CN105236411B - A kind of high-specific area nano mesoporous silicon carbide hollow ball and preparation method thereof - Google Patents
A kind of high-specific area nano mesoporous silicon carbide hollow ball and preparation method thereof Download PDFInfo
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Abstract
Present invention relates particularly to a kind of high-specific area nano mesoporous silicon carbide hollow ball and preparation method thereof.Its technical scheme is：Different amount silica precursor tetraethyl orthosilicates is added dropwise in the water of different proportion, absolute ethyl alcohol mixed solution, it is set to be hydrolyzed into the silica solid nanospheres of different-diameter size, synthetic silica medicine ball is disperseed to held for some time in the distilled water of different volumes, prepares the mesoporous nano silicon dioxide hollow ball of different-diameter size.Then, hollow silica ball inside and outside shell is wrapped up into one layer of organic matter and caused in organic matter insertion shell wall, carbonization, being incubated a few hours after reaction product is well mixed with magnesium powder and metal salt under an inert atmosphere obtains the adjustable mesoporous nano carborundum hollow ball of the homogeneous size of structure.Reaction temperature of the present invention is relatively low, and cost control is relatively low, and obtained hollow carborundum has structure homogeneous, and size is adjustable, and the specific surface area (648m with superelevation2/ g), the advantages that meso-hole structure is excellent.
Description
Technical field
The invention belongs to nano-functional material technical field.It is empty more particularly to a kind of high-specific area nano mesoporous silicon carbide
Bulbus cordis and preparation method thereof.
Background technology
Carborundum (SiC) material has an excellent properties such as high temperature resistant, acid-alkali-corrosive-resisting and high mechanical properties, and with compared with
High energy gap, high critical breakdown electric field and higher thermal conductivity, small dielectric constant and the migration of higher electronics saturation
Rate, therefore have excellent mechanics, chemistry, calorifics, electric property, while there is resistance to irradiation, radioresistance, inhale the characteristics such as ripple, it is
The important nuclear reactor material of resistance to neutron irradiation and wave-absorbing and camouflage material and high performance structure ceramic material, and electronics and photoelectricity
The ideal material of sub- device, it is generally considered to be expected to the important composition unit as third generation wide bandgap semiconductor materials.Research
As a result show, the carrier material with high-specific surface area and hollow nuclear structure can load more heterogenous catalysts, so as to carry
The catalytic performance of high catalyst.Therefore, prepare while the SiC material with high-specific surface area and hollow nuclear structure is with important
Application value.The methods of traditional carbothermic reduction reaction, SHS process and polymer thermally decomposes is preparing hollow-core construction
Significant limitation be present in SiC, building-up process is considerably complicated and synthesis temperature all more than 1300 DEG C even up to 2000 DEG C, the energy
It is lost larger, cost is high, can not mass produce, it is often more important that the SiC hollow ball structures of synthesis can not ensure integrality
[Vix-Guterlc,Alix I,Gibot P.etal.Appl Surf Sci[J],2003,210:329-337]。
The content of the invention
The present invention using it is a kind of simple, reliable, can be mass-produced high-specific area nano mesoporous silicon carbide hollow ball and
Its preparation method, SiC hollow balls prepared by this method have that structure is homogeneous, size is adjustable, high-specific surface area, mesoporous is evenly distributed
The advantages that, and have the advantages that energy-conservation, it is inexpensive.
