CN108383103B - Preparation method of hollow carbon cage - Google Patents
Preparation method of hollow carbon cage Download PDFInfo
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- CN108383103B CN108383103B CN201810565238.7A CN201810565238A CN108383103B CN 108383103 B CN108383103 B CN 108383103B CN 201810565238 A CN201810565238 A CN 201810565238A CN 108383103 B CN108383103 B CN 108383103B
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Abstract
The invention discloses a preparation method of a hollow carbon cage, which comprises the steps of reacting ion exchange resin containing identification cations in an atmosphere according to a certain temperature control mode, carrying out post-treatment, cleaning to be neutral, and drying. The preparation method is a one-step reaction method, has simple and convenient steps, convenient and easy operation, rich raw material sources, low equipment requirements and easy large-scale production. The obtained carbon material is of a hollow and porous structure, has large internal holes, can realize controllable exchange of substances inside and outside the hollow cage, and can be applied to the fields of high-efficiency heat dissipation, supercapacitors, metal air batteries, absorption of refractory organic matters, slow-release drug carriers, catalyst carriers and the like.
Description
Technical Field
The invention relates to a preparation method of a hollow carbon cage, belongs to the field of novel carbon materials, and is widely applied to the fields of efficient heat dissipation, supercapacitors, metal-air batteries, adsorption of refractory organic matters, slow-release drug carriers, catalyst carriers and the like.
Background
The porous carbon has the characteristics of large specific surface area, adjustable pore structure and interface property, good chemical stability and the like, and is applied to the fields of new energy, environmental protection, gas separation and storage, drug carriers, catalyst carriers and the like. The porous carbon is generally granular, spherical or even hollow spherical structures rarely appear, and the controllability of the morphology structure is poor. The porous carbon microsphere is generally determined by the shape of a precursor, wherein the patent 'an ultrahigh specific surface area hollow carbon nanosphere and a preparation method and application thereof' (application number: 201510010474.9) prepares the porous carbon microsphere by using an organic spherical precursor prepared by a sol-gel method and optimizing reaction conditions. The rich pore channels of the carbon material are generally prepared by a chemical activation method rather than a physical method, and the chemical activation process has the problems of environmental pollution, harsh equipment conditions, poor safety, accompanied with gaseous or liquid pollutants, large water consumption in the cleaning step, low yield and the like, so that the industrialization and the further development of the carbon material are limited. For example, the preparation method of an ion exchange resin-based carbon material (application No. 201610633986.5), the preparation method of a resin-based carbon microsphere adsorption material (application No. 201710222647.2), the preparation method of a liquefied aquatic plant-based carbon microsphere (application No. 201610886579.5), and the preparation method of spherical activated carbon with high specific surface area (application No. 200710041059.5) are used for preparing carbon materials by a chemical activation method, so that the process has high requirements on equipment, is complicated to operate, has poor safety, and is not easy to produce in large scale.
Organometallic framework compounds (MOFs) are one of the effective precursors of carbon cages, and particularly comprise zinc MOFs. Researchers form pores by pyrolysis and zinc gasification to produce carbon balls or carbon cages with structures which can be regulated and controlled at the atomic level. However, the idea still needs to solve the problems of high cost and complex preparation process of the MOFs, such as "a porous carbon material for a power lithium ion battery cathode and a preparation method thereof" (application No. 201510367076.2), "a method for preparing a magnetic carbon material from a core # shell metal organic framework material" (application No. 201611233463.8), "a method for preparing a carbon material with a high specific surface area using a metal organic framework material as a template" (application No. 201010222986.9). The carbon microspheres can be prepared by a template method, such as 'a high specific surface area mesoporous-microporous carbon microsphere for a supercapacitor and a preparation method thereof' (CN201510765168.6), but templates used in the method are all in a nanometer scale, so that the cost is high, a subsequent treatment process is added, and the method is not beneficial to large-scale production. The crystal structure of the carbon spheres obtained by the existing activation scheme is basically an amorphous structure, a graphite-like structure (application number: 201710165850.0) is rarely generated, and the assumption that the graphite degree of the carbon spheres is effectively regulated in the radial direction cannot be basically realized.
