CN108854874A - A kind of ultrapure carbon aerogels and preparation method thereof with superhigh specific surface area based on air-activated pore-creating - Google Patents
A kind of ultrapure carbon aerogels and preparation method thereof with superhigh specific surface area based on air-activated pore-creating Download PDFInfo
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- C01B32/00—Carbon; Compounds thereof
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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Abstract
The present invention provides a kind of carbon aerogels, the carbon aerogels, which have, is accumulated the three-dimensional net structure formed by carbon particle；The carbon particle surface has microcellular structure.Carbon aerogels prepared by the present invention show uniform meso-hole structure, and the three-dimensional sense of three-dimensional network is strong, and spacial framework is accumulated by carbon bead, the arrangement between bead with connect closely, overall structure is complete.And not only there is carbon aerogels carbon bead to accumulate the meso-hole structure to be formed, and carbon bead itself also has a large amount of microcellular structure, to greatly enhance the specific surface area of carbon aerogels, BET specific surface area can reach 1200m2/ g or so.And the present invention has obtained carbon aerogels using constant pressure and dry, without solvent exchange step, and inorganic metal basic catalyst is not used, realize fabulous biocompatibility, ultrapure carbon aerogels are obtained, in food-grade drug loading, catalyst load, substance adsorber, the fields such as energy storage material are widely used.
Description
Technical field
The present invention relates to aeroge technical field, it is related to a kind of carbon aerogels and preparation method thereof more particularly to a kind of base
In the ultrapure carbon aerogels and preparation method thereof with superhigh specific surface area of air-activated pore-creating.
Background technique
Aeroge, also known as xerogel are a kind of solid matter forms, are mutually coalesced by colloidal particle or the high-polymer molecule
Nanoporous network structure is constituted, and is full of a kind of high dispersive solid-state material of gaseous state decentralized medium in hole, is had super
The performances such as low-density, high-specific surface area, high porosity and excellent thermal insulation, in ultra heat insulating material, acoustic material, particle detection
Device, low-k aerogel, inertia targeting material etc., which have, to be widely applied.
There are many type of aeroge, there is silicon systems, carbon system, sulphur system, metal oxide system or metal system etc., wherein carbon airsetting
Glue is a kind of special condensed state functional material, is made of many interconnections and uniform little particle, is had specific mesoporous
Structure.Carbon aerogels have excellent properties, high porosity (>95%), high-specific surface area (>400m2/ g), superpower leads
Electrically, high thermal conductivity ability, enough corrosion resistant types, low thermal coefficient of expansion, extremely-low density and elasticity, these brilliant characteristics make
It becomes a kind of functional material being widely used.Carbon aerogels have in energy storage material, catalyst carrier material and environment
The fields such as evil substance adsorbent material have important application value and status.The characteristic of high-ratio surface and high conductivity make its
Energy storage material and device, especially lithium ion battery plus-negative plate material, by favor on electric chemical super capacitor.In addition, high
The features such as porosity and high-specific surface area, nontoxic and good biocompatibility, makes carbon aerogels in sorbent material again, urges
Agent carrier and pharmaceutical carrier etc. are widely used and approve, have a good application prospect and open with huge
Send out potentiality.
Thus, also increasing about the research for preparing carbon aerogels in recent years, wherein GloriaRasines team is sharp
Use resorcinol, formaldehyde and melamine as polymerized monomer, using sodium carbonate as basic catalyst, to promote cross-linking reaction,
Novolac polymer gel is obtained.Then it handles to obtain carbon aerogels using the dry simultaneously high temperature cabonization of supercritical carbon dioxide.Jun
Li et al. people utilizes resorcinol and formalin, novolac polymer is obtained under the catalytic action of sodium carbonate, then with low surface
The acetone of tension carries out exchange of solvent, and dry and high temperature cabonization has obtained carbon aerogels in atmospheric conditions.The carbon aerogels
Specific surface area is 400-600m2/g.But basic catalyst can be introduced in above-mentioned carbon aerogels preparation process, such as sodium carbonate or
The incorporation of potassium carbonate etc., these metal salts can introduce metal impurities in carbon aerogels, cannot obtain ultrapure carbon aerogels material,
Which limits carbon aerogels to be used for the application possibility that human body or other biological are directly swallowed in drug loading.And in text
It can be found that the specific surface area of preparation-obtained carbon aerogels is generally not high enough in offering, it is high negative that it is not able to satisfy some needs
The demand in the field of carrying capacity.And the drying means of carbon aerogels generallys use supercritical drying drying method at present, such as
Katsuhiko Muroyama team is using resorcinol and formaldehyde as polymerized monomer, and potassium carbonate is as catalyst, in dioxy
High temperature cabonization after change carbon supercritical drying, has obtained carbon aerogels.Gene Dresselhaus team is also with resorcinol
With formaldehyde as monomer, sodium carbonate is as base catalyst, and with use ethanol as supercritical fluid, dry and high temperature cabonization obtains carbon
Aeroge.The preparation of supercritical drying drying method has required time short, theoretically can be avoided the capillary pressure in drying process,
But equally there is also many drawbacks, need high temperature and pressure such as to reach the Supercritical Conditions of substance used, set to instrument
Standby requirement is relatively high, to substantially increase preparation cost.Simultaneously under conditions of high temperature and pressure, the degree of danger of operation also phase
It should improve.Therefore, constant pressure and dry method prepares the emphasis that carbon aerogels have become scientists study.
