CN113336223A - Synthesis method of mesoporous carbon material - Google Patents
Synthesis method of mesoporous carbon material Download PDFInfo
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- CN113336223A CN113336223A CN202110589077.7A CN202110589077A CN113336223A CN 113336223 A CN113336223 A CN 113336223A CN 202110589077 A CN202110589077 A CN 202110589077A CN 113336223 A CN113336223 A CN 113336223A
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Abstract
The invention provides a preparation method of a mesoporous carbon material. Mixing saccharide material and ZnCl2Uniformly mixing eutectic salt according to the mass ratio of 0.25-10: 1: 0-1, and carrying out hydrothermal treatment on the obtained substance at 150-250 ℃ in a hydrothermal kettle for 8-36 hours; and (3) placing the obtained substance in a nitrogen atmosphere, activating for 1-6 hours at 450-800 ℃, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying at 70-100 ℃ to obtain the mesoporous carbon material. The specific surface area of the obtained mesoporous carbon can reach 1800m2The pore volume can reach 2.50cm3(ii) in terms of/g. The method takes biomass and eutectic salt as raw materials, adopts an ion hydrothermal method to synthesize the mesoporous carbon material, has mild conditions and simple and easy operation steps, can recycle the saline water generated in the water washing process after concentration, and has low production cost.
Description
Technical Field
The invention relates to a method for synthesizing a mesoporous carbon material by an ionic hydrothermal method, and belongs to the technical field of new material synthesis.
Background
The mesoporous carbon material has the structural advantages of large specific surface area, uniform aperture, ordered pore distribution and the like, has potential huge application value in the fields of catalysis, separation, electrode material preparation and the like, and has become a hotspot of material science research. In the prior art, many methods for preparing mesoporous carbon materials mainly include: catalytic activation, organosol-gel, hard-template, and soft-template methods, among others.
The catalytic activation method is to synthesize mesoporous carbon by using the catalytic action of metals and compounds thereof on carbon gasification. Patent CN102774822 uses ZnO and organic polymer such as polyacrylamide capable of dispersing ZnO ions, after carbonizing the polymer at high temperature, using organic acid or inorganic acid or alkali to remove ZnO to generate mesopores, the pore size of which is completely consistent with the size of ZnO particles. The mesoporous carbon prepared by the method is difficult to accurately control the structure, the size and the pore distribution of mesopores, and the problem of metal residue in a final product is serious because the catalyst is metal-containing salts.
Patent CN1821182A describes a method for preparing mesoporous carbon material by sol-gel method, which introduces organic polymer and silicon source into a surfactant self-assembly reaction system, and forms ordered mesoporous carbon material with high specific surface area and large space through the mutual competition, polymerization crosslinking and synergistic assembly between organic-organic, inorganic-inorganic and organic-inorganic. The mesoporous carbon prepared by the sol-gel method has wide pore size distribution, needs expensive and complicated supercritical drying equipment and is difficult to commercialize.
The hard template method is a reverse phase synthesis method, and is characterized in that a material with a special pore structure is selected as a template, a target material or a precursor is introduced and reacts in pores of the template material, and after the reaction is finished, the hard template is removed by hydrofluoric acid and the like to obtain the reverse phase mesoporous carbon material. The method utilizes the confinement effect of a template material to achieve the purpose of regulating and controlling physical and chemical reactions in the preparation process, and mostly adopts mesoporous silica as a hard template. The method has complex process, is time-consuming and uneconomical, and the reversed phase synthesized mesoporous carbon material has relatively poor stability, thereby limiting the large-scale production and application thereof.
