CN112897505B - Preparation method of mesoporous carbon material - Google Patents
Preparation method of mesoporous carbon material Download PDFInfo
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- CN112897505B CN112897505B CN202110317875.4A CN202110317875A CN112897505B CN 112897505 B CN112897505 B CN 112897505B CN 202110317875 A CN202110317875 A CN 202110317875A CN 112897505 B CN112897505 B CN 112897505B
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Abstract
The invention relates to a preparation method of a mesoporous carbon material. The method comprises the following steps: preparing a phenolic resin precursor solution; (2) blending the precursor and a template agent; (3) curing; (4) carbonizing; and (5) post-treatment. Mixing the phenolic resin precursor and a template agent according to a certain proportion, curing, placing the mixture in an inert gas atmosphere, carrying out temperature programming, removing the template agent, carbonizing the phenolic resin, crushing a carbonized product, cleaning, removing impurities, filtering and drying to obtain the mesoporous carbon material. The template agent used by the invention has wide source, low price and easy obtaining, the preparation method is simple, and the prepared mesoporous carbon has the advantages of controllable aperture size, uniform pore channel, stable structure and the like, and can be widely applied to the fields of energy storage, catalysis, adsorption and the like.
Description
Technical Field
The invention belongs to the field of carbon materials, and relates to a preparation method of a mesoporous carbon material.
Background
In recent years, there has been much interest in the research of carbon nanomaterials and their application in industry. Carbon nanomaterials are excellent in optical properties, hardness, corrosion resistance, heat resistance, chemical resistance, radiation resistance, electrical insulation properties, electrical conductivity, surface and interface properties, and the like, and thus carbon nanomaterials are widely used in the fields of hydrogen storage, secondary batteries, supercapacitors, sensors, catalyst carriers, and the like.
The porous carbon material is a carbon material with various pore channel structures. As specified by the international union of pure applied chemistry: the pores with the diameter below 0.8nm are submicron pores, the pores with the diameter between 0.8 and 2nm are called micropores, the pores with the diameter between 2 and 50nm are called mesopores, and the pores with the diameter more than 50nm are called macropores. Therefore, porous materials can be classified into microporous materials, mesoporous materials, and macroporous materials according to the size of the pore diameter. The method for preparing the mesoporous carbon material comprises an organic gel carbonization method, a catalytic gasification method and a template method. However, the organogel carbonization method and the catalytic gasification method are not capable of precisely controlling the pore structure, size and pore size distribution, and thus are less used in the method for synthesizing mesoporous carbon materials. The template method can accurately control the pore size and the distribution thereof, and can synthesize the mesoporous carbon material with a regular pore channel structure, so the template method is widely applied to the preparation of the mesoporous carbon material in recent years.
The template method is further classified into a hard template method and a soft template method. The hard template method is that a pre-prepared mesoporous silicon molecular sieve with a certain specific pore channel structure is used as a template, a carbon precursor is filled in the pore channel of the molecular sieve, and then the silicon template is removed by sodium hydroxide or hydrofluoric acid to obtain a mesoporous carbon material; the soft template method is characterized in that a surfactant is directly used as a structure directing agent, the structure directing agent is combined with a carbon precursor through the action of hydrogen bonds, the original positions occupied by the surfactant are changed into mesopores through the crosslinking and carbonization processes, and the carbon precursor is carbonized to form a porous framework. Although the template method has the advantage of precisely controlling the pore size and pore distribution, it also has certain disadvantages. The hard template method usually needs to synthesize a hard template first and remove the template by corrosion finally when preparing the mesoporous carbon material, and the method has serious consumption on the hard template and extremely high cost. In addition, the hard template method has higher requirements on carbon materials, for example, the intermiscibility between the precursor and the hard template is good, and a structure for supporting the pore channels mutually is required, so that the carbon material structure is prevented from being dislocated after the template is washed away. Compared with a hard template method, the soft template method does not need the participation of a silicon source and the removal of a silicon template, avoids the complexity of steps and the waste of resources, but generally needs a block copolymer with high price as a soft template, has high template agent dosage, can form the phase distribution required by the mesoporous material only under specific conditions, and has high requirements on the preparation process. Therefore, it is very important to explore a method for preparing mesoporous carbon materials with simple process and accurate synthesis.