China Patent Publication No. CN1891622 reports a kind of preparation method of normal pressure carbon aerogels, in order to realize normal pressure
The contraction and structure for not causing hole under drying destroy, and are filled using the acetone of low surface tension, butanone, hexamethylene equal solvent
The exchange of solvent divided, to replace the fluids such as the formaldehyde in hole, so that realizing constant pressure and dry prepares carbon aerogels, but this is often
Pressing dry drying method needs a large amount of solvent to swap, and considerably increases the waste of cost and raw material.And constant pressure and dry is made
The specific surface area of standby obtained carbon aerogels is not still high.
Therefore, a kind of simple preparation method how is found, carbon aerogels is obtained, overcomes drawbacks described above, obtains superelevation ratio
The ultrapure carbon aerogels of surface area and free from admixture, widen carbon aerogels promotion prospect, it has also become many application study people in the industry
One of the focus of member's extensive concern.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of carbon aerogels and preparation method thereof, especially
It is a kind of ultrapure carbon aerogels with superhigh specific surface area based on air-activated pore-creating, it is living that present invention employs partial airs
Change the method for pore-creating, normal pressure is prepared for carbon aerogels, and process is simple easily controllable, low in cost, is convenient for utilization and extention, and obtain
The ultrapure carbon aerogels with superhigh specific surface area have been arrived, have been expected in food-grade drug loading, catalyst load, substance absorption
Agent, the fields such as energy storage material are widely used.
The present invention provides a kind of carbon aerogels, the carbon aerogels, which have, is accumulated the three-dimensional network knot formed by carbon particle
Structure；
The carbon particle surface has microcellular structure.
Preferably, the carbon aerogels include phenolic resin base carbon aerogel；
The specific surface area of the carbon aerogels is 1000~3000m2/g；
The aperture of the micropore is 0.01~2nm；
The partial size of the carbon particle is 16~20nm.
Preferably, the carbon particle accumulation is specially carbon particle accumulation interconnected；
The carbon aerogels have meso-hole structure；
The mesoporous aperture is 2~45nm；
The carbon aerogels are the ultrapure carbon aerogels without elementary metal impurities.
Preferably, the porosity of the carbon aerogels is 85%~98%；
The ratio of micropore is 55%~85% in the carbon aerogels；
The ratio of the carbon aerogels intermediary hole is 15%~45%；
The carbon aerogels are obtained after constant pressure and dry, carbonization and pore-creating by organogel.
The present invention provides a kind of preparation methods of carbon aerogels, include the following steps：
1) after being mixed phenolic compound, aldehyde compound, organic basic catalysts and solvents, in confined conditions
Aging is carried out, solid product is obtained；
2) solid product for obtaining above-mentioned steps obtains novolac polymer after drying；
3) organogel for obtaining above-mentioned steps obtains carbon aerogels after carbonization treatment and activation pore-creating；
The carbonization treatment and activation pore-creating are lived while including first carbonization treatment reactivation pore-creating or carbonization treatment
Change pore-creating.
Preferably, the phenolic compound include resorcinol, phenol, cresols, dimethyl phenol, nonyl phenol, bisphenol-A,
One of Bisphenol F, propylphenol and ethyl -phenol are a variety of；
The aldehyde compound includes monoaldehyde；
The organic basic catalyst includes nonmetallic aminated compounds；
The solvent includes one of ethyl alcohol, methanol, isopropanol, propyl alcohol, N-Methyl pyrrolidone and acetone or a variety of.
Preferably, the molal volume of the phenolic compound and aldehyde compound ratio is 1mol：(20~600) mL；
The mass ratio of the organic basic catalyst and phenolic compound is (0.001~0.4)：1；
The mass volume ratio of the organic basic catalyst and the solvent is 1g：(0.05~30) L；
The aldehyde compound includes one of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, furfural and valeral or a variety of；
The organic basic catalyst includes hexamethylenetetramine, triethylamine, ethylenediamine, urea, melamine and pyrazoles
One of or it is a variety of.
Preferably, the step 1) is specially：
11) phenolic compound and aldehyde compound are pre-mixed, obtain solution；
12) into the solution that above-mentioned steps obtain, organic basic catalysts and solvents is sequentially added and are mixed again, are then existed
Aging is carried out under confined conditions, obtains solid product；
The temperature of the premixing is 20~80 DEG C；The time of the premixing is 5~120min；
The temperature mixed again is 20~80 DEG C；The time mixed again is 10~90min；
The temperature of the aging is 30~90 DEG C；The time of the aging is 1~10 day.
Preferably, the temperature of the drying is 30~150 DEG C；
The time of the drying is 1~15 day；
The temperature of the carbonization treatment is 500~1200 DEG C；The time of the carbonization treatment is 1.5~6h；The carbonization
The atmosphere of processing is nitrogen and/or inert gas；
The temperature of the activation pore-creating is 700~1200 DEG C；The time of the activation pore-creating is 10~180min；
The mode of the activation pore-creating is to be passed through air to carry out activation pore-creating.
Preferably, carried out while the carbonization treatment activation pore-creating the specific steps are：
In carbonisation, it is passed through air into the inert atmosphere of carbonization, carries out activation pore-creating；
The initial time for being passed through air is 50~120min after carbonization starts；
The flow for being passed through air is 5~50mL/min；The duration for being passed through air is 0.5~10min.
The present invention provides a kind of carbon aerogels, the carbon aerogels, which have, is accumulated the three-dimensional network knot formed by carbon particle
Structure；The carbon particle surface has microcellular structure.The present invention also provides a kind of preparation methods of carbon aerogels.With the prior art
It compares, the present invention has that specific surface area is low for existing carbon aerogels, and the incorporation of metal salt can be in carbon airsetting
Glue introduces metal impurities, cannot obtain ultrapure carbon aerogels material, and then limits carbon aerogels in drug loading for people
The defect for the application possibility that body or other biological are directly swallowed.
