CN108854874B - Ultra-pure carbon aerogel with ultra-high specific surface area based on air-activated pore-forming and preparation method thereof - Google Patents
Ultra-pure carbon aerogel with ultra-high specific surface area based on air-activated pore-forming and preparation method thereof Download PDFInfo
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Abstract
The invention provides a carbon aerogel, which has a three-dimensional network structure formed by stacking carbon particles; the surface of the carbon particles has a microporous structure. The carbon aerogel prepared by the method has a uniform mesoporous structure, the three-dimensional sense of a three-dimensional network is strong, the spatial network structure is formed by stacking carbon pellets, the arrangement and connection among the pellets are very tight, and the whole structure is complete. The carbon aerogel not only has a mesoporous structure formed by stacking the carbon spheres, but also has a large number of microporous structures, so that the specific surface area of the carbon aerogel is greatly enhanced, and the BET specific surface area can reach 1200m2And about/g. The method adopts normal pressure drying to obtain the carbon aerogel, does not need a solvent exchange step, does not use an inorganic metal alkaline catalyst, realizes excellent biocompatibility, obtains the ultra-pure carbon aerogel, and has wide application in the fields of food-grade drug loading, catalyst loading, substance adsorbents, energy storage materials and the like.
Description
Technical Field
The invention relates to the technical field of aerogels, relates to a carbon aerogel and a preparation method thereof, and particularly relates to an ultra-high specific surface area ultra-pure carbon aerogel based on air-activated pore-forming and a preparation method thereof.
Background
Aerogel, also called xerogel, is a solid matter form, is a highly dispersed solid material with a nano-porous network structure formed by mutual coalescence of colloidal particles or high polymer molecules, and is filled with gaseous dispersion media in pores, has the performances of ultralow density, high specific surface area, high porosity, excellent heat insulation and the like, and has wide application in the aspects of super heat insulation materials, sound insulation materials, particle detectors, low-dielectric-constant aerogel films, inertia targeting materials and the like.
There are many kinds of aerogels, including silicon-based, carbon-based, sulfur-based, metal oxide-based or metal-based ones, among which carbon aerogel is a special condensed functional material, which is composed of many interconnected and uniform small particles, and has a definite mesoporous structure. The carbon aerogel has excellent properties and high porosityA ratio of (>95%) high specific surface area (>400m2The material has excellent characteristics of ultra-strong electrical conductivity, high thermal conductivity, sufficient corrosion resistance, low thermal expansion coefficient, ultra-low density and elasticity, and the excellent characteristics make the material become a functional material which is widely applied. The carbon aerogel has important application value and position in the fields of energy storage materials, catalyst carrier materials, harmful substance adsorption materials in the environment and the like. The characteristics of high specific surface area and high conductivity make the material popular in energy storage materials and devices, especially positive and negative electrode materials of lithium ion batteries and electrochemical supercapacitors. In addition, the carbon aerogel has the characteristics of high porosity, high specific surface area, no toxicity, no harm, good biocompatibility and the like, is widely applied and accepted in the aspects of adsorbent materials, catalyst carriers, drug carriers and the like, and has good application prospect and huge development potential.
Thus, there has been an increasing search in recent years for the preparation of carbon aerogels, where the Gloriarasines group utilized resorcinol, formaldehyde and melamine as the polymerization monomers, and sodium carbonate as the basic catalyst to promote the crosslinking reaction to give phenolic polymer gels. Then drying by adopting supercritical carbon dioxide and carrying out high-temperature carbonization treatment to obtain the carbon aerogel. Jun Li et al utilize resorcinol and formaldehyde solutions to produce phenolic polymers under the catalytic action of sodium carbonate, then perform solvent exchange with acetone of low surface tension, dry under normal pressure and carbonize at high temperature to produce carbon aerogels. The specific surface area of the carbon aerogel is 400-600m2(ii) in terms of/g. However, in the preparation process of the carbon aerogel, an alkaline catalyst such as sodium carbonate or potassium carbonate is introduced, and the incorporation of the metal salt can introduce metal impurities into the carbon aerogel, so that an ultra-pure carbon aerogel material cannot be obtained, and the application possibility of the carbon aerogel in drug loading for direct swallowing by a human body or other organisms is limited. And the literature can find that the specific surface area of the prepared carbon aerogel is generally not high enough, and the carbon aerogel can not meet the requirements of some fields needing extremely high loading capacity. Furthermore, supercritical drying methods are currently commonly used for drying carbon aerogels, for example, Katsuhiko Muroyama group using resorcinol and formaldehyde as polymerization agentsAnd (3) taking a monomer and potassium carbonate as a catalyst, and performing supercritical drying on carbon dioxide and then carbonizing at high temperature to obtain the carbon aerogel. The Gene Dresselhaus group similarly uses resorcinol and formaldehyde as monomers, sodium carbonate as a base catalyst, and ethanol as a supercritical fluid, and dries and carbonizes at high temperature to obtain carbon aerogel. The supercritical drying method has the advantages of short preparation time, theoretically capability of avoiding capillary pressure in the drying process, but also has many disadvantages, such as high temperature and high pressure are needed to reach the supercritical fluid state of the used substances, the requirement on instruments and equipment is higher, and the preparation cost is greatly increased. Meanwhile, the operation danger degree is correspondingly improved under the conditions of high temperature and high pressure. Therefore, the preparation of carbon aerogel by the atmospheric drying method has become the focus of research of scientists.