Cellulose is the most abundant natural renewable resource on the earth, and is a biopolymer which is widely distributed in nature. The nano-cellulose is a nano-cellulose obtained by mechanical action or hydrolysis of natural cellulose, and mainly comprises cellulose nanocrystals and cellulose nano-fibers. The nano-cellulose generally has a higher length-diameter ratio, and the diameter distribution of the nano-cellulose is generally distributed in the range of 3-50nm and accords with the diameter range of mesopores. In addition, the thermal degradation temperature of the nano-cellulose is generally lower than that of the carbon material, so that the mesoporous carbon material can be conveniently synthesized by taking the nano-cellulose as a template agent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing a mesoporous carbon material by using nanocellulose as a template, which is simple and reliable, can accurately control the size and distribution of the pore diameter of the carbon material according to the size and the using amount of the template agent, and provides a new, simple and convenient method for preparing the mesoporous carbon material.
The technical scheme adopted by the invention is as follows:
the preparation method of the mesoporous carbon material is characterized by comprising the following steps:
(1) Preparing a phenolic resin precursor solution: mixing phenol, a formaldehyde solution and an alkali solution, heating to a reaction temperature, reacting for a period of time, and cooling to room temperature to obtain a phenolic resin precursor solution;
(2) Blending the precursor and the template: blending the phenolic resin precursor solution obtained in the step (1) with a template agent, and carrying out ultrasonic treatment for a period of time;
(3) And (3) curing: heating the mixture obtained in the step (2) to a curing temperature, and curing for a period of time;
(4) Carbonizing: carrying out programmed heating carbonization on the cured product obtained in the step (3) for a period of time in an inert gas atmosphere;
(5) And (3) post-treatment: crushing the carbonized product obtained in the step (4), cleaning, removing impurities, filtering and drying to obtain a mesoporous carbon material;
the alkali solution in the step (1) is at least one of a sodium hydroxide solution, a potassium hydroxide solution and ammonia water; the phenol, formaldehyde solution and alkali solution have the following components: formaldehyde: the molar ratio of the alkali is 1:0.5 to 3:0.1 to 0.5; the reaction temperature is 50-100 ℃; the reaction time is 0.5 to 4 hours;
the template agent in the step (2) is at least one of cellulose nanocrystalline and cellulose nanofiber; the mass ratio of the phenolic resin precursor solution to the template agent is 1:0.05 to 2, and the ultrasonic time is 5 to 60 minutes;
the curing temperature in the step (3) is 120-180 ℃; the reaction time is 5 to 60 minutes;
the inert gas in the step (4) is at least one of nitrogen and argon; the temperature programming is to heat up to 300-400 ℃ at the speed of 1-10 ℃/min, keep the temperature for 0.5-2 hours, continue to heat up to 600-900 ℃ at the speed of 1-10 ℃/min, keep the temperature for 0.5-4 hours, and then naturally cool to room temperature.
The invention has the following remarkable advantages:
compared with other mesoporous carbon material preparation methods, the operation method is simple and easy to implement and low in production cost, and the prepared mesoporous carbon material has the advantages of controllable pore size, uniform pore channel, stable structure and the like.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
Example 1
(1) Preparing a phenolic resin precursor solution: weighing 9.4 g of phenol, 16.2 g of formaldehyde solution and 2.8 g of 20% potassium hydroxide solution, mixing, heating in a constant-temperature water bath kettle at 70 ℃, reacting for 1 hour, and cooling to room temperature to obtain the phenolic resin precursor solution.
(2) Blending the precursor and the template: weighing 4.75 g of the phenolic resin prepared in the step (1) and 0.25 g of the cellulose nanocrystal, mixing, and carrying out ultrasonic treatment for 5 minutes.
(3) And (3) curing: heating the product obtained in the step (2) to 150 ℃, and curing for 1 hour.
(4) Carbonizing: and (4) carrying out programmed heating carbonization on the cured product obtained in the step (3) for a period of time in the nitrogen atmosphere, wherein the programmed heating is carried out at the temperature of 3 ℃/min to 300 ℃, the temperature is kept for 1 hour, the temperature is continuously raised to 700 ℃ at the temperature of 2 ℃/min, the temperature is kept for 2 hours, and then the temperature is naturally reduced to the room temperature.