There is the carbon particle of microcellular structure to accumulate the three-dimensional network knot to be formed on a kind of surface of having obtained of the invention
The carbon aerogels of structure.The carbon aerogels show uniform meso-hole structure, and the three-dimensional sense of three-dimensional network is strong, and spatial network knot
Structure is that the carbon bead for being about 20nm by diameter is accumulated, the arrangement between bead with connect closely, overall structure is complete.
And not only there is carbon aerogels provided by the invention carbon bead to accumulate the meso-hole structure to be formed, and carbon bead itself also has largely
Microcellular structure compare existing carbon aerogels, increase up to greatly enhance the specific surface area of carbon aerogels
150% or so.
And the present invention is by chemically synthesized method, using resorcinol and monoaldehyde as raw material, with hexamethylenetetramine
Phenolic aldehyde high polymer is formed for organic catalyst, carbon aerogels have been obtained using constant pressure and dry method and subsequent high temperature cabonization, it is real
The normal pressure preparation for having showed carbon aerogels, avoids the high cost and risk of conventional supercritical fluid drying means, while also abandoning
Solvent exchange step during conventional atmospheric drying means greatly reduces the generation of environmental pollution.Meanwhile the present invention also mentions
Go out and be passed through dry air appropriate during carbonization, to carry out partial air activation pore-creating, has further increased gained carbon gas
The specific surface area of gel optimizes the specific surface area feature and microscopic void characteristic of carbon aerogels.Carbon airsetting provided by the invention
The preparation method of glue effectively overcomes, and it is poor to generate biggish capillary pressure during constant pressure and dry, leads to carbon aerogels three
It ties up network structure part to collapse, the defect for causing the specific surface area of carbon aerogels less than normal.
In addition, it is contemplated that the requirement with drug loading to carbon aerogels free from admixture and high-purity, the present invention particularly use
Organic catalyst avoids traditional inorganic metal basic catalyst to the shadow of carbon aerogels purity as phenolic aldehyde polymerization accelerant
It rings, realizes fabulous biocompatibility.Ultrapure carbon aerogels prepared by the present invention with superhigh specific surface area are in food-grade
Drug loading, catalyst load, substance adsorber, the fields such as energy storage material are widely used, and preparation method process is simply easy
In control, it is low in cost, be convenient for utilization and extention, be suitable for industrialized large-scaled production application.
The experimental results showed that the BET specific surface area for the carbon aerogels that the present invention is prepared is up to about 1200m2/ g, in medicine
Object load and energy-storage lithium battery electrode material or supercapacitor etc. have broad application prospects.
Detailed description of the invention
Fig. 1 is the field emission scanning electron microscope FESEM figure of ultrapure carbon aerogels prepared by the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope TEM figure of ultrapure carbon aerogels prepared by the embodiment of the present invention 2；
Fig. 3 is the isothermal nitrogen adsorption desorption curve of ultrapure carbon aerogels prepared by the embodiment of the present invention 3.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described below with reference to embodiment, but
It is it should be appreciated that these descriptions only require the invention patent to further illustrate the features and advantages of the present invention
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or carbon aerogels material
The common purity in material field.
All raw materials of the present invention, the trade mark and abbreviation belong to this field routine trade mark and abbreviation, each trade mark and abbreviation
In the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and corresponding purposes,
It can be commercially available from city's mid-sales or conventional method is prepared.
The present invention provides a kind of carbon aerogels, and the carbon aerogels, which have, is accumulated the three-dimensional network knot formed by carbon particle
Structure；
The carbon particle surface has microcellular structure.
Other patterns and parameter of the carbon particle are not particularly limited in the present invention, with well known to those skilled in the art
The conventional pattern and parameter of carbon particle, those skilled in the art can be according to practical situations, product quality and productions
Moral character can be carried out selection and adjustment, and carbon particle of the present invention is preferably carbon bead.The partial size of carbon particle of the present invention is preferred
For 16~25nm, more preferably 17~23nm, more preferably 18~21nm, more preferably 19~20nm, it is specifically as follows 16~
20nm。
Carbon particle surface of the present invention has microcellular structure, and the present invention is not special to the pattern and parameter of the micropore
Limitation, with the conventional pattern and parameter of micropore well known to those skilled in the art, those skilled in the art can be according to reality
Border applicable cases, product quality and properties of product are selected and are adjusted, and the aperture of micropore of the present invention is preferably 0.01
~2nm, more preferably 0.05~1.8nm, more preferably 0.1~1.5nm, more preferably 0.5~1.0nm.In the present invention, institute
Meso-hole structure can also be had by stating carbon particle surface, and the mesoporous aperture is preferably smaller than equal to 5nm, i.e. 2~5nm, more preferably
For 2.5~4.5nm, more preferably 3~4nm.
The present invention accumulates the specific stacked form for the three-dimensional net structure to be formed to the carbon particle and network structure does not have
There is special limitation, the three-dimensional net structure with the stacked form of carbon particle well known to those skilled in the art and carbon aerogels is
Can, those skilled in the art can select and adjust, this hair according to practical situations, product quality and properties of product
The bright carbon particle accumulation is particularly preferred as carbon particle accumulation interconnected.It is preferably straight chain between carbon particle of the present invention
Carbon beam is attached.Carbon particle accumulates to form three-dimensional net structure in carbon aerogels of the present invention, while in network structure
Also form the meso-hole structure of carbon aerogels.