The soft template method generally selects organic surfactant molecules with amphipathy as templates, assembles a regular mesostructure through the interaction between block copolymers and the surfactants, and then removes the template agent through high-temperature carbonization to obtain the mesoporous carbon material. In patent CN101486459B, resorcinol and formaldehyde are adopted to form oligomeric resol resin, and triblock copolymer F127 is subjected to low-temperature hydrothermal treatment to form a resol resin/F127 compound under the weak acid condition, and the massive ordered mesoporous carbon material is formed after aging, washing, drying and carbonization. The method has simple preparation process, is easy to regulate and control the aperture size, the pore structure and the like, but has high cost of used raw materials, is toxic, and causes potential harm to the environment and human bodies. Therefore, the method has practical significance for finding a green synthesis method which is cheap, low in toxicity, simple, convenient and quick.
Patent CN107827095A describes a method for preparing mesoporous carbon material by eutectic salt ion hydrothermal method, which comprises mixing saccharide substance and ZnCl2And uniformly mixing the eutectic salt and water according to a certain proportion, carrying out ultrasonic treatment, carrying out hydrothermal treatment on the obtained substance in a hydrothermal kettle, drying, then placing the obtained substance in a nitrogen atmosphere for high-temperature activation, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying to obtain the mesoporous carbon material. The raw materials adopted by the method are easy to obtain, but the specific surface area and the pore volume of the prepared mesoporous carbon material are small, ultrasonic treatment is needed in the process, the primary product needs a separate drying process, and the hydrothermal reaction temperature and the activation reaction temperature are high.
Aiming at the defects of the methods, the invention uses the eutectic salt as the solvent, the template and the catalyst, adopts the ion hydrothermal synthesis method to prepare the mesoporous carbon material, has simpler process and milder conditions, can recycle the eutectic salt, and has high specific surface area and large pore volume of the obtained mesoporous carbon material.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a mesoporous carbon material. The method takes sugar as a precursor of a carbon source, ZnCl2The eutectic salt is used as template agent, catalyst and solvent, and is hydrothermally treated at high temperatureThe mesoporous carbon material with high specific surface area and large pore volume is obtained by activation, the specific surface area of the obtained mesoporous carbon is higher, the reaction conditions are milder, and the preparation cost is effectively reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
(1) mixing saccharide material and ZnCl2The eutectic salt and water are uniformly mixed according to the mass ratio of 0.25-10: 1: 0-2, preferably 1-4: 1: 0.2-1.
(2) And (2) treating the substance obtained in the step (1) in a hydrothermal kettle at 150-250 ℃, preferably 150-210 ℃ for 8-36 hours, preferably 12-24 hours.
(3) And (3) placing the substance obtained in the step (2) in a nitrogen atmosphere, activating at a high temperature of 450-800 ℃, preferably 450-650 ℃ for 1-6 hours, preferably 2-4 hours, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying at 70-100 ℃ to obtain the mesoporous carbon material.
The saccharide substance in the step (1) is one or a mixture of sucrose, glucose or fructose.
ZnCl in the step (1)2The second component of the eutectic salt is LiCl, NaCl and FeCl3、MgCl2、CaCl2、BaCl2One of urea and choline chloride, ZnCl2The molar ratio of the second component to the second component is 1.0: 0.25-1.5, and the preferred molar ratio is 1.0: 0.5-1.0.
And (4) performing high-temperature activation in the step (3) by adopting temperature programming, wherein the temperature raising rate is 1-10 ℃/min.
And (4) the high-temperature activation time in the step (3) is 2-4 hours.
The specific surface area of the obtained mesoporous carbon material can reach 1800m at most2The pore volume can reach 2.50cm3/g。
The invention is characterized in that: using a saccharide as a carbon source precursor, ZnCl2The eutectic salt is used as a template agent, and is subjected to hydrothermal treatment at 150-250 ℃ and high-temperature activation at 450-800 ℃ to synthesize the mesoporous carbon material. The mesoporous carbon material prepared by the preparation method has high specific surface area and large pore volume, does not use expensive organic additives, has simple and easy operation steps, and is generated by water washingThe salt solution can be recycled after being concentrated, and the production cost is low.