Chinese patent publication No. CN1891622 reports a method for preparing atmospheric carbon aerogel, in order to achieve normal pressure drying without causing pore shrinkage and structural damage, acetone, butanone, cyclohexane and other solvents with low surface tension are used to perform sufficient solvent exchange to replace formaldehyde and other fluids in pores, thereby achieving normal pressure drying to prepare carbon aerogel. And the specific surface area of the carbon aerogel prepared by normal pressure drying is still not high.
Therefore, how to find a simple preparation method to obtain the carbon aerogel, overcome the defects, obtain the ultra-high specific surface area and impurity-free ultra-pure carbon aerogel, and widen the popularization prospect of the carbon aerogel becomes one of the focuses of wide attention of a plurality of application researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a carbon aerogel and a preparation method thereof, and particularly, to an ultra-pure carbon aerogel with an ultra-high specific surface area based on air-activated pore-forming, wherein a partial air-activated pore-forming method is adopted in the present invention, the carbon aerogel is prepared at normal pressure, the process is simple and easy to control, the cost is low, and the popularization and utilization are convenient, and the obtained ultra-pure carbon aerogel with an ultra-high specific surface area is expected to be widely applied in the fields of food-grade drug loading, catalyst loading, substance adsorbents, energy storage materials, and the like.
The invention provides a carbon aerogel, which has a three-dimensional network structure formed by stacking carbon particles;
the surface of the carbon particles has a microporous structure.
Preferably, the carbon aerogel comprises a phenolic resin-based carbon aerogel;
the specific surface area of the carbon aerogel is 1000-3000 m2/g；
The aperture of the micropore is 0.01-2 nm;
the particle size of the carbon particles is 16-20 nm.
Preferably, the carbon particle packing is specifically interconnected carbon particle packing;
the carbon aerogel has a mesoporous structure;
the aperture of the mesopores is 2-45 nm;
the carbon aerogel is ultrapure carbon aerogel containing no metal element impurities.
Preferably, the porosity of the carbon aerogel is 85% -98%;
the proportion of micropores in the carbon aerogel is 55-85%;
the proportion of mesopores in the carbon aerogel is 15-45%;
the carbon aerogel is obtained by drying, carbonizing and pore-forming organic gel under normal pressure.
The invention provides a preparation method of carbon aerogel, which comprises the following steps:
1) mixing a phenolic compound, an aldehyde compound, an organic basic catalyst and a solvent, and then aging under a closed condition to obtain a solid product;
2) drying the solid product obtained in the step to obtain a phenolic aldehyde polymer;
3) carbonizing the organogel obtained in the above step and activating and forming pores to obtain carbon aerogel;
the carbonization treatment and the activation pore-forming comprise carbonization treatment and activation pore-forming, or activation pore-forming is carried out while the carbonization treatment is carried out.
Preferably, the phenolic compound comprises one or more of resorcinol, phenol, cresol, dimethylphenol, nonylphenol, bisphenol a, bisphenol F, propylphenol, and ethylphenol;
the aldehyde compound comprises a monoaldehyde;
the organic basic catalyst comprises a non-metallic amine compound;
the solvent comprises one or more of ethanol, methanol, isopropanol, propanol, N-methyl pyrrolidone and acetone.
Preferably, the molar volume ratio of the phenolic compound to the aldehyde compound is 1 mol: (20-600) mL;
the mass ratio of the organic basic catalyst to the phenolic compound is (0.001-0.4): 1;
the mass volume ratio of the organic basic catalyst to the solvent is 1 g: (0.05-30) L;
the aldehyde compound comprises one or more of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfural and valeraldehyde;
the organic basic catalyst comprises one or more of hexamethylenetetramine, triethylamine, ethylenediamine, urea, melamine and pyrazole.
Preferably, the step 1) is specifically:
11) premixing a phenolic compound and an aldehyde compound to obtain a solution;
12) sequentially adding an organic alkaline catalyst and a solvent into the solution obtained in the step, mixing again, and then aging under a closed condition to obtain a solid product;
the temperature of the premixing is 20-80 ℃; the premixing time is 5-120 min;
the temperature of the secondary mixing is 20-80 ℃; the remixing time is 10-90 min;
the aging temperature is 30-90 ℃; the aging time is 1-10 days.
Preferably, the drying temperature is 30-150 ℃;
the drying time is 1-15 days;
the temperature of the carbonization treatment is 500-1200 ℃; the carbonization time is 1.5-6 h; the atmosphere of the carbonization treatment is nitrogen and/or inert gas;
the temperature of the activated pore-forming is 700-1200 ℃; the time for activating and pore-forming is 10-180 min;
the activating pore-forming mode is to introduce air to carry out activating pore-forming.