To realize above-mentioned requirements, the technical solution adopted by the present invention is：
A kind of preparation method of high-specific area nano mesoporous silicon carbide hollow ball, it comprises the following steps：
(1) pore creating material is added in the in the mixed solvent of absolute ethyl alcohol and water, is stirred in water-bath at 35 DEG C；Again to the above
Solution adds ammoniacal liquor and continues quick stirring；Then it is added dropwise tetraethyl orthosilicate, strong stirring 24h at a temperature of 35 DEG C；Using from
Scheming is multiple by white emulsion absolute ethyl alcohol and distilled water cross washing；
(2) white pigmented samples washed are disperseed to be dissolved in appropriate solvent, scattered solution is placed in Water Tank with Temp.-controlled
Insulation, time 6-48h prepare that the homogeneous size of structure is adjustable, the thick controllable nano-silicon dioxide hollow sphere of shell；
(3) by wet chemical method in silicon dioxide nano hollow sphere outer surface one layer of organic matter of homogeneous parcel：By dioxy
SiClx hollow ball ultrasonic disperse adds triblock copolymer, is subsequently added into trishydroxymethylaminomethane, strongly stirs in distilled water
Mixing, which makes solution be added after clarifying after Dopamine hydrochloride continues strong stirring some hours, filters, and is finally freeze-dried, is then protecting
Its carbonization is set to obtain carbon parcel silica SiO under shield atmosphere argon gas2@C；
(4) by SiO2@C are 1 according to mol ratio with magnesium：The amount of (0.1~3) uniformly mixes, and is then added using molten-salt growth method
With SiO2@C in mass ratio 1：The metal salt of (1~20), it is put into after well mixed in tube furnace under an inert atmosphere first with 1~30
DEG C/min programming rate is warming up to 500~900 DEG C and is incubated 1~12h and magnesium thermit occurs, make SiO2@C are reduced into carbon completely
SiClx, cool to room temperature with the furnace；By products therefrom cleaning filtering and after being freeze-dried, 200~800 DEG C of annealing are gone in atmosphere again
Except unnecessary carbon, mesoporous nano carborundum hollow ball is obtained.
In such scheme, absolute ethyl alcohol volume is 10~500ml in the step (1), and water volume is 10~1000ml, nothing
Water-ethanol：The volume ratio of water is 0.1~10.
In such scheme, pore creating material is 0.1~10g cetyl trimethylammonium bromide in the step (1).
In such scheme, solvent is 100~1000ml distilled water in the step (2), and the holding temperature of Water Tank with Temp.-controlled is
20~95 DEG C.
In such scheme, hollow silica ball 0.1~10g of content in the step (3), 0.1~5g three blocks are added
Copolymer, the triblock copolymer are PEO-PPOX-PEO triblock copolymer or polyoxy second
Alkene-polyethenoxy ether triblock copolymer, 0.1~12g of trishydroxymethylaminomethane, 0.01~10g of Dopamine hydrochloride, is strongly stirred
Filtered after mixing 1~24h.
In such scheme, the metal salt that molten-salt growth method uses in the step (4) includes NaCl, KCl, LiCl, MgCl2、
ZnCl2、AlCl3、CaCl2, one or two kinds of any of the above ratio in LiF, NaCl, KF, NaF, NaI or KI mixing.
In such scheme, when being mixed for two kinds of metal salts, two kinds of mass ratio is 1：(0.1~10).
The high-specific area nano mesoporous silicon carbide hollow ball that the above method is prepared.
The present invention general principle be：It is hydrolyzed into first with tetraethyl orthosilicate in the ethanol, water mixed solution of alkalescence
SiO2Nanosphere, then according to SiO2Ball external and internal compositionses have different rigidity (shell is rigidly better than kernel) utilization
Kirkendall effects, kernel finally can slowly be dissolved by water and form hollow-core construction, then be wrapped on hollow ball inside and outside shell surface
Wrap up in one layer of organic matter and cause in organic matter insertion shell wall, the carbon source after carbonization as reaction；And then using magnesium powder as reducing agent
Under the conditions of existing for metal salt, using the method for fused salt auxiliary at moderate temperatures by SiO2Elemental silicon is reduced into, due to this
React for self-propagating reaction, be enough to promote silicon-carbon reaction to generate SiC so releasing substantial amounts of heat, two reactions can be complete with a step
Into.On the one hand the metal salt of addition is melted into fused salt at high temperature can absorb substantial amounts of heat to ensure nano material at high temperature
Structural intergrity, on the other hand can control crystal grain homoepitaxial prevent reunite produce so that the shell of SiC hollow balls is by a large amount of
The superhigh specific surface area meso-hole structure that forms of 2-4nm crystal grain accumulation.
The present invention has good effect using new method synthesis SiC hollow balls：
1) present invention synthesis hollow ball structure is homogeneous, integrity degree is high, and size can any modulation between 100~1000nm；
There is large specific surface area simultaneously, meso-hole structure is evenly distributed；With resistance to irradiation, radioresistance, the characteristics such as ripple are inhaled, are important
The nuclear reactor material of resistance to neutron irradiation, wave-absorbing and camouflage material and high performance structure ceramic material.
