CN107117623A - A kind of preparation method with micropore and order mesoporous silica/carbon nanomaterial - Google Patents
A kind of preparation method with micropore and order mesoporous silica/carbon nanomaterial Download PDFInfo
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- CN107117623A CN107117623A CN201710474571.2A CN201710474571A CN107117623A CN 107117623 A CN107117623 A CN 107117623A CN 201710474571 A CN201710474571 A CN 201710474571A CN 107117623 A CN107117623 A CN 107117623A
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The present invention discloses a kind of preparation method with micropore and order mesoporous silica/carbon nanomaterial, mainly includes the following steps that：Template is dissolved, resorcinol and formaldehyde is then sequentially added, silane coupler is added, ammoniacal liquor is eventually adding, gel is obtained；Obtained gel is fitted into reactor and carries out crystallization, then then suction filtration, washing dried to neutrality；Gained sample is flowed back, removed template method；Sample obtained in the previous step is put into tube furnace, in being calcined under inert gas atmosphere, finally given with micropore and order mesoporous silica/carbon nanomaterial.The present invention provides the preparation method with micropore and order mesoporous silica/carbon nanomaterial of synthesis, its material prepared has micro- Jie's bimodulus type hole, and the preparation method has preparation technology simple, with low cost, it is mesoporous in order, size is controllable and the advantages of narrow distribution range.
Description
Technical field
The invention belongs to Inorganic synthese it is micro--mesoporous materials field, more particularly to it is a kind of have micropore and order mesoporous oxygen
The preparation method of SiClx/carbon nanomaterial.
Background technology
Porous material has obtained extensive research in current science and technology field, includes the purifying of water and air, point
From, catalysis, the storage and conversion of sensor, semi-conducting material and the energy etc..Because it has high specific surface area, big hole body
Product, preferably chemically and thermally mechanical stability the features such as, especially orderly mesoporous material has pore-size distribution compared with narrow and aperture is big
Small and space structure can be adjusted in a wide range.
The features such as silica/carbon nanometer material has the chemistry, thermodynamics and mechanical stability of uniqueness, and by more and more
Scholar concern.Its synthetic method is more, Shi Yifeng et al. (Chem.Mater., 2007,19:1761-1771) synthesize
Mesoporous silicon SBA-15 materials as hard template, polysiloxanes is impregnated into by organic solvent evaporation nm immersion method mesoporous
In, its silica/carbon material synthesized has preferably single order mesoporous.But, the synthesis step of the synthetic method it is many, it is necessary to
The deficiencies such as the conditions such as high temperature.One-step method for synthesizing is simple to operation, therefore Tamayo Aitana et al. (Journal of Non-
Crystalline Solids,2010,356:1742-1748) tetraethyl orthosilicate and polymer are closed by the step of sol-gel one
Into the mixing material for obtaining macropore, the process of preparation by colloidal sol, hydrolysis, polymerization etc., mixing material be sufficiently mixed it is organic with
Inorganic two parts.But this mixing material, aperture is macropore and pore size distribution range is wide, will limit the extensive of mixing material
Application.In addition to preparing silica/carbon nanomaterial by organic and inorganic mixing crosslinking, Assefa et al. (Ceramics
International,2016,42:11805-11809) it is crosslinked using two kinds of organopolysiloxanes, one-step synthesis goes out mixing
Material, but the material has the problems such as carburizing temperature is high, specific surface area is small, pore size distribution range is wide.Mietek Jaronie
Et al. (J.Mater.Chem., 2012,22:The effect for adding tetraethyl orthosilicate 12636-12642) is investigated in article, just
The combination of silester and phenolic resin (RF) helps to increase the specific surface area of carbon ball micropore.Work before our seminar
(Langmuir 2017,33:Conclusion above also 1248-1255) is demonstrated in the synthesis of carbon material, tetraethyl orthosilicate is not only
Can as micropore perforating agent, can also play meso-porous carbon material assistance drilling effect.Dai et al. (Nano
Lett.2013,13:207-212) using the copolymerization of tetraethyl orthosilicate (TEOS), resorcinol (R) and formaldehyde (F), and with 16
Alkyl trimethyl ammonium chloride (CTAC) is prepared with mesoporous carbon ball as template.Based on research above, it is proposed that two
Silica assists self assembly preparating mechanism, and the anion and cation template of silica surface have very strong interaction
Power, this is successfully to prepare mesoporous key.Sun et al. (Chem.Commun., 2015:51-10517) equally with side above
Method, the course of reaction based on sol-gel prepares mesoporous carbon spheres.Yu et al. (J.Mater.Chem.A, 2016:4-9063) adopt
With tetraethyl orthosilicate (TEOS) and DOPA amine copolymer, the principle based on slica-polymer produces meso-porous hollow carbon after removing silicon
Ball.