Mesoporous parameter of the present invention is not particularly limited, with the mesoporous of carbon aerogels well known to those skilled in the art
Parameter, those skilled in the art can select and adjust according to practical situations, product quality and properties of product
Whole, mesoporous aperture of the present invention is preferably 2~45nm, more preferably 7~40nm, more preferably 12~35nm, more preferably
For 17~30nm, more preferably 22~25nm.
The specific carbon source selection of the carbon aerogels is not particularly limited in the present invention, with well known to those skilled in the art
The conventional carbon source of carbon aerogels, those skilled in the art can be according to practical situations, product quality and products
It can be carried out selection and adjustment, the present invention is the special construction for guaranteeing carbon aerogels, and the carbon aerogels preferably include phenolic resin
Base carbon aerogels.
The parameter of the carbon aerogels is not particularly limited in the present invention, and those skilled in the art can be according to practical application
Situation, product quality and properties of product are selected and are adjusted, and carbon aerogels provided by the invention are preferably ultrapure carbon airsetting
Glue is specifically as follows the ultrapure carbon aerogels without elementary metal impurities.The specific surface area of carbon aerogels of the present invention is preferred
For 1000~3000m2/ g, more preferably 1100~2500m2/ g, more preferably 1200~2000m2/ g, more preferably 1300~
1500m2/g.Carbon aerogels porosity of the present invention is preferably 85%~98%, and more preferably 87%~96%, more preferably
89%~94%, more preferably 91%~92%.The ratio of micropore is preferably 55%~85% in carbon aerogels of the present invention,
More preferably 60%~80%, more preferably 65%~75%.The ratio of carbon aerogels intermediary hole of the present invention is preferably
15%~45%, more preferably 20%~40%, more preferably 25%~35%.
In the present invention, the carbon aerogels are preferably obtained after constant pressure and dry, carbonization and pore-creating by organogel, more excellent
Choosing is obtained after constant pressure and dry, carbonization and air pore-creating by organogel.The present invention is to the organogel (organic aerogel)
Source be not particularly limited, can be according to routine with the usual sources of organogel well known to those skilled in the art
Preparation method preparation or commercially available purchase, those skilled in the art can according to practical situations, product quality and
Properties of product are selected and are adjusted, and organogel of the present invention is preferably organic pure condensate glue.
The present invention also provides a kind of preparation methods of carbon aerogels, include the following steps：
1) after being mixed phenolic compound, aldehyde compound, organic basic catalysts and solvents, in confined conditions
Aging is carried out, solid product is obtained；
2) solid product for obtaining above-mentioned steps obtains novolac polymer after drying；
3) organogel for obtaining above-mentioned steps obtains carbon aerogels after carbonization treatment and activation pore-creating；
The carbonization treatment and activation pore-creating are lived while including first carbonization treatment reactivation pore-creating or carbonization treatment
Change pore-creating.
Selection, ratio and parameter and the corresponding optimum principle of raw material or product in the above-mentioned preparation method of the present invention
Deng equal with raw material selection, ratio and the parameter in aforementioned carbon aerogels, and corresponding optimum principle etc. if nothing especially indicates
It corresponds to each other, this is no longer going to repeat them.
After the present invention first mixes phenolic compound, aldehyde compound, organic basic catalysts and solvents, close
Aging is carried out under the conditions of closing, and obtains solid product.
The selection of the phenolic compound is not particularly limited in the present invention, prepares phenol with well known to those skilled in the art
The routine phenol compound of aldehyde polymer, those skilled in the art can according to practical situations, product quality and
Properties of product are selected and are adjusted, and phenolic compound of the present invention preferably includes resorcinol, phenol, cresols, dimethyl
One of phenol, nonyl phenol, bisphenol-A, Bisphenol F, propylphenol and ethyl -phenol are a variety of, more preferably resorcinol, benzene
Phenol, cresols, dimethyl phenol, nonyl phenol, bisphenol-A, Bisphenol F, propylphenol or ethyl -phenol.
The selection of the aldehyde compound is not particularly limited in the present invention, prepares phenol with well known to those skilled in the art
The conventional aldehyde compound of aldehyde polymer, those skilled in the art can according to practical situations, product quality and
Properties of product are selected and are adjusted, and aldehyde compound of the present invention preferably includes monoaldehyde, more preferably include formaldehyde, second
One of aldehyde, propionic aldehyde, butyraldehyde, furfural and valeral are a variety of, more preferably formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, furfural or valeral.
The dosage of the phenolic compound and aldehyde compound is not particularly limited in the present invention, with those skilled in the art
The well known conventional amount used for preparing novolac polymer, those skilled in the art can be according to practical situations, product matter
Amount and properties of product are selected and are adjusted, and the molal volume of phenolic compound and aldehyde compound of the present invention is than preferred
For 1mol：(20~600) mL, more preferably 1mol：(120~500) mL, more preferably 1mol：(220~400) mL, more preferably
For 1mol：(270~350) mL.
The selection of the organic basic catalyst is not particularly limited in the present invention, with system well known to those skilled in the art
The Conventional organic base catalyst of standby novolac polymer, those skilled in the art can be according to practical situations, product
Quality and properties of product are selected and are adjusted, and the present invention obtains the ultrapure carbon aerogels of not metal impurities, described organic
Basic catalyst preferably includes nonmetallic aminated compounds, more preferably include hexamethylenetetramine, triethylamine, ethylenediamine, urea,
One of melamine and pyrazoles are a variety of, more preferably hexamethylenetetramine, triethylamine, ethylenediamine, urea, melamine
Or pyrazoles.