2) added in the reaction relative to the preparation method such as traditional carbon thermal reduction or the direct pyroreaction of carbon silicon, this invention
A certain amount of magnesium metal, first makes SiO2Elemental silicon is obtained with reactive magnesium, recycles the hot self-heat generation of magnesium make it that silicon is in situ raw with carbon
Into SiC, nano SiC and traditional reaction temperature (1300~2000 DEG C) phase can be synthesized in relatively low temperature (500-900 DEG C)
It is cost-effective than greatly reducing the energy consumption in production process.
3) present invention synthesis hollow ball structure use template-free method, and experimentation is simple and easy to control, therefore of the invention can
Industrially mass produce and apply.
4) present invention can produce substantial amounts of heat with absorbing reaction to ensure synthesis SiC shape using the method for fused salt auxiliary
Complete, the homogeneous and its special meso-hole structure of looks, therefore the widespread adoption of special dimension can be met.
Brief description of the drawings
Fig. 1 is the preparation flow schematic diagram of mesoporous nano carborundum hollow ball prepared by the present invention；
Fig. 2 is the mesoporous nano SiC hollow ball X ray diffracting spectrums that embodiment 1 obtains；
Fig. 3 is the stereoscan photograph for the mesoporous nano SiC hollow balls that embodiment 1 obtains；
Fig. 4 is the transmission electron microscope photo for the mesoporous nano SiC hollow balls that embodiment 1 obtains；
Fig. 5 is ratio surface and the pore analysis for the mesoporous nano SiC hollow balls that embodiment 1 obtains；
Fig. 6,7 are absorption property of the obtained mesoporous nano SiC hollow balls of embodiment 1 to rhodamine b dyestuffs.
Embodiment
The present invention will be further described with reference to the accompanying drawings and examples, and certain following embodiments should not be construed as pair
The limitation of the present invention.
Embodiment 1
(1) first by 30ml C2H5OH adds 0.1g CTAB as pore creating material, 35 in water-bath in 100ml distilled water
30min is stirred at DEG C；2ml NH is added to above solution again3·H2O continues quick stirring；Then 1ml TEOS is added dropwise,
Strong stirring 24h at a temperature of 35 DEG C；Using under centrifuge 4000rmp speed conditions by white emulsion C2H5OH and distilled water are handed over
Fork washing is three times.
(2) white pigmented samples washed are scattered in 160ml distilled water, scattered solution is placed in Water Tank with Temp.-controlled
It is incubated under the conditions of 20 DEG C, soaking time 6h, prepares the homogeneous Nano-meter SiO_2 of structure2Hollow ball.
(3) by wet chemical method in SiO2Wrap up one layer of organic matter and cause organic matter in nano-hollow ball inside and outside shell surface
Concretely comprised the following steps in embedded shell wall：By 0.1g SiO2Hollow ball ultrasonic disperse adds 0.1g three blocks in 100ml distilled water
Copolymer, 0.2g Tris being subsequently added into, strong stirring makes solution be filtered after adding 0.2g DA continuation strong stirrings 1h after clarifying,
Finally it is freeze-dried.Then its carbonization is made to obtain SiO under argon gas2@C。
(4) by SiO2@C, magnesium, metal salt NaCl are 1 according to mol ratio：2.2：1 it is well mixed after be put into tube furnace
First 500 DEG C and 1h are warming up under inert atmosphere (Ar) with 5 DEG C/min programming rate magnesium thermit occurs, make SiO2@C are completely also
Original cools to room temperature with the furnace into SiC；Products therefrom is cleaned with 1mol/L HCl respectively and stirs 12h, then uses mass fraction
5%HF is cleaned and is stirred 0.5h, and 400 DEG C of annealing remove unnecessary carbon in atmosphere again after filtering and being freeze-dried, and obtain purity
It is higher that (icp analysis, more than 99%), diameter is in 200 rans, the SiC hollow balls that about 30 nanometers of hollow thickness of the shell, from Fig. 4
TEM figures find out that the shell of SiC hollow balls is made up of the specific surface area (468m for causing it to have superelevation countless nanocrystals2/ g,
Shown in Fig. 5).