Preferably, the specific steps of activating and pore-forming while carbonizing include:
in the carbonization process, introducing air into the carbonized inert atmosphere to carry out activation and pore-forming;
the starting time of air introduction is 50-120 min after carbonization begins;
the flow rate of the introduced air is 5-50 mL/min; and the duration time of the air introduction is 0.5-10 min.
The invention provides a carbon aerogel, which has a three-dimensional network structure formed by stacking carbon particles; the surface of the carbon particles has a microporous structure. The invention also provides a preparation method of the carbon aerogel. Compared with the prior art, the invention aims at the problem that the existing carbon aerogel has low specific surface area, and metal impurities can be introduced into the carbon aerogel by doping metal salt, so that an ultra-pure carbon aerogel material cannot be obtained, and the defect of application possibility of the carbon aerogel in drug loading for direct swallowing of a human body or other organisms is further limited.
The invention creatively obtains the carbon aerogel with a three-dimensional network structure formed by stacking the carbon particles with the microporous structures on the surfaces. The carbon aerogel presents a uniform mesoporous structure, the three-dimensional sense of a three-dimensional network is strong, the spatial network structure is formed by stacking carbon pellets with the diameter of about 20nm, the arrangement and the connection among the pellets are very tight, and the whole structure is complete. The carbon aerogel provided by the invention not only has a mesoporous structure formed by stacking the carbon spheres, but also has a large number of microporous structures, so that the specific surface area of the carbon aerogel is greatly increased by about 150% compared with the existing carbon aerogel.
The invention adopts a chemical synthesis method, takes resorcinol and monoaldehyde as raw materials, takes hexamethylenetetramine as an organic catalyst to form phenolic aldehyde high polymer, adopts a normal-pressure drying method and subsequent high-temperature carbonization to obtain the carbon aerogel, realizes the normal-pressure preparation of the carbon aerogel, avoids the high cost and the danger of the traditional supercritical drying method, simultaneously abandons the solvent exchange step in the traditional normal-pressure drying method, and greatly reduces the occurrence of environmental pollution. Meanwhile, the invention also provides a method for introducing proper dry air during carbonization so as to carry out partial air activation pore-forming, further increase the specific surface area of the obtained carbon aerogel and optimize the specific surface area characteristics and the micro-porosity characteristics of the carbon aerogel. The preparation method of the carbon aerogel effectively overcomes the defect that the specific surface area of the carbon aerogel is smaller due to partial collapse of the three-dimensional network structure of the carbon aerogel caused by larger capillary pressure difference generated in the normal-pressure drying process.
In addition, considering the requirements of no impurities and high purity of carbon aerogel in drug loading, the invention more particularly adopts the organic catalyst as the phenolic aldehyde polymerization accelerator, avoids the influence of the traditional inorganic metal alkaline catalyst on the purity of the carbon aerogel and realizes excellent biocompatibility. The ultra-pure carbon aerogel with the ultra-high specific surface area, prepared by the invention, is widely applied in the fields of food-grade drug loading, catalyst loading, substance adsorbents, energy storage materials and the like, and the preparation method has the advantages of simple and easily-controlled process, low cost, convenience for popularization and utilization and suitability for industrial mass production and application.
Experimental results show that the BET specific surface area of the carbon aerogel prepared by the invention is up to about 1200m2The material has wide application prospect in drug loading, electrode materials of energy storage lithium batteries or super capacitors and the like.
Drawings
FIG. 1 is a FESEM image of a field emission scanning electron microscope of the ultra-pure carbon aerogel prepared in example 1 of the present invention;
FIG. 2 is a TEM image of an ultrapure carbon aerogel prepared in example 2 of the present invention;
fig. 3 is a nitrogen isothermal adsorption and desorption curve of the ultrapure carbon aerogel prepared in example 3 of the present invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs a purity commonly used in the field of analytically pure or carbon aerogel materials.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The present invention provides a carbon aerogel having a three-dimensional network structure formed by stacking carbon particles;
the surface of the carbon particles has a microporous structure.
The present invention is not limited to other shapes and parameters of the carbon particles, and the carbon particles are preferably carbon beads, which are conventional shapes and parameters of carbon particles well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to practical application, product quality and product performance. The particle size of the carbon particles is preferably 16-25 nm, more preferably 17-23 nm, more preferably 18-21 nm, more preferably 19-20 nm, and particularly 16-20 nm.
The carbon particle surface has a micropore structure, the shape and parameters of the micropore are not particularly limited, the conventional shape and parameters of the micropore known by a person skilled in the art can be used, the person skilled in the art can select and adjust the shape and parameters according to the actual application condition, the product quality and the product performance, and the pore diameter of the micropore is preferably 0.01-2 nm, more preferably 0.05-1.8 nm, more preferably 0.1-1.5 nm, and more preferably 0.5-1.0 nm. In the invention, the surface of the carbon particle can also have a mesoporous structure, and the aperture of the mesopores is preferably less than or equal to 5nm, namely 2-5 nm, more preferably 2.5-4.5 nm, and more preferably 3-4 nm.