The content of the invention
To solve the above problems, there is micropore and order mesoporous silica/carbon nanomaterial the invention provides a kind of
Preparation method, solve the difficult functionalization of carbon nanomaterial, the problems such as building-up process is complicated and carbon distribution is remained.
A kind of preparation method with micropore and order mesoporous silica/carbon nanomaterial of present invention offer, including with
Lower step：
Step 1, template dissolved, then sequentially adds resorcinol and formaldehyde, add silane coupler, finally plus
Enter ammoniacal liquor, obtain gel；
Step 2, obtained gel be fitted into reactor carry out crystallization, then suction filtration, wash to neutrality, then dry；
Step 3, the sample that step 2 is obtained flowed back, removed template method；
Step 4, the sample for obtaining step 3 are finally given with micropore and orderly Jie in being calcined under inert gas atmosphere
Silica/the carbon nanomaterial in hole.
The preparation method is specially：
Step 1, addition 54-104mL water and 0-50mL absolute ethyl alcohols into 2-3g templates, dissolve it, then successively
Add the analytically pure resorcinols of 0.984-3.28g and 372-1240 μ L mass fractions are 37-40% formaldehyde, then be added dropwise
The mass fraction of 4-10mL silane coupler, wherein silane coupler meets its correspondence SiO2Mass fraction for 28% with
On, the ammoniacal liquor that 1200-2400 μ L mass fractions are 25%-28% is finally added dropwise, gel is obtained；
Step 2, obtained gel is fitted into reactor carries out crystallization, the crystallization 20-30h in 80-120 DEG C of baking oven, so
Suction filtration, washing are then placed in baking oven and dried to neutrality afterwards；
Step 3, gained sample are added to the hydrochloric acid solution institute of 200mL absolute ethyl alcohols and 1.5mL mass fractions for 36-38%
In the mixed solution of formation, 70-80 DEG C of backflow, removed template method；
Step 4, the sample that step 3 is obtained is put into tube furnace, firing chamber's temperature rise is to 350- under inert gas atmosphere
400 DEG C, constant temperature 2-3h, heating rate is 1-3 DEG C/min；600-650 DEG C, constant temperature 4-5h, heating speed are risen to by 350-400 DEG C again
Rate is 1-3 DEG C/min, is obtained with micropore and order mesoporous silica/carbon nanomaterial.
The template is quaternary ammonium salt cationic surfactant.
The quaternary ammonium salt cationic surfactant is cetyl trimethylammonium bromide or hexadecyltrimethylammonium chloride.
The silane coupler is tetraethyl orthosilicate, methyl silicate, MTMS, methyltriethoxy silane
Alkane, propyl trimethoxy silicane, propyl-triethoxysilicane, mercaptopropyl trimethoxysilane or mercaptopropyltriethoxysilane.
The molar ratio of the resorcinol and silane coupler is 20-167%.
The mol ratio of the resorcinol and formaldehyde is 1：5.
Inert gas used is nitrogen or helium.
The gas flow optimized of the inert gas is in 60-100mL/min.
Present invention has the advantage that：The preparation method for silica/carbon nanomaterial that the present invention is provided, it uses one
Step synthetic method, simplifies preparation process, it is easy to operate, and can prepare containing micropore and orderly mesoporous multi-stage porous material
Material, the size of its intermediary hole can be adjustable within the specific limits, improves the scope of materials application, is conducive to it in fields such as catalysis
Application.In addition, using the extracting method of the mesoporous template of material in the present invention so that the carbon distribution on mesoporous inwall is gone
Remove, advantageously in the application of mesoporous material.The preparation process of the present invention is low for equipment requirements without precision instrument, can save
Production cost.