The dosage of the organic basic catalyst is not particularly limited in the present invention, with system well known to those skilled in the art
The conventional amount used of standby novolac polymer, those skilled in the art can be according to practical situations, product quality and production
Moral character can be carried out selection and adjustment, and the mass ratio of organic basic catalyst and phenolic compound of the present invention is preferably (0.001
~0.4)：1, more preferably (0.001~0.4)：1, more preferably (0.005~0.35)：1, more preferably (0.01~0.3)：
1, more preferably (0.05~0.25)：1, more preferably (0.1~0.2)：1.
The selection of the solvent is not particularly limited in the present invention, prepares phenolic aldehyde polymerization with well known to those skilled in the art
The conventional organic solvent of object, those skilled in the art can be according to practical situations, product quality and properties of product
It is selected and is adjusted, solvent of the present invention preferably includes ethyl alcohol, methanol, isopropanol, propyl alcohol, N-Methyl pyrrolidone and third
One of ketone is a variety of, more preferably ethyl alcohol, methanol, isopropanol, propyl alcohol, N-Methyl pyrrolidone or acetone.
The dosage of the solvent is not particularly limited in the present invention, prepares phenolic aldehyde polymerization with well known to those skilled in the art
The conventional amount used of object, those skilled in the art can carry out according to practical situations, product quality and properties of product
The mass volume ratio of selection and adjustment, organic basic catalyst of the present invention and the solvent is preferably 1g：(0.05~30)
L, more preferably 1g：(0.1~25) L, more preferably 1g：(0.05~30) L, more preferably 1g：(0.05~30) L, more preferably
For 1g：(0.05~30) L.
The present invention is to further increase reaction efficiency, guarantees the performance of final products, complete and refinement preparation process, above-mentioned
Step, i.e. step 1) are specifically as follows：
11) phenolic compound and aldehyde compound are pre-mixed, obtain solution；
12) into the solution that above-mentioned steps obtain, organic basic catalysts and solvents is sequentially added and are mixed again, are then existed
Aging is carried out under confined conditions, obtains solid product；
The concrete mode and parameter of the premixing is not particularly limited in the present invention, with well known to those skilled in the art
Hybrid mode and parameter, those skilled in the art can according to practical situations, product quality and properties of product into
Row selection and adjustment, premixing of the present invention are preferably stirred, and more preferably stirring in water bath mixes.It is of the present invention pre-
Mixed temperature is preferably 20~80 DEG C, more preferably 30~70 DEG C, more preferably 40~60 DEG C.Premixing of the present invention
Time is preferably 5~120min, more preferably 25~100min, more preferably 45~80min.
The concrete mode mixed again and parameter is not particularly limited in the present invention, known to those skilled in the art
Hybrid mode and parameter, those skilled in the art can be according to practical situations, product quality and properties of product
It is selected and is adjusted, mixing again of the present invention is preferably stirred, and more preferably stirring in water bath mixes.Institute of the present invention
Stating the temperature mixed again is preferably 20~80 DEG C, more preferably 30~70 DEG C, more preferably 40~60 DEG C.It is of the present invention again
The secondary mixed time is preferably 10~90min, more preferably 20~80min, more preferably 30~70min, more preferably 40~
60min。
The concrete mode and parameter of the aging is not particularly limited in the present invention, with well known to those skilled in the art old
Change mode and parameter, those skilled in the art can carry out according to practical situations, product quality and properties of product
Selection and adjustment, the temperature of aging of the present invention is preferably 20~80 DEG C, more preferably 30~70 DEG C, more preferably 40~60
℃.The time of aging of the present invention is preferably 1~10 day, more preferably 3~8 days, more preferably 5~6 days.
The solid product that the present invention then obtains above-mentioned steps obtains novolac polymer after drying, i.e., organic solidifying
Glue.
The concrete mode and parameter of the drying is not particularly limited in the present invention, with baking well known to those skilled in the art
Dry mode and parameter, those skilled in the art can carry out according to practical situations, product quality and properties of product
Selection and adjustment, the present invention are further to refine preparation process, and it is also preferable to include drying steps before the drying.It is of the present invention
It is dry preferably to spontaneously dry, the time of the natural drying is preferably 5~for 24 hours, more preferably 8~21h, more preferably 12~
18h.The temperature of the drying is preferably 30~150 DEG C, more preferably 50~120 DEG C, more preferably 70~100 DEG C.The present invention
The time of the drying is preferably 1~15 day, more preferably 4~12 days, more preferably 7~9 days.
The organogel that the present invention finally obtains above-mentioned steps obtains carbon airsetting after carbonization treatment and activation pore-creating
Glue.
The concrete mode and parameter of the carbonization treatment is not particularly limited in the present invention, known to those skilled in the art
Carbonization treatment mode and parameter, those skilled in the art can be according to practical situations, product quality and product
Performance is selected and is adjusted, and the present invention is further to refine preparation process, guarantees the performance of final products, the carbonization treatment
Time be preferably 1.5~6h, more preferably 2.5~5h, more preferably 3.5~4h.The temperature of the carbonization treatment is preferably
500~1200 DEG C, more preferably 600~1100 DEG C, more preferably 700~1000 DEG C, more preferably 800~900 DEG C.The present invention
The atmosphere of the carbonization treatment is preferably nitrogen and/or inert gas, more preferably nitrogen or inert gas, more preferably nitrogen
Or argon gas.