(5) And (3) post-treatment: and (4) crushing, cleaning, removing impurities, filtering and drying the carbonized product obtained in the step (4) to obtain the mesoporous carbon material.
Example 2
(1) Preparing a phenolic resin precursor solution: weighing 9.4 g of phenol, 11.9 g of formaldehyde solution and 2.8 g of 20% potassium hydroxide solution, mixing, heating in a constant-temperature water bath kettle at 70 ℃, reacting for 1 hour, and cooling to room temperature to obtain the phenolic resin precursor solution.
(2) Blending the precursor and the template: weighing 4.5 g of phenolic resin prepared in the step (1) and 0.5 g of cellulose nanocrystalline, mixing, and carrying out ultrasonic treatment for 15 minutes.
(3) And (3) curing: heating the product obtained in the step (2) to 160 ℃, and curing for 1 hour.
(4) Carbonizing: and (4) carrying out programmed heating carbonization on the cured product obtained in the step (3) for a period of time in the nitrogen atmosphere, wherein the programmed heating is carried out at the temperature of 3 ℃/min to 350 ℃, the temperature is kept for 1 hour, the temperature is continuously raised to 750 ℃ at the temperature of 2 ℃/min, the temperature is kept for 2 hours, and then the temperature is naturally reduced to the room temperature.
(5) And (3) post-treatment: and (4) crushing, cleaning, removing impurities, filtering and drying the carbonized product obtained in the step (4) to obtain the mesoporous carbon material.
Example 3
(1) Preparing a phenolic resin precursor solution: weighing 9.4 g of phenol, 17.8 g of formaldehyde solution and 2.8 g of 20% potassium hydroxide solution, mixing, heating in a constant-temperature water bath kettle at 80 ℃, reacting for 0.5 hour, and cooling to room temperature to obtain the phenolic resin precursor solution.
(2) Blending the precursor and the template: weighing 4 g of the phenolic resin prepared in the step (1) and 1 g of the cellulose nanocrystal, mixing, and carrying out ultrasonic treatment for 30 minutes.
(3) And (3) curing: heating the product obtained in the step (2) to 170 ℃ and curing for 1 hour.
(4) Carbonizing: and (4) carrying out programmed heating carbonization on the cured product obtained in the step (3) in the nitrogen atmosphere for a period of time, wherein the programmed heating is carried out at the temperature of 5 ℃/min to 400 ℃, the temperature is kept for 1.5 hours, the temperature is continuously raised to 800 ℃ at the temperature of 5 ℃/min, the temperature is kept for 2 hours, and then the temperature is naturally reduced to the room temperature.
(5) And (3) post-treatment: and (4) crushing, cleaning, removing impurities, filtering and drying the carbonized product obtained in the step (4) to obtain the mesoporous carbon material.
Example 4
(1) Preparing a phenolic resin precursor solution: weighing 9.4 g of phenol, 16.2 g of formaldehyde solution and 14 g of 20% sodium hydroxide solution, mixing, heating in a constant-temperature water bath kettle at 70 ℃, reacting for 1 hour, and cooling to room temperature to obtain the phenolic resin precursor solution.
(2) Blending the precursor and the template: weighing 4.75 g of the phenolic resin prepared in the step (1) and 0.25 g of cellulose nano-fiber, mixing, and carrying out ultrasonic treatment for 40 minutes.
(3) And (3) curing: heating the product obtained in the step (2) to 150 ℃, and curing for 1 hour.
(4) Carbonizing: and (4) carrying out programmed heating carbonization on the cured product obtained in the step (3) for a period of time in the nitrogen atmosphere, wherein the programmed heating is carried out at the temperature of 3 ℃/min to 350 ℃, the temperature is kept for 1 hour, the temperature is continuously raised to 700 ℃ at the temperature of 2 ℃/min, the temperature is kept for 2 hours, and then the temperature is naturally reduced to the room temperature.
(5) And (3) post-treatment: and (4) crushing, cleaning, removing impurities, filtering and drying the carbonized product obtained in the step (4) to obtain the mesoporous carbon material.