The method adopts cheap and easily-obtained green environment-friendly raw materials, utilizes the eutectic salt as a solvent, a template agent and a catalyst, and adopts an ion hydrothermal method to prepare the mesoporous carbon material, and the obtained mesoporous carbon not only has high specific surface area and large pore volume, but also has mild hydrothermal reaction temperature and activation temperature, simple process, recyclable eutectic salt and economic and industrial application value.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples.
Example 1:
25.24g of glucose, 2.52g of ZnCl2Mixing the obtained mixture with co-molten salt formed by 0.20g of LiCl and 5.04g of water uniformly, treating the obtained substance in a hydrothermal kettle at 250 ℃ for 8 hours, placing the obtained substance in a nitrogen atmosphere, activating at high temperature for 6 hours at 500 ℃ and at the heating rate of 5 ℃/min, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying at 100 ℃ to obtain the mesoporous carbon material 1.
Example 2:
2.04g of fructose, 8.178g of ZnCl2And 2.850g MgCl2And uniformly mixing the formed eutectic salt, treating the obtained substance in a hydrothermal kettle at 150 ℃ for 36 hours, placing the obtained substance in a nitrogen atmosphere, activating at a high temperature of 800 ℃ and at a heating rate of 1 ℃/min for 1 hour, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying at 70 ℃ to obtain the mesoporous carbon material 2.
Example 3: 9.66g of sucrose, 8.18g of ZnCl2And co-molten salt formed by 8.37g of choline chloride and 1.31g of water are uniformly mixed, the obtained substance is treated in a hydrothermal kettle at 180 ℃ for 12 hours, the obtained substance is placed in a nitrogen atmosphere, high-temperature activation is carried out for 6 hours at 450 ℃ and at the heating rate of 10 ℃/min, after cooling to room temperature, the obtained black solid substance is washed by water until the pH value is neutral, and the mesoporous carbon material 3 is obtained after drying at 80 ℃.
Example 4:
mixing 2.35g glucose, 2.2 g6g fructose, 7.18g ZnCl2And (2) uniformly mixing the fused salt formed by the urea 5.40g and water 3.12g, treating the obtained substance in a hydrothermal kettle at 200 ℃ for 16h, placing the obtained substance in a nitrogen atmosphere, activating at 550 ℃ and at the heating rate of 5 ℃/min for 4h at high temperature, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying at 90 ℃ to obtain the mesoporous carbon material 4.
Example 5:
4.35g of sucrose, 7.26g of fructose and 8.15g of ZnCl2And 3.20g BaCl2And uniformly mixing the formed eutectic salt and 2.15g of water, treating the obtained substance in a hydrothermal kettle at 160 ℃ for 24 hours, placing the obtained substance in a nitrogen atmosphere, activating at 480 ℃ and at a heating rate of 5 ℃/min for 6 hours at a high temperature, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying at 90 ℃ to obtain the mesoporous carbon material 5.
Example 6:
11.36g of glucose, 7.26g of sucrose and 5.18g of ZnCl2And 3.40g CaCl2And (3) uniformly mixing the formed eutectic salt and 3.18g of water, treating the obtained substance in a hydrothermal kettle at 190 ℃ for 12 hours, placing the obtained substance in a nitrogen atmosphere, activating at a high temperature of 650 ℃ and at a heating rate of 5 ℃/min for 2 hours, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying at 80 ℃ to obtain the mesoporous carbon material 6.
Example 7:
mixing 9.36g glucose, 9.36g sucrose, 7.18g ZnCl2And co-molten salt formed by 5.40g of NaCl and 1.15g of water are uniformly mixed, the obtained substance is treated in a hydrothermal kettle for 18 hours at the temperature of 170 ℃, the obtained substance is placed in a nitrogen atmosphere, high-temperature activation is carried out for 5 hours at the temperature of 550 ℃ and the heating rate of 2 ℃/min, after cooling to room temperature, the obtained black solid substance is washed by water until the pH value is neutral, and the mesoporous carbon material 7 is obtained after drying at the temperature of 100 ℃.
