CN114044509A - Preparation method of ordered microporous carbon with precise pore diameter - Google Patents
Preparation method of ordered microporous carbon with precise pore diameter Download PDFInfo
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- CN114044509A CN114044509A CN202111628999.0A CN202111628999A CN114044509A CN 114044509 A CN114044509 A CN 114044509A CN 202111628999 A CN202111628999 A CN 202111628999A CN 114044509 A CN114044509 A CN 114044509A
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Abstract
The invention relates to a preparation method of ordered microporous carbon with precise pore diameter. The carbon material obtained by the method has a periodically arranged three-dimensional microporous structure, the pore size is distributed in a narrow range of 1.1-1.4nm, the pore size is accurate and uniform, the pore structure is regular and ordered, and the specific surface area is up to 2780m2g–1The method is characterized in that a molecular sieve with an ordered microporous structure is taken as a template, and active sites Zn are introduced into the molecular sieve through cation exchange2+The method comprises the steps of decomposing a carbon source and depositing carbon by utilizing a chemical vapor deposition technology under the conditions of medium and low temperature of 350-550 ℃ and medium and low pressure of 200-600Torr, and finally removing a molecular sieve template by etching to obtain the ordered microporous carbon with precise pore diameter. Compared with the traditional porous carbon material synthesis method, the preparation method provided by the invention is simple in process and mild in condition, and the obtained microporous carbon has important application prospects in the fields of catalysis, gas adsorption separation, energy storage and the like.
Description
The technical field is as follows:
the invention belongs to the technical field of porous carbon materials, and particularly relates to a preparation method of ordered microporous carbon with precise pore diameter. The method is characterized in that: taking a molecular sieve with an ordered microporous structure as a template, and introducing active site Zn into the molecular sieve through cation exchange2+The decomposition of the carbon source is realized under the conditions of medium and low temperature and medium and low pressure by utilizing the chemical vapor deposition technologyAnd deposition of carbon, and finally etching to remove the molecular sieve template to obtain ordered microporous carbon with precise pore size. The key point of the invention is that the active site Zn is introduced into the molecular sieve2+And controlling the chemical vapor deposition at the medium and low temperature of 350-550 ℃ and the medium and low pressure of 200-600Torr to realize the rapid growth and uniform deposition of carbon in the molecular sieve template.
Background art:
the microporous material is a porous material with the pore size less than 2nm, and is widely applied to various technical fields of heterogeneous catalysis, adsorption, separation, gas storage and the like. Common microporous materials include molecular sieves, porous carbon materials, metal-organic framework compounds (MOFs), and Microporous Organic Polymers (MOPs), depending on composition and structure. Volume
The microporous carbon material has the excellent properties of the carbon material, such as high chemical stability, good conductivity, low price and the like, and the introduction of the microporous structure enables the microporous carbon material to have the excellent properties of large specific surface area, many active sites and the like. The ordered microporous carbon material has uniform aperture and regular and ordered pore channel arrangement, and thus has important application in the fields of catalysis, adsorption separation, energy storage and the like. The traditional ordered microporous carbon material is generally prepared by taking natural precursors such as coconut shells, coal, wood and the like or phenolic resin and the like as precursors, and the ordered microporous carbon obtained by the method has the outstanding defects of wide pore size distribution and difficult control of porosity, thereby greatly limiting the application of the ordered microporous carbon. The document "the Formation of New Type of Porous Carbon by Carbon catalysis in Zeolite Nanochannels" (Chemistry of Materials, 1997,9,2, 609-plus 615) uses acrylonitrile and furfuryl alcohol as Carbon sources, and Y-Type molecular sieve as a template to obtain ordered microporous Carbon, but the method has harsh conditions, the reaction temperature needs to reach more than 800 ℃, and the obtained ordered microporous Carbon has low quality and an unobvious ordered structure. The documents "A porous brick-like structure of zeolite-structured Carbon" (Carbon, Volume 47, Issue 5, April 2009, Pages 1220-The conditions of vapor deposition are still harsh, the required temperature is as high as 700 ℃, and the microporous carbon prepared by the method under the high-temperature condition is easy to form non-catalytic deposition on the outer surface of the molecular sieve, and can generate early deposition of carbon in the pore channels of the molecular sieve to cause pore channel blockage, thereby greatly influencing the preparation of high-quality ordered microporous carbon. The documents "Lanthanum-catalyzed synthesis of microporosius 3D graphene-lithium carboxylate" (Nature Volume 535, Pages 131. about. 135(2016)), "facility large-scale synthesis of needle-dimensional graphene-lithium ordered microporosius carbide via ethylene carboxylate synthesis in CaX zeolite template" (Carbon, Volume 118, July 2017, Pages 517. about. 523) are prepared by introducing La into the cavities of a molecular sieve3+Ion and Ca2+The method for preparing the microporous carbon material by carbon deposition of carbon source gas under ion catalysis solves the problems of carbon deposition on the surface of a molecular sieve and pore channel blockage, but the preparation process still needs high temperature of 900 ℃, the traditional preparation method needs to be carried out under normal pressure, and the high temperature and normal pressure condition aggravate the sorting selectivity thermal decomposition of the carbon source to cause pore channel blockage and outer surface deposition, thereby reducing the quality of ordered microporous carbon.