Example 5
(1) Preparing a phenolic resin precursor solution: weighing 9.4 g of phenol, 16.2 g of formaldehyde solution and 2.8 g of ammonia water solution, mixing, heating in a constant-temperature water bath kettle at 70 ℃, reacting for 1 hour, and cooling to room temperature to obtain the phenolic resin precursor solution.
(2) Blending the precursor and the template: weighing 4 g of phenolic resin prepared in the step (1) and 1 g of cellulose nano-fiber, mixing, and carrying out ultrasonic treatment for 60 minutes.
(3) And (3) curing: heating the product obtained in the step (2) to 150 ℃, and curing for 1 hour.
(4) Carbonizing: and (4) carrying out programmed heating carbonization on the cured product obtained in the step (3) in the nitrogen atmosphere for a period of time, wherein the programmed heating is carried out at the temperature of 3 ℃/min to 350 ℃, the temperature is kept for 1 hour, the temperature is continuously raised to 700 ℃ at the temperature of 2 ℃/min, the temperature is kept for 2 hours, and then the temperature is naturally reduced to the room temperature.
(5) And (3) post-treatment: and (4) crushing, cleaning, removing impurities, filtering and drying the carbonized product obtained in the step (4) to obtain the mesoporous carbon material.
Claims (1)
1. The preparation method of the mesoporous carbon material is characterized by comprising the following steps:
(1) Preparing a phenolic resin precursor solution: mixing phenol, a formaldehyde solution and an alkali solution, heating to a reaction temperature, reacting for a period of time, and cooling to room temperature to obtain a phenolic resin precursor solution;
(2) Blending the precursor and the template: blending the phenolic resin precursor solution obtained in the step (1) with a template agent, and carrying out ultrasonic treatment for a period of time;
(3) And (3) curing: heating the mixture obtained in the step (2) to a curing temperature, and curing for a period of time;
(4) Carbonizing: carrying out programmed heating carbonization on the cured product obtained in the step (3) for a period of time in an inert gas atmosphere;
(5) And (3) post-treatment: crushing the carbonized product obtained in the step (4), cleaning, removing impurities, filtering and drying to obtain a mesoporous carbon material;
the alkali solution in the step (1) is at least one of a sodium hydroxide solution, a potassium hydroxide solution and ammonia water; the phenol, formaldehyde solution and alkali solution have the following components: formaldehyde: the molar ratio of the alkali is 1:0.5 to 3:0.1 to 0.5; the reaction temperature is 50-100 ℃; the reaction time is 0.5 to 4 hours;
the template agent in the step (2) is at least one of cellulose nanocrystalline and cellulose nanofiber; the mass ratio of the phenolic resin precursor solution to the template is 1:0.05 to 0.25, and the ultrasonic time is 5 to 60 minutes;
the curing temperature in the step (3) is 120-180 ℃; the reaction time is 5 to 60 minutes;
the inert gas in the step (4) is at least one of nitrogen and argon; the temperature programming is to heat up to 300-400 ℃ at the speed of 1-10 ℃/min, keep the temperature for 0.5-2 hours, continue to heat up to 600-900 ℃ at the speed of 1-10 ℃/min, keep the temperature for 0.5-4 hours, and then naturally cool to room temperature.
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| CN101367514A (en) * | 2007-08-17 | 2009-02-18 | 北京化工大学 | Method for preparing ordered mesoporous carbon with organic mould plate method |
| CN102190316B (en) * | 2010-03-03 | 2013-01-09 | 中国石油化工股份有限公司 | Method for synthesizing mesoporous mordenite |
| US20140227325A1 (en) * | 2013-02-13 | 2014-08-14 | Ut-Battelle, Llc | Lignin-derived porous carbon composition, methods of preparation, and use thereof |
| CN103803524B (en) * | 2014-01-15 | 2016-06-08 | 河海大学 | It is a kind of that to adopt industrial phenolic aldehyde resin be the method that raw material prepares ordered mesoporous carbon |
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| US10017391B2 (en) * | 2015-04-23 | 2018-07-10 | Ut-Battelle, Llc | Direct polymer templating synthesis of mesoporous carbon |
| CN109021297A (en) * | 2018-06-21 | 2018-12-18 | 常州大学 | A kind of preparation method and applications of phenol-formaldehyde resin modified cellulose composite membrane |
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