Embodiment 2
(1) first by 50ml C2H5OH adds 0.5g CTAB as pore creating material, 35 in water-bath in 250ml distilled water
30min is stirred at DEG C；3ml NH is added to above solution again3·H2O continues quick stirring；Then 2ml TEOS is added dropwise,
Strong stirring 24h at a temperature of 35 DEG C；Using under centrifuge 4000rmp speed conditions by white emulsion C2H5OH and distilled water are handed over
Fork washing is three times.
(2) white pigmented samples washed are scattered in 160ml distilled water, by scattered solution as in Water Tank with Temp.-controlled
It is incubated under the conditions of 25 DEG C, soaking time 12h, prepares the homogeneous Nano-meter SiO_2 of structure2Hollow ball.
(3) by wet chemical method in SiO2Wrap up one layer of organic matter and cause organic matter in nano-hollow ball inside and outside shell surface
Concretely comprised the following steps in embedded shell wall：By 0.5g SiO2It is embedding to add 0.25g tri- in 200ml distilled water for hollow ball ultrasonic disperse
Section copolymer, 0.5g Tris are subsequently added into, after strong stirring makes solution add 0.5g DA continuation strong stirrings 3.5h after clarifying
Filter, be finally freeze-dried.Then its carbonization is made to obtain SiO under argon gas2@C。
(4) by SiO2@C, magnesium, metal salt KCl are 1 according to mol ratio：2.2：5 amount is put into tube furnace after uniformly mixing
First it is warming up to 600 DEG C with 5 DEG C/min programming rate under inert atmosphere (Ar) and is incubated 2h and magnesium thermit occurs, makes SiO2@C
SiC is reduced into completely, cools to room temperature with the furnace；Products therefrom is cleaned with 1mol/L HCl respectively and stirs 12h, then uses matter
Amount fraction 5%HF is cleaned and is stirred 0.5h, and 500 DEG C of annealing remove unnecessary carbon in atmosphere again after filtering and being freeze-dried, and obtain
To purity it is higher (icp analysis, more than 99%), nano SiC hollow ball of the diameter in 180 rans.
Embodiment 3
(1) first by 20ml C2H5OH adds 1g CTAB as pore creating material, 35 DEG C in water-bath in 250ml distilled water
Lower stirring 30min；4ml NH is added to above solution again3·H2O continues quick stirring；Then it is added dropwise 3ml TEOS, 35
Strong stirring 24h at a temperature of DEG C；Using under centrifuge 4000rmp speed conditions by white emulsion C2H5OH and distilled water intersect
Washing is three times.
(2) white pigmented samples washed are scattered in 450ml distilled water, by scattered solution as in Water Tank with Temp.-controlled
It is incubated under the conditions of 30 DEG C, soaking time 18h, prepares the homogeneous Nano-meter SiO_2 of structure2Hollow ball.
(3) by wet chemical method in SiO2Wrap up one layer of organic matter and cause organic matter in nano-hollow ball inside and outside shell surface
Concretely comprised the following steps in embedded shell wall：By 1g SiO2Hollow ball ultrasonic disperse adds 2g triblock copolymers in 250ml distilled water
Thing, 2g Tris are subsequently added into, strong stirring makes solution be filtered after adding 0.5g DA continuation strong stirrings 8h after clarifying, last cold
It is lyophilized dry.Then its carbonization is made to obtain SiO under argon gas2@C。
(4) by SiO2@C, magnesium, metal salt NaCl are 1 according to mol ratio：2.2：10 amount is put into tube furnace after uniformly mixing
In under inert atmosphere (Ar) first with 5 DEG C/min programming rate be warming up to 650 DEG C and be incubated 3h occur magnesium thermit, make
SiO2@C are reduced into SiC completely, cool to room temperature with the furnace；Products therefrom is cleaned with 1mol/L HCl respectively and stirs 12h, so
Cleaned afterwards with mass fraction 5%HF and stir 0.5h, 500 DEG C of annealing removals are unnecessary in atmosphere again after filtering and being freeze-dried
Carbon, obtain purity it is higher (icp analysis, more than 99%), nano SiC hollow ball of the diameter in 100 rans.
Embodiment 4
(1) first by 250ml C2H5OH adds 1.5g CTAB as pore creating material, in water-bath in 300ml distilled water
30min is stirred at 35 DEG C；6ml NH is added to above solution again3·H2O continues quick stirring；Then it is added dropwise 5ml's
TEOS, strong stirring 24h at a temperature of 35 DEG C；Using under centrifuge 4000rmp speed conditions by white emulsion C2H5OH and distillation
Water cross washing is three times.
