applications of zeolite imidazolate frameworks in catalysis: synthesis of quinazolines using ZIF-67 as an efficient heterogeneous catalyst;Thanh Truong，at al.;《RSC Advances》;20150226;第5卷(第31期);第24769-24776页 * |
| Metal-organic framework-74-Ni/carbon nanotube composite as sulfur host for high performance lithium-sulfur batteries;Guodong Xu，et al.;《Journal of Electroanalytical Chemistry》;20181017;第830卷;第43-49页 * |
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