The specific stacking form and network structure of the three-dimensional network structure formed by stacking the carbon particles are not particularly limited in the present invention, and the stacking form of the carbon particles and the three-dimensional network structure of the carbon aerogel, which are well known to those skilled in the art, may be selected and adjusted by those skilled in the art according to the actual application, the product quality and the product performance, and the stacking of the carbon particles in the present invention is particularly preferably stacking of interconnected carbon particles. The carbon particles of the present invention are preferably linked by straight carbon rods. Carbon particles in the carbon aerogel are stacked to form a three-dimensional network structure, and a mesoporous structure of the carbon aerogel is formed in the network structure.
The parameters of the mesopores of the carbon aerogel are not particularly limited, and the parameters of the mesopores of the carbon aerogel known by the skilled in the art can be selected and adjusted according to the actual application condition, the product quality and the product performance, and the pore diameter of the mesopores of the carbon aerogel is preferably 2-45 nm, more preferably 7-40 nm, more preferably 12-35 nm, more preferably 17-30 nm, and more preferably 22-25 nm.
The selection of the specific carbon source of the carbon aerogel is not particularly limited, and the carbon source is a conventional carbon source of the carbon aerogel known to those skilled in the art, and those skilled in the art can select and adjust the carbon source according to the actual application condition, the product quality and the product performance.
The invention has no reference to the parameters of the carbon aerogelThe carbon aerogel provided by the invention is preferably ultrapure carbon aerogel, and specifically may be ultrapure carbon aerogel containing no metal element impurities. The specific surface area of the carbon aerogel is preferably 1000-3000 m2(ii)/g, more preferably 1100 to 2500m2(iv)/g, more preferably 1200 to 2000m2(iv) 1300 to 1500m is more preferable2(ii) in terms of/g. The porosity of the carbon aerogel is preferably 85% to 98%, more preferably 87% to 96%, more preferably 89% to 94%, and more preferably 91% to 92%. The proportion of micropores in the carbon aerogel is preferably 55-85%, more preferably 60-80%, and more preferably 65-75%. The proportion of mesopores in the carbon aerogel is preferably 15-45%, more preferably 20-40%, and more preferably 25-35%.
In the invention, the carbon aerogel is preferably obtained by drying, carbonizing and pore-forming the organic gel at normal pressure, and more preferably obtained by drying, carbonizing and pore-forming the organic gel at normal pressure. The source of the organogel (organic aerogel) in the present invention is not particularly limited, and may be any conventional source of organogel known to those skilled in the art, and may be prepared according to conventional preparation methods or commercially available, and those skilled in the art can select and adjust the organogel according to the actual application, the product quality and the product performance, and the organogel in the present invention is preferably an organic pure gel.
The invention also provides a preparation method of the carbon aerogel, which comprises the following steps:
1) mixing a phenolic compound, an aldehyde compound, an organic basic catalyst and a solvent, and then aging under a closed condition to obtain a solid product;
2) drying the solid product obtained in the step to obtain a phenolic aldehyde polymer;
3) carbonizing the organogel obtained in the above step and activating and forming pores to obtain carbon aerogel;
the carbonization treatment and the activation pore-forming comprise carbonization treatment and activation pore-forming, or activation pore-forming is carried out while the carbonization treatment is carried out.
The selection, proportion and parameters of the raw materials or the products in the preparation method of the present invention, and the corresponding preferred principles, etc., correspond to the selection, proportion and parameters of the raw materials in the carbon aerogel, and the corresponding preferred principles, etc., if not specifically noted, and are not described in detail herein.
The invention firstly mixes the phenolic compound, the aldehyde compound, the organic alkaline catalyst and the solvent, and then carries out aging under the closed condition to obtain the solid product.
The selection of the phenolic compound is not particularly limited by the present invention, and may be a conventional phenolic compound for preparing phenolic polymer, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application, product quality and product performance, and the phenolic compound of the present invention preferably includes one or more of resorcinol, phenol, cresol, dimethylphenol, nonylphenol, bisphenol a, bisphenol F, propylphenol and ethylphenol, and more preferably resorcinol, phenol, cresol, dimethylphenol, nonylphenol, bisphenol a, bisphenol F, propylphenol or ethylphenol.
The selection of the aldehyde compound is not particularly limited in the present invention, and may be a conventional aldehyde compound for preparing phenolic polymer, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application, product quality and product performance, and the aldehyde compound of the present invention preferably includes a monoaldehyde, more preferably includes one or more of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfural and valeraldehyde, and more preferably includes formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfural or valeraldehyde.
The amount of the phenolic compound and the aldehyde compound is not particularly limited in the present invention, and may be any amount conventionally used for preparing phenolic polymers, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application, the product quality and the product performance, and the molar volume ratio of the phenolic compound to the aldehyde compound in the present invention is preferably 1 mol: (20 to 600) mL, more preferably 1 mol: (120-500) mL, more preferably 1 mol: (220-400) mL, more preferably 1 mol: (270-350) mL.