Brief description of the drawings
Fig. 1 is the XRD with micropore and order mesoporous silica/carbon nanomaterial of the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph with micropore and order mesoporous silica/carbon nanomaterial of the embodiment of the present invention 1
Piece；
Fig. 3 is the cryogenic nitrogen aspiration with micropore and order mesoporous silica/carbon nanomaterial of the embodiment of the present invention 1
Desorption curve；
Fig. 4 divides for the micropore size with micropore and order mesoporous silica/carbon nanomaterial of the embodiment of the present invention 1
Cloth curve (HK methods)；
Fig. 5 divides for the mesoporous pore size with micropore and order mesoporous silica/carbon nanomaterial of the embodiment of the present invention 1
Cloth curve (BJH methods).
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
A part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill people
The every other embodiment that member is obtained on the premise of creative work is not made, belongs to the scope of protection of the invention.
In the description of the invention, it is necessary to explanation, term " " center ", " on ", " under ", "left", "right", " vertical ",
The orientation or position relationship of the instruction such as " level ", " interior ", " outer " be based on orientation shown in the drawings or position relationship, merely to
Be easy to the description present invention and simplify description, rather than indicate or imply signified device or element must have specific orientation,
With specific azimuth configuration and operation, therefore it is not considered as limiting the invention.In addition, term " first ", " second ",
" the 3rd " is only used for describing purpose, and it is not intended that indicating or implying relative importance.
In the description of the invention, in addition it is also necessary to explanation, unless otherwise clearly defined and limited, term " installation ",
" connected ", " connection " should be interpreted broadly, for example, it may be being fixedly connected or being detachably connected, or integratedly be connected
Connect；Can be mechanical connection or electrical connection；Can be joined directly together, can also be indirectly connected to by intermediary, can
To be the connection of two element internals.For the ordinary skill in the art, above-mentioned term can be understood with concrete condition
Concrete meaning in the present invention.
A kind of preparation method with micropore and order mesoporous silica/carbon nanomaterial of present invention offer, including with
Lower step：
Step 1,2-3g templates (such as alkyl trimethyl ammonium bromide) (analysis is pure) are added in flask, then add 54-
(analytically pure liquid ethanol, mass fraction is more than 99.7%), magnetic agitation to ten in 104mL water and 0-50mL absolute ethyl alcohols
Six alkyl trimethyl ammonium bromides be completely dissolved to clarification (dissolving can be allowed to molten by the way of 40-60 DEG C of heating water bath
Solution, mixing speed is not restricted), moving on to magnetic agitation under room temperature (25 DEG C), (mixing speed is slower, generally 100-300r/
Min), 0.984-3.28g resorcinols (analysis is pure) are then sequentially added, (mass fraction is 37- to 372-1240 μ L formaldehyde
40%), then be added dropwise 4-10mL silane couplers (be added dropwise silane coupler when mixing speed accelerate, generally 800r/
Min), the concentration requirement of silane coupler is its corresponding SiO2Mass fraction meet more than 28% and calculate, lasting stirring
5min-10min, then 1200-2400 μ L ammoniacal liquor (mass fraction is 25%-28%) is added dropwise, more than 24h is stirred at room temperature, is coagulated
Glue；
Step 2, the gel that step 1 is obtained is fitted into reactor, in 80-120 DEG C of (preferably 100 DEG C) baking oven crystallization 20-
30h (preferably 24h), then suction filtration, deionized water are washed to neutrality, are then placed in oven dried overnight and (are dried three times, do every time
The dry time is 3h)；
Step 3, the sample that step 2 is obtained is added to 200mL ethanol (analysis is pure, and mass fraction is more than 99.7%) and
In the mixed solution that 1.5mL hydrochloric acid (mass fraction is by 36-38%) solution is formed, 70-80 DEG C of backflow removed template method, backflow
The method for deviating from template is oil bath continuous heating, is prior art means with condensing tube condensation volatilization ethanol；
Step 4, the sample that step 3 is obtained is put into tube furnace, firing chamber's temperature rise is to 350- under inert gas atmosphere
400 DEG C, constant temperature 2-3h, heating rate is 1-3 DEG C/min；600-650 DEG C, constant temperature 4-5h, heating speed are risen to by 350-400 DEG C again
Rate is 1-3 DEG C/min, is obtained with micropore and order mesoporous silica/carbon nanomaterial.