(2) white pigmented samples washed are scattered in 640ml distilled water, by scattered solution as in Water Tank with Temp.-controlled
It is incubated under the conditions of 60 DEG C, soaking time 24h, prepares the homogeneous Nano-meter SiO_2 of structure2Hollow ball.
(3) by wet chemical method in SiO2Wrap up one layer of organic matter and cause organic matter in nano-hollow ball inside and outside shell surface
Concretely comprised the following steps in embedded shell wall：By 4g SiO2Hollow ball ultrasonic disperse adds 2g triblock copolymers in 350ml distilled water
Thing, 4g Tris are subsequently added into, strong stirring makes solution be filtered after adding 5g DA continuation strong stirrings 12h after clarifying, last cold
It is lyophilized dry.Then its carbonization is made to obtain SiO under argon gas2@C。
(4) by SiO2@C, magnesium, metal salt mixture (mass ratio NaCl：KCl=1：0.1) it is 1 according to mol ratio：
2.2：10 amount is put into tube furnace after uniformly mixing and is first warming up under inert atmosphere (Ar) with 5 DEG C/min programming rate
700 DEG C and be incubated 4h occur magnesium thermit, make SiO2@C are reduced into SiC completely, cool to room temperature with the furnace；Products therefrom is distinguished
Cleaned with 1mol/L HCl and stir 12h, then cleaned with mass fraction 5%HF and stir 0.5h, after filtering and being freeze-dried
500 DEG C of annealing remove unnecessary carbon in atmosphere again, and obtaining purity, higher (icp analysis, more than 99%), diameter is at 800 nanometers
The nano SiC hollow ball of left and right.
Embodiment 5
(1) first by 200ml C2H5OH adds 4g CTAB as pore creating material, 35 in water-bath in 300ml distilled water
30min is stirred at DEG C；8ml NH is added to above solution again3·H2O continues quick stirring；Then 6ml TEOS is added dropwise,
Strong stirring 24h at a temperature of 35 DEG C；Using under centrifuge 4000rmp speed conditions by white emulsion C2H5OH and distilled water are handed over
Fork washing is three times.
(2) white pigmented samples washed are scattered in 480ml distilled water, by scattered solution as in Water Tank with Temp.-controlled
It is incubated under the conditions of 80 DEG C, soaking time 32h, prepares the homogeneous Nano-meter SiO_2 of structure2Hollow ball.
(3) by wet chemical method in SiO2Wrap up one layer of organic matter and cause organic matter in nano-hollow ball inside and outside shell surface
In embedded shell wall and to concretely comprise the following steps in organic matter insertion shell wall：By 8g SiO2Hollow ball ultrasonic disperse steams in 500ml
In distilled water, 3g triblock copolymers are added, are subsequently added into 6g Tris, it is strong that strong stirring makes solution add 6g DA continuation after clarifying
Filter after power stirring 16h, be finally freeze-dried.Then its carbonization is made to obtain SiO under argon gas2@C。
(4) by SiO2@C, magnesium, metal salt mixture (mass ratio NaF：KF=1：0.1) it is 1 according to mol ratio：2.2：
10 amount is put into tube furnace after uniformly mixing and is first warming up to 750 DEG C with 5 DEG C/min programming rate under inert atmosphere (Ar)
And be incubated 4h and magnesium thermit occurs, make SiO2@C are reduced into SiC completely, cool to room temperature with the furnace；Products therefrom is used respectively
1mol/L HCl are cleaned and are stirred 12h, are then cleaned with mass fraction 5%HF and are stirred 0.5h, after filtering and being freeze-dried again
500 DEG C of annealing remove unnecessary carbon in atmosphere, and obtaining purity, higher (icp analysis, more than 99%), diameter is on 500 nanometers of left sides
Right nano SiC hollow ball.
Embodiment 6
(1) first by 250ml C2H5OH adds 8g CTAB as pore creating material, 35 in water-bath in 200ml distilled water
30min is stirred at DEG C；8ml NH is added to above solution again3·H2O continues quick stirring；Then 8ml TEOS is added dropwise,
Strong stirring 24h at a temperature of 35 DEG C；Using under centrifuge 4000rmp speed conditions by white emulsion C2H5OH and distilled water are handed over
Fork washing is three times.