The selection of the organic basic catalyst is not particularly limited in the present invention, and may be a conventional organic basic catalyst for preparing phenolic polymer, which is well known to those skilled in the art, and can be selected and adjusted according to the actual application, product quality and product performance, and the present invention provides the ultra-pure carbon aerogel free of metal impurities, wherein the organic basic catalyst preferably comprises non-metal amine compounds, more preferably comprises one or more of hexamethylenetetramine, triethylamine, ethylenediamine, urea, melamine and pyrazole, and more preferably hexamethylenetetramine, triethylamine, ethylenediamine, urea, melamine or pyrazole.
The amount of the organic basic catalyst used in the present invention is not particularly limited, and may be any amount conventionally used for preparing phenolic polymers, which is well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to the actual application, the product quality and the product performance, and the mass ratio of the organic basic catalyst to the phenolic compound in the present invention is preferably (0.001-0.4): 1, more preferably (0.001 to 0.4): 1, more preferably (0.005 to 0.35): 1, more preferably (0.01 to 0.3): 1, more preferably (0.05 to 0.25): 1, more preferably (0.1 to 0.2): 1.
the selection of the solvent is not particularly limited in the present invention, and may be any conventional organic solvent for preparing phenolic polymer, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application, product quality and product performance, and the solvent of the present invention preferably includes one or more of ethanol, methanol, isopropanol, propanol, N-methylpyrrolidone or acetone, and more preferably ethanol, methanol, isopropanol, propanol, N-methylpyrrolidone or acetone.
The amount of the solvent used in the present invention is not particularly limited, and may be any amount conventionally used for preparing phenolic polymers, which is well known to those skilled in the art, and can be selected and adjusted according to the actual application, the product quality and the product performance, and the mass-to-volume ratio of the organic basic catalyst to the solvent in the present invention is preferably 1 g: (0.05-30) L, more preferably 1 g: (0.1-25) L, more preferably 1 g: (0.05-30) L, more preferably 1 g: (0.05-30) L, more preferably 1 g: (0.05-30) L.
In order to further improve the reaction efficiency and ensure the performance of the final product, complete and refine the preparation process, the steps, namely the step 1), can be specifically as follows:
11) premixing a phenolic compound and an aldehyde compound to obtain a solution;
12) sequentially adding an organic alkaline catalyst and a solvent into the solution obtained in the step, mixing again, and then aging under a closed condition to obtain a solid product;
the specific mode and parameters of the premixing are not particularly limited by the present invention, and the premixing mode and parameters are well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application, the product quality and the product performance, and the premixing in the present invention is preferably stirring mixing, and more preferably water bath stirring mixing. The temperature of the premixing is preferably 20-80 ℃, more preferably 30-70 ℃, and more preferably 40-60 ℃. The pre-mixing time is preferably 5-120 min, more preferably 25-100 min, and more preferably 45-80 min.
The specific mode and parameters of the remixing in the present invention are not particularly limited, and may be selected and adjusted by those skilled in the art according to the practical application, the product quality and the product performance, and the remixing in the present invention is preferably stirring mixing, more preferably stirring mixing in a water bath. The temperature of the remixing in the invention is preferably 20-80 ℃, more preferably 30-70 ℃, and more preferably 40-60 ℃. The remixing time is preferably 10-90 min, more preferably 20-80 min, more preferably 30-70 min, and more preferably 40-60 min.
The specific aging mode and parameters are not particularly limited, and the aging mode and parameters known by the technicians in the field can be selected and adjusted by the technicians in the field according to the actual application condition, the product quality and the product performance, and the aging temperature is preferably 20-80 ℃, more preferably 30-70 ℃, and more preferably 40-60 ℃. The aging time is preferably 1 to 10 days, more preferably 3 to 8 days, and even more preferably 5 to 6 days.
According to the invention, the solid product obtained in the above step is dried to obtain the phenolic aldehyde polymer, namely the organogel.
The specific drying manner and parameters are not particularly limited in the present invention, and those skilled in the art can select and adjust the drying manner and parameters according to the actual application, product quality and product performance. The drying is preferably natural drying, and the natural drying time is preferably 5-24 hours, more preferably 8-21 hours, and more preferably 12-18 hours. The drying temperature is preferably 30-150 ℃, more preferably 50-120 ℃, and more preferably 70-100 ℃. The drying time is preferably 1-15 days, more preferably 4-12 days, and more preferably 7-9 days.
Finally, carbonizing the organogel obtained in the above steps and activating and forming pores to obtain the carbon aerogel.
The specific mode and parameters of the carbonization treatment are not particularly limited, and the carbonization treatment mode and parameters known by the technicians in the field can be selected and adjusted by the technicians in the field according to the actual application condition, the product quality and the product performance, the preparation process is further refined to ensure the performance of the final product, and the carbonization treatment time is preferably 1.5-6 hours, more preferably 2.5-5 hours, and more preferably 3.5-4 hours. The carbonization treatment temperature is preferably 500-1200 ℃, more preferably 600-1100 ℃, more preferably 700-1000 ℃, and more preferably 800-900 ℃. The atmosphere for the carbonization treatment in the present invention is preferably nitrogen and/or an inert gas, more preferably nitrogen or an inert gas, and still more preferably nitrogen or argon.