In view of this, the invention introduces active sites in the molecular sieve template by using simple ion exchange, realizes the preparation of the ordered microporous carbon under the conditions of medium-low temperature and medium-low pressure with the temperature of 350-. The preparation method of the ordered microporous carbon material based on the invention has simple process flow and mild conditions, and the obtained ordered microporous carbon has accurate and uniform aperture and regular and ordered pore structure.
The invention content is as follows:
the invention provides a preparation method of ordered microporous carbon with precise pore diameter, which is characterized by comprising the following steps: introduction of active site Zn in molecular sieve2+The preparation of the ordered microporous carbon is realized by using chemical vapor deposition under the conditions of medium and low pressure and medium and low temperature with the pressure of 200-. Simple preparation process and mild conditionsThe prepared ordered micropore carbon has large specific surface area, rich micropore structure, uniform pore diameter and regular and ordered pore channels.
In order to realize microporous carbon with the characteristics, the preparation method adopted by the invention is as follows:
step 1: ion exchange: dispersing molecular sieves to Zn (NO)3)2Heating and stirring the solution, and filtering the solution to obtain Zn2+Exchanged molecular sieves.
Step 2: chemical vapor deposition: zn is added2+The exchanged molecular sieve is placed in a tubular furnace, mixed gas of nitrogen and acetylene is introduced, and acetylene decomposition and carbon deposition are realized through a chemical vapor deposition process.
And step 3: etching: and (3) etching and dissolving the sample treated in the step (2) in a mixed solution of hydrofluoric acid and hydrochloric acid, and removing the molecular sieve template to obtain the ordered microporous carbon with the precise pore diameter.
The molecular sieve selected in step 1 is microporous molecular sieve, optionally Y-type molecular sieve, and Zn is introduced2+The active site agent is Zn (NO)3)2。
In the chemical vapor deposition process in the step 2, the pressure of carbon growth is 200-600 Torr.
In the chemical vapor deposition process in the step 2, the temperature of carbon growth is 350-550 ℃.
The invention has the beneficial effects that: a method for preparing ordered microporous carbon with precise pore diameter is provided. The method can be carried out under the conditions of medium and low temperature and medium and low pressure, the preparation process is simple in process and mild in condition, the prepared ordered microporous carbon material is large in specific surface area, rich in microporous structure, uniform in pore diameter and regular and ordered in pore channel.
Description of the drawings:
FIG. 1 is an X-ray diffraction pattern of an ordered microporous carbon material prepared according to the preparation method of the present invention. As can be seen from the figure, the prepared ordered microporous carbon structure has an obvious and clear diffraction peak at the 2 theta (6.5 degrees), the diffraction peak is obtained by diffraction of a (111) crystal face of the Y-type molecular sieve, the occurrence of the diffraction peak indicates that the carbon material retains the ordered microporous structure of the Y-type molecular sieve, and the size of the obtained ordered micropores is 1.36nm according to the calculation of the Sheble formula.
FIG. 2 is a nitrogen adsorption curve of an ordered microporous carbon material prepared according to the preparation method of the present invention. As can be seen from the figure, the adsorption-desorption isotherm is type I, the obtained material can be judged to be a typical microporous material from the characteristics of rapid increase of the adsorption quantity in a low-pressure region, gradual increase of a medium-high pressure region, a small adsorption-desorption hysteresis loop and the like, and the specific surface area calculated from the adsorption isotherm is as high as 2780m2 g–1。
FIG. 3 is a pore size distribution diagram of an ordered microporous carbon material prepared according to the preparation method of the present invention. As can be seen from the figure, the pore size distribution of the obtained carbon material is in the range of 1.1 to 1.4nm, indicating its microporous character, while a narrower pore size distribution indicates its precise, uniform pore size.
FIG. 4 is a scanning electron microscope image of an ordered microporous carbon material prepared according to the preparation method of the present invention. As can be seen from the figure, the carbon particles have sharp angular boundaries and smooth surfaces, indicating that non-catalytic deposition of carbon on the particle surfaces is effectively inhibited.
FIG. 5 is a transmission electron microscope image of an ordered microporous carbon material prepared according to the preparation method of the present invention. As can be seen from the figure, the obtained carbon material has a regular periodic structure, and the average distance of the periodic structure is read to be 1.3nm from the figure, indicating a highly ordered microporous structure.