(2) white pigmented samples washed are scattered in 960ml distilled water, by scattered solution as in Water Tank with Temp.-controlled
It is incubated under the conditions of 90 DEG C, soaking time 48h, prepares the homogeneous Nano-meter SiO_2 of structure2Hollow ball.
(3) by wet chemical method in SiO2Wrap up one layer of organic matter and cause organic matter in nano-hollow ball inside and outside shell surface
Concretely comprised the following steps in embedded shell wall：By 6g SiO2Hollow ball ultrasonic disperse adds 4g triblock copolymers in 700ml distilled water
Thing, 8g Tris are subsequently added into, strong stirring makes solution be filtered after adding 6g DA continuation strong stirrings 20h after clarifying, last cold
It is lyophilized dry.Then its carbonization is made to obtain SiO under argon gas2@C。
(4) by SiO2@C, magnesium, metal salt mixture (mass ratio NaCl：KCl=1：1) it is 1 according to mol ratio：2.2：5
Amount be uniformly put into tube furnace and be first warming up to 800 DEG C simultaneously with 5 DEG C/min programming rate under inert atmosphere (Ar) after mixing
It is incubated 4h and magnesium thermit occurs, makes SiO2@C are reduced into SiC completely, cool to room temperature with the furnace；Products therefrom is used into 1mol/ respectively
L HCl are cleaned and are stirred 12h, are then cleaned with mass fraction 5%HF and are stirred 0.5h, again in air after filtering and being freeze-dried
In 500 DEG C of annealing remove unnecessary carbon, obtain that purity is higher, nano SiC hollow ball of the diameter in 1000 rans.
Embodiment 7
(1) first by 500ml C2H5OH adds 10g CTAB as pore creating material, in water-bath in 1000ml distilled water
30min is stirred at 35 DEG C；10ml NH is added to above solution again3·H2O continues quick stirring；Then it is added dropwise 8ml's
TEOS, strong stirring 24h at a temperature of 35 DEG C；Using under centrifuge 4000rmp speed conditions by white emulsion C2H5OH and distillation
Water cross washing is three times.；
(2) white pigmented samples washed are scattered in 1000ml distilled water, by scattered solution as Water Tank with Temp.-controlled
In be incubated under the conditions of 95 DEG C, soaking time 60h, prepare the homogeneous Nano-meter SiO_2 of structure2Hollow ball.
(3) by wet chemical method in SiO2Wrap up one layer of organic matter and cause organic matter in nano-hollow ball inside and outside shell surface
Concretely comprised the following steps in embedded shell wall：By 10g SiO2Hollow ball ultrasonic disperse adds 5g three blocks and is total in 1000ml distilled water
Polymers, 8g Tris are subsequently added into, strong stirring makes solution be filtered after adding 10g DA continuation strong stirrings 24h after clarifying, finally
Freeze-drying.Then its carbonization is made to obtain SiO under argon gas2@C。
(4) by SiO2@C, magnesium, metal salt mixture (mass ratio NaCl：KCl=1：2) it is 1 according to mol ratio：2.2：
10 amount is put into tube furnace after uniformly mixing and is first warming up to 900 DEG C with 5 DEG C/min programming rate under inert atmosphere (Ar)
And be incubated 6h and magnesium thermit occurs, make SiO2@C are reduced into SiC completely, cool to room temperature with the furnace；Products therefrom is used respectively
1mol/L HCl are cleaned and are stirred 12h, are then cleaned with mass fraction 5%HF and are stirred 0.5h, after filtering and being freeze-dried again
500 DEG C of annealing remove unnecessary carbon in atmosphere, obtain that purity is higher, nano SiC hollow ball of the diameter in 450 rans.
Present embodiment compared with prior art, has the positive effect that：
1) present invention synthesis hollow ball structure is homogeneous, integrity degree is high, and size can any modulation between 100~1000nm；
There is large specific surface area (468m simultaneously2/ g, as shown in Figure 5), meso-hole structure is evenly distributed；With excellent mechanics, chemistry,
Calorifics, electric property, while there is resistance to irradiation, radioresistance, inhale the characteristics such as ripple, it is the important nuclear reactor material of resistance to neutron irradiation
Material and wave-absorbing and camouflage material and high performance structure ceramic material.