The specific mode and parameters of the activating pore-forming are not particularly limited, and the activating pore-forming mode and parameters known by the technicians in the field can be used, and the technicians in the field can select and adjust the activating pore-forming mode and parameters according to the actual application condition, the product quality and the product performance. The time for activating and pore-forming is preferably 10-180 min, more preferably 30-150 min, and more preferably 60-120 min. The activating and pore-forming temperature is preferably 700-1200 ℃, more preferably 800-1100 ℃, and more preferably 900-1000 ℃.
The carbonization treatment and the activation pore-forming preferably include carbonization treatment and activation pore-forming, or activation pore-forming is performed while the carbonization treatment is performed, and more preferably, activation pore-forming is performed while the carbonization treatment is performed. In order to better improve the performance of a final product, ensure the structure of the final product and better optimize the preparation process, the specific step of activating and pore-forming while carbonizing is to introduce air into the carbonized inert atmosphere to activate and pore-form in the carbonizing process.
The starting time of the air introduction is preferably within 50-120 min after the carbonization starts, more preferably 60-110 min, more preferably 70-100 min, and more preferably 80-90 min. The flow rate of the introduced air is preferably 5-50 mL/min, more preferably 15-40 mL/min, and more preferably 25-30 mL/min. The duration time of the air introduction is preferably 0.5-10 min, more preferably 2.5-8 min, and more preferably 4.5-6 min.
The invention provides ultra-high-purity carbon aerogel with an ultrahigh specific surface area based on air-activated pore-forming and a preparation method thereof. According to the invention, resorcinol and monoaldehyde are used as raw materials, hexamethylenetetramine is used as an organic catalyst to form a phenolic aldehyde high polymer, a normal-pressure drying method and subsequent high-temperature carbonization are adopted to obtain the carbon aerogel, so that the normal-pressure preparation of the carbon aerogel is realized, the high cost and the danger of the traditional supercritical drying method are avoided, the solvent exchange step in the traditional normal-pressure drying method is also abandoned, and the occurrence of environmental pollution is greatly reduced. The invention adopts organic matters as the catalyst, avoids the doping of metallic element impurities, sodium element, potassium element and the like in the carbon aerogel by the traditional alkaline catalyst (such as sodium carbonate and potassium carbonate), and lays an important foundation for obtaining the ultra-pure carbon aerogel. In addition, the invention adopts a normal pressure drying process, and abandons the complex process of high cost and high danger of the traditional supercritical drying process. In order to improve the specific surface area of the carbon aerogel dried under normal pressure, the invention creatively provides that small-flow air is properly added to activate and form pores during high-temperature carbonization treatment, the specific surface area of the obtained carbon aerogel is further increased, the specific surface area characteristic and the microscopic pore characteristic of the carbon aerogel are optimized, a large number of micropores below 5nm are successfully obtained by etching the surface of the carbon aerogel particles at the level of 20nm, the specific surface area of the carbon aerogel is greatly increased, and the defect that the specific surface area of the carbon aerogel is smaller due to partial collapse of a three-dimensional network structure of the carbon aerogel caused by large capillary pressure difference generated in the normal-pressure drying process is overcome.
The invention obtains the carbon aerogel with a three-dimensional network structure formed by stacking the carbon particles with the microporous structures on the surfaces. The carbon aerogel presents a uniform mesoporous structure, the three-dimensional sense of a three-dimensional network is strong, the spatial network structure is formed by stacking carbon pellets with the diameter of about 20nm, the arrangement and the connection among the pellets are very tight, and the whole structure is complete. The carbon aerogel provided by the invention not only has a mesoporous structure formed by stacking the carbon spheres, but also has a large number of microporous structures, so that the specific surface area of the carbon aerogel is greatly increased by about 150% compared with the existing carbon aerogel.
In addition, considering the requirements of no impurities and high purity of carbon aerogel in drug loading, the invention more particularly adopts the organic catalyst as the phenolic aldehyde polymerization accelerator, avoids the influence of the traditional inorganic metal alkaline catalyst on the purity of the carbon aerogel and realizes excellent biocompatibility. The ultra-pure carbon aerogel with the ultra-high specific surface area, prepared by the invention, is widely applied in the fields of food-grade drug loading, catalyst loading, substance adsorbents, energy storage materials and the like, and the preparation method has the advantages of simple and easily-controlled process, low cost, convenience for popularization and utilization and suitability for industrial mass production and application.
Experimental results show that the BET specific surface area of the carbon aerogel prepared by the invention is up to about 1200m2The material has wide application prospect in drug loading, electrode materials of energy storage lithium batteries or super capacitors and the like.