Disclosure of Invention
The invention aims to solve the problems of complex preparation process, high cost, difficult formation of a controllable structure, small storage capacity, difficult regulation and control of pore ion diffusion and the like of carbon materials in the application of the cross field, and provides a preparation method of a hollow porous carbon cage which can be produced in a large scale, has rich raw materials, is simple to operate and has a controllable structure, so that the application field of novel carbon materials is expanded and the requirements of special fields on the carbon materials are met.
The technical scheme of the invention is as follows:
a process for preparing the hollow carbon cage with controllable structure includes such steps as reaction of ion exchange resin containing the identified cations in atmosphere in a temp-controlled mode, post-treating, washing to neutral state, and baking.
The ion exchange resin is one or more of weak acid, chelating property, oxidation reduction property or amphoteric ion exchange resin.
The marked cations are one or more of cations containing A-type and B-type metals.
The space distribution of the positive ions marked from inside to outside is spherical distribution, and the distribution form is one or more of A, B, C, AB, BA, AC, CA, BC, CB, ABC, ACB, CAB, CBA, CAB and BAC.
A is H+B is K+、Na+、Li+C is one or more of corresponding cations of Zn, Mg, Ca, Si, Ge, Ti, V, Cr, Mn, Fe, Co, Ni, Al, Zr, Nb, Mo, Hf, Ta, W and B.
The preparation method of the ion exchange resin containing the marked cations comprises the steps of soaking the ion exchange resin in a solution containing the marked cations and drying the ion exchange resin to obtain the ion exchange resin. If a plurality of cations need to be marked, soaking the solution in the solution containing the marked cations in sequence according to the spatial distribution of the marked cations.
The atmosphere is one or more of vacuum, air and inert atmosphere, and the atmosphere state is one of static or flowing.
The certain temperature control mode is as follows:
and (3) low-temperature stage: heating to 150 ℃ and 500 ℃ at the speed of 0.5-50 ℃/min, and reacting for 0-12 h;
a medium temperature stage: heating to 500 and 950 ℃ at the speed of 0.5-50 ℃/min, and reacting for 0-12 h;
and (3) high-temperature stage: the temperature is raised to 950 ℃ and 1600 ℃ at the speed of 0.5-50 ℃/min, and the reaction is carried out for 0-12 h.
The certain temperature control mode also comprises natural cooling to room temperature.
The post-treatment method is one or two of atmosphere heating and solution reaction.
The solution treatment is one of acid washing, alkali washing or acid-alkali alternate immersion washing.
The invention has the beneficial effects that:
the invention is a simple method for producing nano carbon microspheres in a large scale, and the specific surface area, pore structure, hollow volume, crystal structure distribution and the like of the material can be effectively regulated and controlled through factors such as resin type, labeled cation selection, cation distribution, temperature control program, post-treatment and the like. The invention has the advantages of large ion exchange resin storage, mature production technology, controllable hollow carbon cage structure, excellent performance, less equipment investment and large storage space, and is a simple and efficient preparation method of the nano carbon microspheres.
The preparation method is a one-step reaction method, has simple and convenient steps, convenient and easy operation, rich raw material sources, low equipment requirements and easy large-scale production. The obtained carbon material is of a hollow and porous structure, has large internal holes, can realize controllable exchange of substances inside and outside the hollow cage, and can be applied to the fields of high-efficiency heat dissipation, supercapacitors, metal air batteries, absorption of refractory organic matters, slow-release drug carriers, catalyst carriers and the like.
Drawings
FIG. 1 is an SEM photograph of a hollow carbon cage of example 6 of the present invention.
FIG. 2 is a graph of graphitization degree of hollow carbon cage according to the present invention and labeled cation relationship in example 3.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. The following examples are intended to illustrate the invention without further limiting it, which can be carried out in any of the ways described in the summary of the invention.