The concrete mode and parameter of the activation pore-creating is not particularly limited in the present invention, known to those skilled in the art
Activation pore-creating mode and parameter, those skilled in the art can be according to practical situations, product quality and product
Performance is selected and is adjusted, and the present invention is further to refine preparation process, guarantees the performance of final products, work of the present invention
The mode for changing pore-creating is preferably to be passed through air to carry out activation pore-creating.The time of activation pore-creating of the present invention is preferably 10~
180min, more preferably 30~150min, more preferably 60~120min.The temperature of the activation pore-creating is preferably 700~
1200 DEG C, more preferably 800~1100 DEG C, more preferably 900~1000 DEG C.
Carbonization treatment of the present invention and activation pore-creating preferably include the reactivation pore-creating of first carbonization treatment or carbonization treatment
It carries out carrying out activation pore-creating while activation pore-creating, more preferably carbonization treatment simultaneously.The present invention is preferably to improve final produce
The performance of product guarantees its structure, preferably optimizes preparation process, and carbonization treatment while carries out the specific step of activation pore-creating
It suddenly is in carbonisation, to be passed through air into the inert atmosphere of carbonization, carry out activation pore-creating.
The initial time of the present invention for being passed through air is preferably to be carbonized in 50~120min after starting, and more preferably 60
~110min, more preferably 70~100min, more preferably 80~90min.The flow for being passed through air is preferably 5~
50mL/min, more preferably 15~40mL/min, more preferably 25~30mL/min.It is of the present invention be passed through air it is lasting when
Between preferably 0.5~10min, more preferably 2.5~8min, more preferably 4.5~6min.
Above-mentioned steps of the present invention provide a kind of ultrapure carbon gas with superhigh specific surface area based on air-activated pore-creating
Gel and preparation method thereof.The present invention is by chemically synthesized method, using resorcinol and monoaldehyde as raw material, with six methines
Tetramine is that organic catalyst forms phenolic aldehyde high polymer, has obtained carbon airsetting using constant pressure and dry method and subsequent high temperature cabonization
Glue realizes the normal pressure preparation of carbon aerogels, avoids the high cost and risk of conventional supercritical fluid drying means, while also getting rid of
The solvent exchange step during conventional atmospheric drying means has been abandoned, the generation of environmental pollution is greatly reduced.The present invention uses
Organic matter avoids conventional alkaline catalyst (such as sodium carbonate, potassium carbonate) and mixes metal member in carbon aerogels as catalyst
Plain impurity, sodium element and potassium element etc. have established important foundation to obtain ultrapure carbon aerogels.Also, the present invention uses normal pressure
Drying process has abandoned the high cost of traditional supercritical drying process, the complicated technology of high-risk.In order to improve constant pressure and dry
The specific surface area of carbon aerogels, the present invention creatively propose to be suitably added the sky of small flow while high temperature cabonization processing
Gas carries out activation pore-creating, further increases the specific surface area of gained carbon aerogels, optimizes the specific surface area feature of carbon aerogels
With microscopic void characteristic, a large amount of 5nm micropore below successfully is obtained in the carbon aerogel particles surface etch of 20nm rank, greatly
The specific surface area of carbon aerogels is increased greatly, compensates for that generate biggish capillary pressure during constant pressure and dry poor, leads to carbon
Aeroge three-dimensional net structure part collapses, the defect for causing the specific surface area of carbon aerogels less than normal.
The present invention has obtained a kind of carbon gas that there is the carbon particle of microcellular structure to accumulate the three-dimensional net structure to be formed on surface
Gel.The carbon aerogels show uniform meso-hole structure, and the three-dimensional sense of three-dimensional network is strong, and spacial framework is by straight
The carbon bead that diameter is about 20nm is accumulated, the arrangement between bead with connect closely, overall structure is complete.And this hair
Not only there is the carbon aerogels of bright offer carbon bead to accumulate the meso-hole structure to be formed, and carbon bead itself also has a large amount of micropore knot
Structure compares existing carbon aerogels, has increased up to 150% or so to greatly enhance the specific surface area of carbon aerogels.
In addition, it is contemplated that the requirement with drug loading to carbon aerogels free from admixture and high-purity, the present invention particularly use
Organic catalyst avoids traditional inorganic metal basic catalyst to the shadow of carbon aerogels purity as phenolic aldehyde polymerization accelerant
It rings, realizes fabulous biocompatibility.Ultrapure carbon aerogels prepared by the present invention with superhigh specific surface area are in food-grade
Drug loading, catalyst load, substance adsorber, the fields such as energy storage material are widely used, and preparation method process is simply easy
In control, it is low in cost, be convenient for utilization and extention, be suitable for industrialized large-scaled production application.
The experimental results showed that the BET specific surface area for the carbon aerogels that the present invention is prepared is up to about 1200m2/ g, in medicine
Object load and energy-storage lithium battery electrode material or supercapacitor etc. have broad application prospects.
In order to further illustrate the present invention, with reference to embodiments to a kind of carbon aerogels provided by the invention and its preparation
Method is described in detail, but it is to be understood that and these embodiments are to be implemented under the premise of the technical scheme of the present invention,
The detailed implementation method and specific operation process are given, only to further illustrate the features and advantages of the present invention, without
It is limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiments.
Embodiment 1
0.5g resorcinol is taken to be slowly added in the formalin of 3.5mL, after 40 DEG C of stirring in water bath 10min of constant temperature, then plus
Enter the hexamethylenetetramine of 0.005g, while pouring into the ethanol solution of 20mL, stirs evenly.Then it is put after acquired solution being sealed
Enter in 80 DEG C of baking ovens, keeps the temperature aging 3 days.Phenolic aldehyde gelatin polymer after aging is taken out, puts and is spontaneously dried in air,
Time 5h.Then phenolic aldehyde gel is placed in 80 DEG C of baking oven 2 days dry.The complete phenolic aldehyde gel of drying is placed in full of argon gas
High temperature furnace in 800 DEG C be carbonized 2 hours.In order to further obtain the carbon aerogels of superhigh specific surface area, during carbonization, simultaneously
It is passed through air, the flow velocity of air is 10mL/min, and being continually fed into the time is 8min, obtains having based on air-activated pore-creating and surpasses
The ultrapure carbon aerogels of high-specific surface area.