2) added in the reaction relative to the preparation method such as traditional carbon thermal reduction or the direct pyroreaction of carbon silicon, this invention
A certain amount of magnesium metal, first makes SiO2Elemental silicon is obtained with reactive magnesium, recycles the hot self-heat generation of magnesium make it that silicon is in situ raw with carbon
Into SiC, nano SiC can be synthesized in relatively low temperature (500-900 DEG C), with traditional reaction temperature (1300~2000 DEG C) phase
It is cost-effective than greatly reducing the energy consumption in production process.
3) present invention synthesis hollow ball structure use template-free method, and experimentation is simple and easy to control, therefore of the invention can
Industrially mass produce and apply.
4) present invention can release heat to ensure that the pattern for synthesizing SiC is complete using the method for fused salt auxiliary with absorbing reaction
Whole, homogeneous and its special meso-hole structure, therefore the widespread adoption of special dimension can be met.
Claims (6)
1. a kind of preparation method of high-specific area nano mesoporous silicon carbide hollow ball, it comprises the following steps：
(1) pore creating material is added in the in the mixed solvent of absolute ethyl alcohol and water, is stirred in water-bath at 35 DEG C；Again to above solution
Add ammoniacal liquor and continue quick stirring；Then it is added dropwise tetraethyl orthosilicate, strong stirring 24h at a temperature of 35 DEG C；Use centrifuge
White emulsion absolute ethyl alcohol and distilled water cross washing is multiple；
(2) white pigmented samples washed are disperseed to be dissolved in appropriate solvent, scattered solution are placed in Water Tank with Temp.-controlled and is incubated,
Time is 6-48h, prepares that the homogeneous size of structure is adjustable, the thick controllable nano-silicon dioxide hollow sphere of shell；
(3) by wet chemical method in silicon dioxide nano hollow sphere surfaces externally and internally one layer of organic matter of homogeneous parcel：By titanium dioxide
Silicon hollow ball ultrasonic disperse adds triblock copolymer, is subsequently added into trishydroxymethylaminomethane, strong stirring in distilled water
Make solution add after clarifying after Dopamine hydrochloride continues strong stirring some hours to filter, be finally freeze-dried, then protecting
Its carbonization is set to obtain carbon parcel silica SiO under atmosphere argon gas2@C, wherein hollow silica ball content 0.1~
10g, 0.1~5g of triblock copolymer, 0.01~10g of Dopamine hydrochloride；
(4) by SiO2@C are 1 according to mol ratio with magnesium：The amount of (0.1~3) uniformly mixes, then using molten-salt growth method add with
SiO2@C in mass ratio 1：The metal salt of (1~20), the metal salt are that mass ratio is 1:1 NaCl and KCl fused salt mixt,
It is put into after well mixed in tube furnace and 500 DEG C and insulation 1 is first warming up to 1~30 DEG C/min programming rate under an inert atmosphere
Magnesium thermit occurs for~12h, makes SiO2@C are reduced into carborundum completely, cool to room temperature with the furnace；Products therefrom is cleaned and filtered
And 200~800 DEG C of annealing remove unnecessary carbon in atmosphere again after being freeze-dried, and obtain mesoporous nano carborundum hollow ball.
2. the method as described in claim 1, it is characterised in that absolute ethyl alcohol volume is 10~500ml in the step (1),
Water volume is 10~1000ml, absolute ethyl alcohol：The volume ratio of water is 0.1~10.
3. the method as described in claim 1, it is characterised in that pore creating material is 0.1~10g hexadecane in the step (1)
Base trimethylammonium bromide.
4. the method as described in claim 1, it is characterised in that solvent is 100~1000ml distilled water in the step (2),
The holding temperature of Water Tank with Temp.-controlled is 20~95 DEG C.
5. the method as described in claim 1, it is characterised in that in the step (3) triblock copolymer be PEO-
PPOX-PEO triblock copolymer or polyoxyethylene polyoxypropylene ether triblock copolymer, strong stirring 1
Filtered after~24h.
6. the high-specific area nano mesoporous silicon carbide hollow ball that the method as described in any one of claim 1 to 5 is prepared.
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| CN106943971A (en) * | 2016-01-07 | 2017-07-14 | 天津科技大学 | Strengthen the method for high molecular microcapsule intensity under a kind of temperate condition |
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