For further illustration of the present invention, the following will describe in detail a carbon aerogel and a preparation method thereof in conjunction with examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific procedures are given, which are only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Slowly adding 0.5g of resorcinol into 3.5mL of formaldehyde solution, stirring in a water bath at the constant temperature of 40 ℃ for 10min, then adding 0.005g of hexamethylenetetramine, simultaneously pouring 20mL of ethanol solution, and uniformly stirring. Then the obtained solution is sealed and put into an oven with the temperature of 80 ℃, and the temperature is kept and the aging is carried out for 3 days. And taking out the aged phenolic gel polymer, and naturally drying in the air for 5 h. The phenolic gel was then dried in an oven at 80 ℃ for 2 days. The completely dried phenolic gel is carbonized for 2 hours at 800 ℃ in a high-temperature furnace filled with argon. In order to further obtain the carbon aerogel with the ultrahigh specific surface area, air is simultaneously introduced during carbonization, the flow rate of the air is 10mL/min, and the continuous introduction time is 8min, so that the ultra-pure carbon aerogel with the ultrahigh specific surface area based on air-activated pore-forming is obtained.
The carbon aerogel prepared in example 1 of the present invention was characterized.
Referring to fig. 1, fig. 1 is a field emission scanning electron microscope FESEM image of ultrapure carbon aerogel prepared in example 1 of the present invention.
As can be seen from FIG. 1, the ultrapure carbon aerogel prepared by the method has a uniform mesoporous structure, the three-dimensional network has very strong stereoscopic impression, the spatial network structure is formed by stacking carbon spheres with the diameter of about 20nm, and the whole structure is very complete.
The carbon aerogel prepared in the example 1 of the invention is subjected to a nitrogen isothermal adsorption and desorption test, and the result shows that the specific surface area of the carbon aerogel prepared in the invention is 1135m2/g。
Example 2
Slowly adding 0.5g of resorcinol into 3.5mL of acetaldehyde solution, stirring in a water bath at the constant temperature of 40 ℃ for 10min, then adding 0.1g of hexamethylenetetramine, simultaneously pouring 50mL of ethanol solution, and uniformly stirring. Then the obtained solution is sealed and put into an oven with the temperature of 80 ℃, and the heat preservation and the aging are carried out for 7 days. And taking out the aged phenolic gel polymer, and naturally drying in the air for 5 h. The phenolic gel was then dried in an oven at 80 ℃ for 2 days. The completely dried phenolic gel is carbonized for 2 hours at 800 ℃ in a high-temperature furnace filled with argon. In order to further obtain the carbon aerogel with the ultrahigh specific surface area, air is simultaneously introduced during carbonization, the flow rate of the air is 10mL/min, and the continuous introduction time is 8min, so that the ultra-pure carbon aerogel with the ultrahigh specific surface area based on air-activated pore-forming is obtained.
The carbon aerogel prepared in example 2 of the present invention was characterized.
Referring to fig. 2, fig. 2 is a TEM image of a transmission electron microscope of the ultrapure carbon aerogel prepared in example 2 of the present invention.
As can be seen from FIG. 2, in the ultrapure carbon aerogel prepared by the method, the diameters of the small spheres in the carbon aerogel are 16-20 nm, the arrangement and connection among the small spheres are very tight, the pore diameter is about 15nm, and the obtained carbon aerogel has a complete pore structure and more mesopores.
The carbon aerogel prepared in the example 2 of the invention is subjected to a nitrogen isothermal adsorption and desorption test, and the result shows that the specific surface area of the carbon aerogel prepared in the invention is 1014m2/g。
Example 3
Slowly adding 0.5g of resorcinol into 3.5mL of acetaldehyde solution, stirring in a water bath at the constant temperature of 40 ℃ for 10min, then adding 0.1g of hexamethylenetetramine, simultaneously pouring 50mL of ethanol solution, and uniformly stirring. Then the obtained solution is sealed and put into an oven with the temperature of 80 ℃, and the heat preservation and the aging are carried out for 7 days. And taking out the aged phenolic gel polymer, and naturally drying in the air for 5 h. The phenolic gel was then dried in an oven at 80 ℃ for 2 days. The completely dried phenolic gel is carbonized for 2 hours at 800 ℃ in a high-temperature furnace filled with argon. In order to further obtain the carbon aerogel with the ultrahigh specific surface area, air is simultaneously introduced during carbonization, the flow rate of the air is 15mL/min, and the continuous introduction time is 5min, so that the ultra-pure carbon aerogel with the ultrahigh specific surface area based on air-activated pore-forming is obtained.
The carbon aerogel prepared in the example 3 of the present invention was subjected to a nitrogen isothermal adsorption and desorption test, and the results showed that the carbon aerogel prepared in the present invention had a specific surface area of 1271m2/g。
Referring to fig. 3, fig. 3 is a nitrogen isothermal sorption and desorption curve of the ultrapure carbon aerogel prepared in example 3 of the present invention.