When the molar ratio of resorcinol and silane coupler is that 20-167% (is preferably 50-100%, further preferably
For 70-80%), in the above range by changing different ratios, resulting mesoporous material is respectively provided with order.
Under inert gas shielding, the roasting to material uses nitrogen or helium, can all reach that it is imitated
Really.
Resorcinol used and the mol ratio of formaldehyde are 1：5.
The gas flow optimized of inert gas used is between 60-100mL/min.
It is quaternary ammonium salt cationic surfactant as the improvement template of the present invention, can is cetyl trimethylammonium bromide
With one kind of hexadecyltrimethylammonium chloride, it can obtain orderly mesoporous.
As the present invention improvement silane coupler selection tetraethyl orthosilicate, methyl silicate, MTMS,
MTES, propyl trimethoxy silicane, propyl-triethoxysilicane, mercaptopropyl trimethoxysilane or mercapto propyl group
One kind in triethoxysilane.
Embodiment 1
The present embodiment provides a kind of preparation method with micropore and order mesoporous silica/carbon nanomaterial, including
Following steps：
Step 1,2.6120g cetyl trimethylammonium bromides are added in flask, then add 96mL water and the anhydrous second of 8mL
Alcohol, clarification is dissolved in water-bath magnetic agitation to cetyl trimethylammonium bromide, moves on to magnetic agitation (mixing speed at room temperature
It is slower), 2.296g resorcinols (analysis is pure), 868 μ L formaldehyde (mass fraction is 37%) are then sequentially added, then add dropwise
SiO in 6mL tetraethyl orthosilicates (mixing speed is very fast), tetraethyl orthosilicate2Mass fraction meet 28%, persistently stir 5min,
1200 μ L ammoniacal liquor (mass fraction is 25%) are added dropwise, 24h is stirred at room temperature, gel is obtained；
Step 2, the gel that step 1 is obtained is fitted into reactor, in 100 DEG C of baking ovens reaction 24h, takes out sample above and take out
Filter about to neutral, is then put into oven dried overnight；
Step 3, the sample of step 2 is put into flask, then sequentially adds 200mL ethanol (analysis is pure) and 1.5mL hydrochloric acid
Solution (mass fraction is 36%), 70 DEG C of backflow removed template methods；
Step 4, the sample that step 3 is obtained is put into tube furnace, (air-flow is in 60mL/min) is roasted under nitrogen gas atmosphere
Burn, room temperature rises to 350 DEG C, and constant temperature 2h, heating rate is 1 DEG C/min；600 DEG C, constant temperature 4h, heating rate are risen to by 350 DEG C again
For 1 DEG C/min, obtain with micropore and order mesoporous silica carbon nanomaterial.
Using prepared by the preparation method of above-described embodiment 1 silica/carbon nanomaterial is through XRD diffraction analysis and sweeps
Electronic microscope photos is retouched, as depicted in figs. 1 and 2, it has obvious order mesoporous, and its mesoporous pore size is 3.3nm (as shown in Figure 5),
Specific surface area is 818m2/ g, it also has obvious micropore, and micropore size is 0.91nm (as shown in Figure 4).Silica/the carbon
The excellent adsorption of nano material, its low temperature nitrogen adsorption curve is as shown in Figure 3.