Example 1
Pretreating 2g of macroporous weak-acidic cation exchange resin D-85 of propionic acid series according to GB5476-1996, soaking in 5% HCl solution for 3h, transferring into 3M KCl solution, soaking for 12h, and placing into 2M FeCl3Standing the solution for 1h, transferring the solution into a vacuum oven at 60 ℃, and drying the solution for 12 h. Putting the obtained resin (dried resin) into a tube furnace, heating to 350 ℃ at a speed of 2 ℃/min (low-temperature stage) under the protection of 20ccm Ar, reacting for 2h, then continuously heating to 750 ℃ at a speed of 5 ℃/min (medium-temperature stage), reacting for 0.5h, heating to 1350 ℃ at a speed of 2 ℃/min (high-temperature stage), reacting for 5h, then naturally cooling to room temperature, immersing the reaction product into 1M HCl solution for 0.5h, then taking out and washing with clear water to be neutral, and drying in a 120 ℃ oven for 24h to obtain the resin with a specific surface area of 745.2M2Pore volume of 0.32 cm/g3A hollow carbon cage with amorphous and graphitized outside and the average pore diameter of 2.3 nm.
Example 2
6g of chelating resin D403 was immersed in 1.5M KCl solution for 12h and placed again in 5M Ni (NO)3)2Standing the solution for 12h, transferring the solution into a vacuum oven at 60 ℃, and drying the solution for 12 h. Putting the obtained resin into a tube furnace, heating to 450 ℃ (low-temperature stage) at a speed of 5 ℃/min under the protection of 60ccm Ar, reacting for 1h, heating to 1600 ℃ (high-temperature stage) at a speed of 20 ℃/min, reacting for 12h, naturally cooling to room temperature, immersing the reaction product into 1.5M HCl solution for 3h, taking out, washing to neutrality with clear water, and drying in a 120 ℃ oven for 24h to obtain the resin with a specific surface area of 843.8M2Pore volume of 0.45 cm/g3A hollow carbon cage with an average pore diameter of 2.1nm, an internal graphitized external amorphous structure.
Example 3
2g of a catechol-type redox exchange resin impregnated into 3M MgCl2Soaking in the solution for 12 hr, adding into 2M LiCl solution, standing for 1 hrThen the mixture is transferred to a vacuum oven with the temperature of 80 ℃ and dried for 12 h. The obtained resin was placed in a tube furnace at 120ccm N2Under protection, heating to 1250 ℃ (high temperature stage) at a speed of 2 ℃/min, reacting for 2h, then naturally cooling to room temperature, immersing the reaction product into 1M hydrochloric acid solution for 5h, then taking out, washing with clear water to be neutral, and drying in an oven at 120 ℃ for 24h to obtain the product with the specific surface area of 545.2M2Pore volume of 0.38 cm/g3A hollow carbon cage with an average pore diameter of 2.7nm, an internal graphitized external amorphous structure.
FIG. 2 is a graph of the graphitization degree of the hollow carbon cage according to the present embodiment with labeled cations. FIG. 2 shows that the crystallite structure of the carbon cage can be controlled by adjusting the molar ratio of K/Zn.
Example 4
10g of a catechol-type redox exchange resin was immersed in 5M MgCl2Soaking in the solution for 12h, putting into 2M LiCl solution again, standing for 1h, transferring into a vacuum oven at 80 deg.C, and drying for 12 h. The obtained resin was put into a tube furnace with a vacuum degree of 10-4Heating Pa and at the speed of 2 ℃/min to 1050 ℃ (high-temperature stage), reacting for 5h, then naturally cooling to room temperature, immersing the reaction product in 0.5M nitric acid solution for 2h, then taking out, washing with clear water to be neutral, and drying in a 120 ℃ oven for 10h to obtain the product with the specific surface area of 635.6M2Per g, pore volume 0.55cm3A hollow carbon cage with an average pore diameter of 2.6nm, an internal graphitized external amorphous structure.
Example 5
Pretreating 2g of macroporous weak-acidic cation exchange resin D-85 of propionic acid alkene according to GB5476-1996, soaking in 1-10% HCl solution for 3h, transferring into 3M KCl solution, soaking for 0.5h, and placing in 2M ZnCl2Standing the solution for 1h, transferring the solution into a vacuum oven at 60 ℃, and drying the solution for 12 h. Putting the obtained resin into a tube furnace, heating to 850 ℃ (middle temperature stage) at a speed of 5 ℃/min under the protection of 20ccm Ar, reacting for 1.0h, heating to 1000 ℃ (high temperature stage) at a speed of 2 ℃/min, reacting for 0.5h, naturally cooling to room temperature, immersing the reaction product into 1M hydrochloric acid solution for 0.5h, taking out, washing to be neutral by clear water, baking in a 120 ℃ oven for 6h, and then putting into Ar atmosphere, heating to 1500 DEG CThe reaction is carried out for 2 hours, and the specific surface area is obtained to be 538.1m2Pore volume of 0.43 cm/g3A hollow carbon cage with amorphous and graphitized outside and the average pore diameter of 2.7 nm.