The carbon aerogels prepared to the embodiment of the present invention 1 characterize.
Referring to Fig. 1, Fig. 1 is the field emission scanning electron microscope of ultrapure carbon aerogels prepared by the embodiment of the present invention 1
FESEM figure.
As shown in Figure 1, ultrapure carbon aerogels prepared by the present invention show uniform meso-hole structure, the solid of three-dimensional network
Feel very strong, which is that the carbon bead for being about 20nm by diameter is accumulated, and overall structure is very complete.
The test of isothermal nitrogen adsorption desorption is carried out to carbon aerogels prepared by the embodiment of the present invention 1, the results showed that, as a result table
Bright, the specific surface area of carbon aerogels prepared by the present invention is 1135m2/g。
Embodiment 2
0.5g resorcinol is taken to be slowly added in the acetaldehyde solution of 3.5mL, after 40 DEG C of stirring in water bath 10min of constant temperature, then plus
Enter the hexamethylenetetramine of 0.1g, while pouring into the ethanol solution of 50mL, stirs evenly.Then it is put into after acquired solution being sealed
In 80 DEG C of baking ovens, aging 7 days are kept the temperature.Phenolic aldehyde gelatin polymer after aging is taken out, puts and is spontaneously dried in air, when
Between 5h.Then phenolic aldehyde gel is placed in 80 DEG C of baking oven 2 days dry.The complete phenolic aldehyde gel of drying is placed in full of argon gas
It is carbonized 2 hours for 800 DEG C in high temperature furnace.In order to further obtain the carbon aerogels of superhigh specific surface area, during carbonization, lead to simultaneously
Enter air, the flow velocity of air is 10mL/min, and being continually fed into the time is 8min, obtains having superelevation based on air-activated pore-creating
The ultrapure carbon aerogels of specific surface area.
The carbon aerogels prepared to the embodiment of the present invention 2 characterize.
Referring to fig. 2, Fig. 2 is the transmission electron microscope TEM figure of ultrapure carbon aerogels prepared by the embodiment of the present invention 2.
As shown in Figure 2, in ultrapure carbon aerogels prepared by the present invention, in carbon aerogels the small ball's diameter 16~20nm it
Between, arrangement between bead with connect closely, about in 15nm or so, obtained carbon aerogels pore structure is complete in aperture
Whole, mesoporous distribution is more.
The test of isothermal nitrogen adsorption desorption is carried out to carbon aerogels prepared by the embodiment of the present invention 2, the results showed that, system of the present invention
The specific surface area of standby carbon aerogels is 1014m2/g。
Embodiment 3
0.5g resorcinol is taken to be slowly added in the acetaldehyde solution of 3.5mL, after 40 DEG C of stirring in water bath 10min of constant temperature, then plus
Enter the hexamethylenetetramine of 0.1g, while pouring into the ethanol solution of 50mL, stirs evenly.Then it is put into after acquired solution being sealed
In 80 DEG C of baking ovens, aging 7 days are kept the temperature.Phenolic aldehyde gelatin polymer after aging is taken out, puts and is spontaneously dried in air, when
Between 5h.Then phenolic aldehyde gel is placed in 80 DEG C of baking oven 2 days dry.The complete phenolic aldehyde gel of drying is placed in full of argon gas
It is carbonized 2 hours for 800 DEG C in high temperature furnace.In order to further obtain the carbon aerogels of superhigh specific surface area, during carbonization, lead to simultaneously
Enter air, the flow velocity of air is 15mL/min, and being continually fed into the time is 5min, obtains having superelevation based on air-activated pore-creating
The ultrapure carbon aerogels of specific surface area.
The test of isothermal nitrogen adsorption desorption is carried out to carbon aerogels prepared by the embodiment of the present invention 3, the results showed that, system of the present invention
The specific surface area of standby carbon aerogels is 1271m2/g。
Referring to Fig. 3, Fig. 3 is the isothermal nitrogen adsorption desorption curve of ultrapure carbon aerogels prepared by the embodiment of the present invention 3.
Embodiment 4
It takes 0.5g resorcinol to be slowly added in the furfuryl aldehyde solution of 10mL, after 60 DEG C of stirring in water bath 10min of constant temperature, adds
The hexamethylenetetramine of 0.02g, while the ethanol solution of 32mL is poured into, it stirs evenly.Then it is put into after acquired solution being sealed
In 80 DEG C of baking ovens, aging 7 days are kept the temperature.Phenolic aldehyde gelatin polymer after aging is taken out, puts and is spontaneously dried in air, when
Between 5h.Then phenolic aldehyde gel is placed in 80 DEG C of baking oven 2 days dry.The complete phenolic aldehyde gel of drying is placed in full of argon gas
It is carbonized 3 hours for 1000 DEG C in high temperature furnace.In order to further obtain the carbon aerogels of superhigh specific surface area, during carbonization, simultaneously
It is passed through air, the flow velocity of air is 15mL/min, and being continually fed into the time is 5min, obtains having based on air-activated pore-creating and surpasses
The ultrapure carbon aerogels of high-specific surface area.