Example 4
Slowly adding 0.5g of resorcinol into 10mL of furfural solution, stirring in a water bath at the constant temperature of 60 ℃ for 10min, then adding 0.02g of hexamethylenetetramine, simultaneously pouring 32mL of ethanol solution, and uniformly stirring. Then the obtained solution is sealed and put into an oven with the temperature of 80 ℃, and the heat preservation and the aging are carried out for 7 days. And taking out the aged phenolic gel polymer, and naturally drying in the air for 5 h. The phenolic gel was then dried in an oven at 80 ℃ for 2 days. The completely dried phenolic gel was carbonized at 1000 ℃ for 3 hours in a high temperature furnace filled with argon. In order to further obtain the carbon aerogel with the ultrahigh specific surface area, air is simultaneously introduced during carbonization, the flow rate of the air is 15mL/min, and the continuous introduction time is 5min, so that the ultra-pure carbon aerogel with the ultrahigh specific surface area based on air-activated pore-forming is obtained.
The carbon aerogel prepared in the example 4 of the invention is subjected to a nitrogen isothermal adsorption and desorption test, and the result shows that the specific surface area of the carbon aerogel prepared in the invention is 1298m2/g。
The ultra-pure carbon aerogel with ultra-high specific surface area based on air-activated pore-forming and the preparation method thereof are provided by the invention. Having described in detail, the principles and embodiments of the present invention have been described herein using specific examples, which are intended to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (8)
1. A carbon aerogel, wherein said carbon aerogel has a three-dimensional network structure formed by packing carbon particles;
the surface of the carbon particle has a micropore structure;
the aperture of the micropore is 0.01-2 nm;
the particle size of the carbon particles is 16-25 nm;
the carbon particle stacking is specifically a stacking of interconnected carbon particles;
the carbon aerogel has a mesoporous structure;
the aperture of the mesopores is 2-45 nm;
the porosity of the carbon aerogel is 85% -98%;
the proportion of micropores in the carbon aerogel is 55-85%;
the proportion of mesopores in the carbon aerogel is 15-45%;
the carbon aerogel is obtained by drying, carbonizing and pore-forming organic gel under normal pressure;
the pore-forming mode is to introduce air to activate and form pores;
the carbon aerogel is ultrapure carbon aerogel containing no metal element impurities.
2. The carbon aerogel of claim 1, wherein the carbon aerogel is selected from the group consisting of phenolic resin-based carbon aerogels;
the specific surface area of the carbon aerogel is 1000-3000 m2/g。
3. The preparation method of the carbon aerogel is characterized by comprising the following steps:
1) mixing a phenolic compound, an aldehyde compound, an organic basic catalyst and a solvent, and then aging under a closed condition to obtain a solid product;
the phenolic compound is selected from one or more of resorcinol, phenol, cresol, dimethylphenol, nonylphenol, bisphenol A, bisphenol F, propyl phenol and ethyl phenol;
the aldehyde compound is selected from monoaldehydes;
the organic basic catalyst is selected from nonmetallic amine compounds;
the molar volume ratio of the phenolic compound to the aldehyde compound is 1 mol: (20-600) mL;
the mass ratio of the organic basic catalyst to the phenolic compound is (0.001-0.4): 1;
2) drying the solid product obtained in the step to obtain a phenolic aldehyde polymer;
3) carbonizing the organogel obtained in the above step and activating and forming pores to obtain carbon aerogel;
the temperature of the carbonization treatment is 500-1200 ℃;
the carbonization time is 1.5-6 h;
the activating pore-forming mode is to introduce air to carry out activating pore-forming;
the temperature of the activated pore-forming is 700-1200 ℃;
the time for activating and pore-forming is 10-180 min;
the carbonization treatment and the activation pore-forming comprise carbonization treatment and activation pore-forming, or activation pore-forming is carried out while the carbonization treatment is carried out;
the specific steps of activating and pore-forming while carbonizing treatment are as follows:
and in the carbonization process, introducing air into the carbonized inert atmosphere to activate and form pores.
4. The method of claim 3, wherein the solvent comprises one or more of ethanol, methanol, propanol, N-methylpyrrolidone, and acetone.
5. The method according to claim 3, wherein the mass-to-volume ratio of the organic basic catalyst to the solvent is 1 g: (0.05-30) L;
the aldehyde compound is selected from one or more of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfural and valeraldehyde;
the organic basic catalyst is selected from one or more of hexamethylenetetramine, triethylamine, ethylenediamine, urea, melamine and pyrazole.
6. The preparation method according to claim 3, wherein the step 1) is specifically:
11) premixing a phenolic compound and an aldehyde compound to obtain a solution;
12) sequentially adding an organic alkaline catalyst and a solvent into the solution obtained in the step, mixing again, and then aging under a closed condition to obtain a solid product;
the temperature of the premixing is 20-80 ℃; the premixing time is 5-120 min;
the temperature of the secondary mixing is 20-80 ℃; the remixing time is 10-90 min;
the aging temperature is 30-90 ℃; the aging time is 1-10 days.
7. The preparation method according to claim 3, wherein the drying temperature is 30-150 ℃;
the drying time is 1-15 days;
the atmosphere of the carbonization treatment is nitrogen and/or inert gas.
8. The production method according to any one of claims 3 to 7, wherein the starting time of the air introduction is 50 to 120min after the start of carbonization;
the flow rate of the introduced air is 5-50 mL/min; and the duration time of the air introduction is 0.5-10 min.
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