Example 8:
mixing 8.38g glucose, 6.55g sucrose, 4.45g ZnCl2And 3.87g FeCl3The resulting eutectic salt and 2.36g of water were mixed uniformly to obtain a mixtureTreating the substance in a hydrothermal kettle at 210 ℃ for 15h, placing the obtained substance in a nitrogen atmosphere, activating at 700 ℃ and at a heating rate of 1 ℃/min for 2h at a high temperature, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying at 100 ℃ to obtain the mesoporous carbon material 8.
Example 9:
a concentrated solution (containing 5.43g of ZnCl) obtained by evaporating 7.18g of glucose, 4.56g of sucrose and the recovered salt solution was concentrated2、2.35g NaCl、H2O8.54 g), treating the obtained substance in a hydrothermal kettle at 170 ℃ for 15h, placing the obtained substance in a nitrogen atmosphere, activating at 700 ℃ and at the heating rate of 1 ℃/min for 6h, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying at 100 ℃ to obtain the mesoporous carbon material 9.
The characterization results of the obtained mesoporous carbon material are shown in table 1:
TABLE 1 characterization results of the mesoporous carbon materials synthesized in the examples
As can be seen from the above examples, the present invention uses a saccharide as a carbon source precursor, ZnCl2The eutectic salt is used as a template agent, the mesoporous carbon material is prepared by adopting an ion hydrothermal synthesis method, the process is simpler, the conditions are milder, the eutectic salt can be recycled, the cost is low, and the obtained mesoporous carbon material has high specific surface area and large pore volume. Solves the problems of complex process, high energy consumption and cost, small specific surface area and pore volume of the prepared mesoporous carbon material and the like in the prior art.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. A method for synthesizing a mesoporous carbon material is characterized by comprising the following steps:
(1) mixing saccharide material and ZnCl2Uniformly mixing the eutectic salt and water according to the mass ratio of 0.25-10: 1: 0-2;
(2) treating the substance obtained in the step (1) in a hydrothermal kettle at the temperature of 150-250 ℃ for 8-36 hours;
(3) placing the substance obtained in the step (2) in a nitrogen atmosphere, activating at a high temperature of 450-800 ℃ for 1-6 hours, cooling to room temperature, washing the obtained black solid substance with water until the pH value is neutral, and drying at 70-100 ℃ to obtain a mesoporous carbon material;
the ZnCl2The second component of the eutectic salt is LiCl, NaCl and FeCl3、MgCl2、CaCl2、BaCl2One of urea and choline chloride, ZnCl2The molar ratio of the second component to the first component is 1.0: 0.25-1.5.
2. The method of claim 1, wherein: the glucide and ZnCl in the step (1)2The mass ratio of the eutectic salt to the water is 1-4: 1: 0.2-1.
3. The method of claim 1, wherein: the saccharide substance in the step (1) is one or a mixture of sucrose, glucose or fructose.
4. The method of claim 1, wherein: ZnCl2The molar ratio of the second component to the first component is 1.0: 0.5-1.0.
5. The method of claim 1, wherein: the hydrothermal treatment temperature in the step (2) is 170-210 ℃.
6. The method of claim 1, wherein: the hydrothermal treatment time in the step (2) is 12-24 hours.
7. The method of claim 1, wherein: the high-temperature activation temperature in the step (3) is 450-650 ℃.
8. The method of claim 1, wherein: and (4) the high-temperature activation heating rate in the step (3) is 1-10 ℃/min.
9. The method of claim 1, wherein: and (4) the high-temperature activation time in the step (3) is 2-4 hours.
10. The method of claim 1, wherein: the specific surface area of the obtained mesoporous carbon material can reach 1800m2The pore volume can reach 2.50cm3/g。
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