Embodiment 2
Using the experimentation of embodiment 1, it is different from part and is that the addition of absolute ethyl alcohol is 30mL, the addition of water
Measure as 74mL；The mesoporous pore size of gained silica/carbon nanomaterial is 2.8nm, and specific surface area is 884m2/ g, micropore size is
0.91nm。
Embodiment 3
Using the experimentation of embodiment 2, it is different from part and is that the amount of absolute ethyl alcohol is 40mL, the amount of water is
64mL；Resulting materials mesoporous pore size is 2.5nm, and specific surface area is 721m2/ g, micropore size is 0.86nm.
Embodiment 4
Using the experimentation of embodiment 3, it is different from part and is to be not added with absolute ethyl alcohol, water addition 104mL；Gained
The mesoporous pore size arrived is 3.5nm, and specific surface area is 645m2/ g, micropore size is 0.83nm.
Embodiment 5
Using the experimentation of embodiment 4, the ratio that part is to change tetraethyl orthosilicate and resorcinol is different from,
0.984g resorcinols and 10mL tetraethyl orthosilicates are added in the present embodiment；Resulting mesoporous pore size is 3.5nm, specific surface area
For 620m2/ g, micropore size is 0.86nm.
Embodiment 6
With the experimentation of embodiment 5, it is different from part and is to change cetyl trimethylammonium bromide into hexadecane
Base trimethyl ammonium chloride, can equally prepare silica/carbon nanomaterial.
Embodiment 7
With the experimentation of embodiment 1, it is different from part and is to change tetraethyl orthosilicate into MTMS.
Embodiment 8
With the experimentation of embodiment 1, it is different from part and is that tetraethyl orthosilicate changes MTES into.
Embodiment 9
With the experimentation of embodiment 1, it is different from part and is that tetraethyl orthosilicate changes propyl-triethoxysilicane into.
Embodiment 10
With the experimentation of embodiment 1, it is different from part and is that tetraethyl orthosilicate changes mercaptopropyl trimethoxysilane into.
Embodiment 11
With the experimentation of embodiment 1, it is different from part and is that tetraethyl orthosilicate changes mercaptopropyltriethoxysilane into.
Embodiment 12
The present embodiment provides a kind of preparation method with micropore and order mesoporous silica/carbon nanomaterial, including
Following steps：
Step 1,2g templates alkyl trimethyl ammonium bromide (analysis is pure) are added in flask, then add 104mL water and 50mL
Absolute ethyl alcohol, is completely dissolved to clarification in water-bath magnetic agitation to cetyl trimethylammonium bromide, moves on under room temperature (25 DEG C)
Magnetic agitation (mixing speed is slower), then sequentially adding 0.984 resorcinol (analysis pure), 372 formaldehyde, (mass fraction is
38%), then 4mL methyl silicates (mixing speed quickening) are added dropwise, persistently stir 10min, then 2400 μ L ammoniacal liquor (matter are added dropwise
Fraction is measured 26%), 24h to be stirred at room temperature, gel is obtained；
Step 2, the gel that step 1 is obtained is fitted into reactor, in 120 DEG C of baking oven crystallization 20h, then suction filtration, washing
To neutral, oven dried overnight is then placed in；
Step 3, step 2 gained sample is added to 200mL ethanol and 1.5mL hydrochloric acid solutions mass fraction is in 37%,
80 DEG C of backflow removed template methods；
Step 4, the sample that step 3 is obtained is put into tube furnace, (the inertia used under inert gas (helium) atmosphere
The air-flow of gas is in 60mL/min).Firing chamber's temperature rise is to 400 DEG C, and constant temperature 3h, heating rate is 3 DEG C/min；Risen again by 400 DEG C
To 650 DEG C, constant temperature 5h, heating rate for DEG C/min, obtain with micropore and order mesoporous silica/carbon nanomaterial.