The specific implementation method comprises the following steps:
the following examples illustrate the specific practice of the present invention in detail, with the following steps:
(1)3.3g NaY type molecular sieves (CVB100, Si/Al 2.6) in 100ml of 0.5M Zn (NO)3)2Stirring in 80 deg.C water bath for 3 hr, filtering, washing with distilled water, repeating the above steps to complete the second ion exchange, drying the obtained solid in 60 deg.C oven for 12 hr to obtain Zn2+Ion exchanged molecular sieves.
(2) And placing the dried molecular sieve template in a tubular furnace, introducing nitrogen to exhaust air, heating to 450 ℃ at the speed of 5 ℃/min, introducing 80sccm nitrogen and 20sccm acetylene at the volume flow rate respectively, preserving heat for 3h, finishing the introduction of acetylene gas after carbon growth, heating to 850 ℃ at the speed of 5 ℃/min, preserving heat for 2h, stopping heating, and stopping the introduction of nitrogen after cooling to room temperature to obtain a grown sample. The pressure during the whole reaction process is controlled at 500 Toor.
(3) Dispersing a sample obtained after carbon growth in 1L of a mixed solution of 0.3M hydrofluoric acid and 0.15M hydrochloric acid, magnetically stirring for 3 hours, etching and dissolving a molecular sieve, filtering, washing, repeating the above operations, washing the etched sample to be neutral after finishing the second etching, and drying in an oven at 60 ℃ for 6 hours to obtain the prepared ordered microporous carbon with the precise pore diameter.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; the present invention can be smoothly implemented by those skilled in the art in the light of the accompanying drawings and the above description; however, those skilled in the art should, upon attaining an understanding of the present disclosure, appreciate that many changes, modifications, and equivalents may be made to the invention without departing from the spirit and scope of the invention; meanwhile, any changes, modifications, evolutions, etc. of the equivalent changes made to the above embodiments according to the implementation technology of the present invention are within the protection scope of the technical solution of the present invention.
Claims (4)
1. A method for preparing ordered microporous carbon with precise pore diameter is characterized by comprising the following steps: taking a molecular sieve with an ordered microporous structure as a template, and introducing active site Zn into the molecular sieve through cation exchange2+The method comprises the following steps of utilizing chemical vapor deposition technology to realize decomposition of a carbon source and deposition of carbon under the conditions of medium and low temperature and medium and low pressure, and finally removing a molecular sieve template by etching to obtain ordered microporous carbon with precise pore diameter:
step 1: dispersing molecular sieves to Zn (NO)3)2Heating and stirring the solution, and filtering the solution to obtain Zn2+An exchanged molecular sieve;
step 2: zn is added2+The exchanged molecular sieve is placed in a tubular furnace, mixed gas of nitrogen and acetylene is introduced, and carbon growth is carried out by utilizing chemical vapor deposition.
And step 3: and (3) etching and dissolving the sample treated in the step (2) in a mixed solution of hydrofluoric acid and hydrochloric acid, and removing the molecular sieve template to obtain the ordered microporous carbon with the precise pore diameter.
2. The method for preparing ordered microporous carbon with a precise pore size according to claim 1, wherein the active site introduced by cation exchange in step 1 is Zn2+。
3. The method for preparing ordered microporous carbon with precise pore size as claimed in claim 1, wherein the pressure required for carbon growth in step 2 is 200-600 Torr.
4. The method for preparing ordered microporous carbon with precise pore size as claimed in claim 1, wherein the temperature required for carbon growth in step 2 is 350-550 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1815665A (en) * | 2004-11-15 | 2006-08-09 | 三星Sdi株式会社 | Carbon-nano tube,electron sending source,electron sending device and producing method |
| CN107427812A (en) * | 2014-10-14 | 2017-12-01 | 沙特***石油公司 | Pass through the synthesizing ordered microporous carbon of chemical vapour deposition technique |
| CN112299388A (en) * | 2020-09-21 | 2021-02-02 | 中国科学院金属研究所 | Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1815665A (en) * | 2004-11-15 | 2006-08-09 | 三星Sdi株式会社 | Carbon-nano tube,electron sending source,electron sending device and producing method |
| CN107427812A (en) * | 2014-10-14 | 2017-12-01 | 沙特***石油公司 | Pass through the synthesizing ordered microporous carbon of chemical vapour deposition technique |
| CN112299388A (en) * | 2020-09-21 | 2021-02-02 | 中国科学院金属研究所 | Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor |
Non-Patent Citations (1)
| Title |
|---|
| WEI ZHAO 等: "The Synthesis of Carbon Nanotubes (CNTs) by Catalytic CVD using a Fe/Co-Supported Zeolite Template", 《ELECTRONIC MATERIALS LETTERS》 * |
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