The test of isothermal nitrogen adsorption desorption is carried out to carbon aerogels prepared by the embodiment of the present invention 4, the results showed that, system of the present invention
The specific surface area of standby carbon aerogels is 1298m2/g。
Above to a kind of ultrapure carbon airsetting with superhigh specific surface area based on air-activated pore-creating provided by the invention
Glue and preparation method thereof.It is described in detail, specific case used herein is to the principle of the present invention and embodiment
It is expounded, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas, including best
Mode, and but also any person skilled in the art can practice the present invention, including any device of manufacture and use or
System, and implement the method for any combination.It should be pointed out that for those skilled in the art, not departing from
, can be with several improvements and modifications are made to the present invention under the premise of the principle of the invention, these improvement and modification also fall into this hair
In bright scope of protection of the claims.The range of the invention patent protection is defined by the claims, and may include this field
Technical staff it is conceivable that other embodiments.If these other embodiments, which have, is not different from claim character express
Structural element, or if they include the equivalent structural elements with the character express of claim without essence difference,
These other embodiments should also be included in the scope of the claims.
Claims (10)
1. a kind of carbon aerogels, which is characterized in that the carbon aerogels, which have, is accumulated the three-dimensional net structure formed by carbon particle；
The carbon particle surface has microcellular structure.
2. carbon aerogels according to claim 1, which is characterized in that the carbon aerogels include phenolic resin base carbon airsetting
Glue；
The specific surface area of the carbon aerogels is 1000~3000m2/g；
The aperture of the micropore is 0.01~2nm；
The partial size of the carbon particle is 16~25nm.
3. carbon aerogels according to claim 1, which is characterized in that the carbon particle accumulation is specially carbon interconnected
Particle packing；
The carbon aerogels have meso-hole structure；
The mesoporous aperture is 2~45nm；
The carbon aerogels are the ultrapure carbon aerogels without elementary metal impurities.
4. carbon aerogels according to claim 1, which is characterized in that the porosity of the carbon aerogels be 85%~
98%；
The ratio of micropore is 55%~85% in the carbon aerogels；
The ratio of the carbon aerogels intermediary hole is 15%~45%；
The carbon aerogels are obtained after constant pressure and dry, carbonization and pore-creating by organogel.
5. a kind of preparation method of carbon aerogels, which is characterized in that include the following steps：
1) it after being mixed phenolic compound, aldehyde compound, organic basic catalysts and solvents, carries out in confined conditions
Aging obtains solid product；
2) solid product for obtaining above-mentioned steps obtains novolac polymer after drying；
3) organogel for obtaining above-mentioned steps obtains carbon aerogels after carbonization treatment and activation pore-creating；
The carbonization treatment and activation pore-creating carry out activation while including first carbonization treatment reactivation pore-creating or carbonization treatment and make
Hole.
6. preparation method according to claim 5, which is characterized in that the phenolic compound include resorcinol, phenol,
One of cresols, dimethyl phenol, nonyl phenol, bisphenol-A, Bisphenol F, propylphenol and ethyl -phenol are a variety of；
The aldehyde compound includes monoaldehyde；
The organic basic catalyst includes nonmetallic aminated compounds；
The solvent includes one of ethyl alcohol, methanol, isopropanol, propyl alcohol, N-Methyl pyrrolidone and acetone or a variety of.
7. preparation method according to claim 5, which is characterized in that mole of the phenolic compound and aldehyde compound
Volume ratio is 1mol：(20~600) mL；
The mass ratio of the organic basic catalyst and phenolic compound is (0.001~0.4)：1；
The mass volume ratio of the organic basic catalyst and the solvent is 1g：(0.05~30) L；
The aldehyde compound includes one of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, furfural and valeral or a variety of；
The organic basic catalyst includes in hexamethylenetetramine, triethylamine, ethylenediamine, urea, melamine and pyrazoles
It is one or more.
8. preparation method according to claim 5, which is characterized in that the step 1) is specially：
11) phenolic compound and aldehyde compound are pre-mixed, obtain solution；
12) into the solution that above-mentioned steps obtain, organic basic catalysts and solvents is sequentially added and are mixed again, then closed
Under the conditions of carry out aging, obtain solid product；
The temperature of the premixing is 20~80 DEG C；The time of the premixing is 5~120min；
The temperature mixed again is 20~80 DEG C；The time mixed again is 10~90min；
The temperature of the aging is 30~90 DEG C；The time of the aging is 1~10 day.
9. preparation method according to claim 5, which is characterized in that the temperature of the drying is 30~150 DEG C；
The time of the drying is 1~15 day；
The temperature of the carbonization treatment is 500~1200 DEG C；The time of the carbonization treatment is 1.5~6h；The carbonization treatment
Atmosphere be nitrogen and/or inert gas；
The temperature of the activation pore-creating is 700~1200 DEG C；The time of the activation pore-creating is 10~180min；
The mode of the activation pore-creating is to be passed through air to carry out activation pore-creating.
10. according to preparation method described in claim 5~9 any one, which is characterized in that while the carbonization treatment into
Row activation pore-creating the specific steps are：
In carbonisation, it is passed through air into the inert atmosphere of carbonization, carries out activation pore-creating；
The initial time for being passed through air is 50~120min after carbonization starts；
The flow for being passed through air is 5~50mL/min；The duration for being passed through air is 0.5~10min.
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| CN113694892A (en) * | 2021-08-27 | 2021-11-26 | 伯克利南京医学研究有限责任公司 | Carbon aerogel composite structure, composite filter element, preparation methods of carbon aerogel composite structure and composite filter element, and application of carbon aerogel composite structure and composite filter element |
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