Embodiment 13
The present embodiment provides a kind of preparation method with micropore and order mesoporous silica/carbon nanomaterial, including
Following steps：
Step 1,3g templates hexadecyltrimethylammonium chloride (analysis pure) are added in flask, then plus 54mL water and
5mL absolute ethyl alcohols, are completely dissolved to clarification in water-bath magnetic agitation to hexadecyltrimethylammonium chloride, move on to room temperature (25 DEG C)
Lower magnetic agitation (mixing speed is slower), then sequentially adds 3.28g resorcinols (analysis is pure), 1240 μ L formaldehyde (quality point
40%) number is, then 10mL tetraethyl orthosilicates (mixing speed quickening) are added dropwise, and persistently stirs 810min, then 1500 μ L are added dropwise
Ammoniacal liquor (mass fraction is 28%), is stirred at room temperature 36h, obtains gel；
Step 2, the gel that step 1 is obtained is fitted into reactor, in 120 DEG C of baking oven crystallization 30h, then suction filtration, washing
To neutral, oven dried overnight is then placed in；
Step 3, step 2 gained sample is added to 200mL ethanol (analysis is pure) and 1.5mL hydrochloric acid, and (mass fraction is
38%) in solution, 75 DEG C of backflow removed template methods；
Step 4, the sample that step 3 is obtained is put into tube furnace, (the inertia used under inert gas (nitrogen) atmosphere
The air-flow of gas is in 100mL/min.) firing chamber's temperature rise is to 380 DEG C, constant temperature 2.5h, heating rate is 2 DEG C/min；Again by 380 DEG C
620 DEG C are risen to, constant temperature 4.5h, heating rate is 2 DEG C/min, obtained with micropore and order mesoporous silica/carbon nanometer material
Material.
The preferred embodiments of the present invention are these are only, are not intended to limit the invention, for those skilled in the art
For member, the present invention can have various modifications and variations.Any modification within the spirit and principles of the invention, being made,
Equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (9)
1. a kind of preparation method with micropore and order mesoporous silica/carbon nanomaterial, it is characterised in that including following
Step：
Step 1, template dissolved, then sequentially add resorcinol and formaldehyde, add silane coupler, be eventually adding ammonia
Water, obtains gel；
Step 2, the gel that step 1 is obtained be fitted into reactor carry out crystallization, then suction filtration, wash to neutrality, then dry；
Step 3, the sample that step 2 is obtained flowed back, removed template method；
Step 4, the sample for obtaining step 3 are finally given with micropore and order mesoporous in being calcined under inert gas atmosphere
Silica/carbon nanomaterial.
2. the preparation method according to claim 1 with micropore and order mesoporous silica/carbon nanomaterial, it is special
Levy and be, the preparation method is specially：
Step 1, addition 54-104mL water and 0-50mL absolute ethyl alcohols into 2-3g templates, dissolve it, then sequentially add
The analytically pure resorcinols of 0.984-3.28g and 372-1240 μ L mass fractions are 37-40% formaldehyde, then 4- is added dropwise
The mass fraction of 10mL silane coupler, wherein silane coupler meets its correspondence SiO2Mass fraction be more than 28%,
The ammoniacal liquor that 1200-2400 μ L mass fractions are 25%-28% is finally added dropwise, gel is obtained；
Step 2, obtained gel is fitted into reactor carries out crystallization, then the crystallization 20-30h in 80-120 DEG C of baking oven takes out
Filter, washing are then placed in baking oven and dried to neutrality；
Step 3, gained sample are added to 200mL absolute ethyl alcohols and 1.5mL mass fractions are formed by 36-38% hydrochloric acid solution
Mixed solution in, 70-80 DEG C backflow, removed template method；
Step 4, the sample that step 3 is obtained is put into tube furnace, firing chamber's temperature rise is to 350-400 under inert gas atmosphere
DEG C, constant temperature 2-3h, heating rate is 1-3 DEG C/min；600-650 DEG C, constant temperature 4-5h, heating rate are risen to by 350-400 DEG C again
For 1-3 DEG C/min, obtain with micropore and order mesoporous silica/carbon nanomaterial.
3. the preparation method according to claim 1 with micropore and order mesoporous silica/carbon nanomaterial, it is special
Levy and be, the template is quaternary ammonium salt cationic surfactant.
4. the preparation method according to claim 3 with micropore and order mesoporous silica/carbon nanomaterial, it is special
Levy and be, the quaternary ammonium salt cationic surfactant is cetyl trimethylammonium bromide or hexadecyltrimethylammonium chloride.