Example 6
Immersing 5g of macroporous weak-acidic cation exchange resin D113 of propionic acid alkene series in 1-10% HCl solution for 3h, and transferring to 2M ZnCl2Soaking in the solution for 12h, placing into 3M NaCl solution again, standing for 1h, transferring into a vacuum oven at 60 deg.C, and drying for 12 h. Putting the obtained resin into a tube furnace, heating to 1050 ℃ (high temperature stage) at the speed of 30 ℃/min under the protection of 60ccm Ar, reacting for 2h, then naturally cooling to room temperature, immersing the reaction product into 1M hydrochloric acid solution for 1.0h, taking out, washing with clear water to be neutral, and drying in a 120 ℃ oven for 24h to obtain the resin with the specific surface area of 445.7M2Pore volume of 0.37 cm/g3(g) hollow carbon cage with average pore diameter of 2.2nm, inner graphite and outer amorphous structure (figure 1).
Claims (6)
1. A preparation method of a hollow carbon cage is characterized in that ion exchange resin containing identification cations is reacted in an atmosphere according to a certain temperature control mode, post-treated, cleaned to be neutral and dried;
the space distribution of the positive ions is marked from inside to outside and is spherical distribution, and the distribution form is one or more of AB, BA, AC, CA, BC, CB, ABC, ACB, CAB, CBA and BAC; a is H+B is K+、Na+、Li+C is one or more of corresponding cations of Mg, Ca, Si, Ge, Ti, V, Cr, Mn, Fe, Co, Ni, Al, Zr, Nb, Mo, Hf, Ta, W and B;
the certain temperature control mode is as follows:
and (3) low-temperature stage: heating to 150 ℃ and 500 ℃ at the speed of 0.5-50 ℃/min, and reacting for 0-12 h;
a medium temperature stage: heating to 500 and 950 ℃ at the speed of 0.5-50 ℃/min, and reacting for 0-12 h;
and (3) high-temperature stage: the temperature is raised to 950-1600 ℃ at the speed of 0.5-50 ℃/min, and the reaction is carried out for 0-12h, not including 0 h.
2. The method for preparing a hollow carbon cage according to claim 1, wherein the ion exchange resin is one or more of weakly acidic, chelating, redox or amphoteric ion exchange resin.
3. The method for preparing a hollow carbon cage according to claim 1, wherein the atmosphere is one or more of vacuum and inert atmosphere, and the atmosphere is one of static or flowing.
4. The method for preparing a hollow carbon cage according to claim 1, wherein the certain temperature control mode further comprises naturally cooling to room temperature.
5. The method for preparing a hollow carbon cage according to claim 1, wherein the post-treatment method is a solution reaction.
6. The method for preparing a hollow carbon cage according to claim 5, wherein the solution treatment is one of acid washing, alkali washing, or acid-alkali alternate immersion washing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20110126300A (en) * | 2010-05-17 | 2011-11-23 | 한국화학연구원 | Visible-light photoactive spherical carbon porous material and its manufacturing method |
| CN102992306A (en) * | 2012-11-14 | 2013-03-27 | 中山大学 | Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof |
| CN106348280A (en) * | 2016-10-21 | 2017-01-25 | 南通绿业中试技术研究院有限公司 | Preparation method for spherical porous carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20110126300A (en) * | 2010-05-17 | 2011-11-23 | 한국화학연구원 | Visible-light photoactive spherical carbon porous material and its manufacturing method |
| CN102992306A (en) * | 2012-11-14 | 2013-03-27 | 中山大学 | Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof |
| CN106348280A (en) * | 2016-10-21 | 2017-01-25 | 南通绿业中试技术研究院有限公司 | Preparation method for spherical porous carbon |
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