5. the preparation method according to claim 1 with micropore and order mesoporous silica/carbon nanomaterial, it is special
Levy and be, the silane coupler is tetraethyl orthosilicate, methyl silicate, MTMS, methyltriethoxy silane
Alkane, propyl trimethoxy silicane, propyl-triethoxysilicane, mercaptopropyl trimethoxysilane or mercaptopropyltriethoxysilane.
6. the preparation method according to claim 1 with micropore and order mesoporous silica/carbon nanomaterial, it is special
Levy and be, the molar ratio of the resorcinol and silane coupler is 20-167%.
7. the preparation method according to claim 1 with micropore and order mesoporous silica/carbon nanomaterial, it is special
Levy and be, the mol ratio of the resorcinol and formaldehyde is 1：5.
8. the preparation method according to claim 1 with micropore and order mesoporous silica/carbon nanomaterial, it is special
Levy and be, inert gas used is nitrogen or helium.
9. the preparation method according to claim 1 with micropore and order mesoporous silica/carbon nanomaterial, it is special
Levy and be, the gas flow optimized of the inert gas is in 60-100mL/min.
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| CN108054387A (en) * | 2017-12-04 | 2018-05-18 | 五行科技股份有限公司 | A kind of preparation method of the hollow multinuclear nano catalytic material of palladium-mesopore silicon oxide |
| CN108598395A (en) * | 2018-03-30 | 2018-09-28 | 武汉理工大学 | The magnanimity preparation method of monodisperse silica/nitrogen-doped carbon composite Nano ball or microballoon |
| CN109718852A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院大连化学物理研究所 | The preparation method of one pot process spherical shell type stable metal nanocatalyst |
| CN111446440A (en) * | 2020-05-22 | 2020-07-24 | 扬州大学 | Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof |
| CN111960911A (en) * | 2020-07-23 | 2020-11-20 | 青岛科技大学 | Method for preparing cis-pinane by hydrogenating alpha-pinene |
| CN114057488A (en) * | 2022-01-17 | 2022-02-18 | 河南科技学院 | Preparation method of porous SiOC ceramic and application of porous SiOC ceramic in negative electrode material of lithium ion battery |
| CN114276681A (en) * | 2022-01-14 | 2022-04-05 | 南开大学 | Polydopamine microsphere with multilevel mesoporous structure and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718852A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院大连化学物理研究所 | The preparation method of one pot process spherical shell type stable metal nanocatalyst |
| CN108054387A (en) * | 2017-12-04 | 2018-05-18 | 五行科技股份有限公司 | A kind of preparation method of the hollow multinuclear nano catalytic material of palladium-mesopore silicon oxide |
| CN108598395A (en) * | 2018-03-30 | 2018-09-28 | 武汉理工大学 | The magnanimity preparation method of monodisperse silica/nitrogen-doped carbon composite Nano ball or microballoon |
| CN111446440A (en) * | 2020-05-22 | 2020-07-24 | 扬州大学 | Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof |
| CN111446440B (en) * | 2020-05-22 | 2022-07-05 | 扬州大学 | Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof |
| CN111960911A (en) * | 2020-07-23 | 2020-11-20 | 青岛科技大学 | Method for preparing cis-pinane by hydrogenating alpha-pinene |
| CN111960911B (en) * | 2020-07-23 | 2022-05-13 | 青岛科技大学 | Method for preparing cis-pinane by hydrogenating alpha-pinene |
| CN114276681A (en) * | 2022-01-14 | 2022-04-05 | 南开大学 | Polydopamine microsphere with multilevel mesoporous structure and preparation method thereof |
| CN114276681B (en) * | 2022-01-14 | 2023-12-22 | 南开大学 | Polydopamine microsphere with multi-stage mesoporous structure and preparation method thereof |
| CN114057488A (en) * | 2022-01-17 | 2022-02-18 | 河南科技学院 | Preparation method of porous SiOC ceramic and application of porous SiOC ceramic in negative electrode material of lithium ion battery |
| CN114057488B (en) * | 2022-01-17 | 2022-04-15 | 河南科技学院 | Preparation method of porous SiOC ceramic and application of porous SiOC ceramic in negative electrode material of lithium ion battery |
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