CN105502403B - Preparation method of ordered mesoporous silicon carbide - Google Patents
Preparation method of ordered mesoporous silicon carbide Download PDFInfo
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- CN105502403B CN105502403B CN201610022824.8A CN201610022824A CN105502403B CN 105502403 B CN105502403 B CN 105502403B CN 201610022824 A CN201610022824 A CN 201610022824A CN 105502403 B CN105502403 B CN 105502403B
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- carborundum
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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Abstract
The invention relates to a method for preparing ordered mesoporous silicon carbide through microwave roasting. The method comprises the steps that 1, an ordered mesoporous SiO2-C composite is prepared; 2, the ordered mesoporous silicon carbide is prepared through microwave reduction. The ordered mesoporous SiO2-C composite is firstly prepared, a microwave radiation carbothermal reduction reaction is performed in an inert atmosphere through the good microwave absorbing property of carbon, and then impurity removing and drying are performed to obtain the ordered mesoporous silicon carbide. The preparation method is short in preparation time, and the product has the advantages of being relatively uniform in pore diameter and larger in specific surface area.
Description
Technical field
The present invention relates to a kind of method that microwave calcining prepares order mesoporous carborundum, belongs to ordered mesoporous material synthesis work
Skill field.
Background technology
Carborundum has the excellent spies such as good chemical stability, high-temperature stability, high pyroconductivity, antioxidant anticorrosive
Property, allow carborundum as high-temperature structural components, the substrate of large scale integrated circuit, it is alternatively arranged as high temperature reaction catalyst
Excellent carrier, is widely used in the industrial circles such as chemical, machinery, metallurgy.Carborundum prepares generally anti-using carbon thermal reduction
Should, requiring heat on 2000 DEG C, obtained carborundum specific surface area is little and non-porous, and the time-consuming power consumption of the method need to improve.
The preparation of mesoporous silicon carbide at present is divided into two methods of hard template and soft template, and such as patent CN201510269148 is
Hard template method prepares mesoporous silicon carbide, and Polycarbosilane is dissolved in into organic solvent, makes Polycarbosilane be filled in order mesoporous titanium dioxide
In silicon, then the high-temperature roasting under inert gas shielding, the compound of carborundum and silica is obtained, hydrofluoric acid removes template,
Obtain ordered nano mesoporous silicon carbide material.For another example sucrose is dissolved in water by patent CN201010152336 so as to enter SBA-
In 15 or KIT-6 mesopore orbit, sucrose carbonization is obtained the compound filled with carbon in mesoporous silicon oxide, in magnesium powder effect
Lower low-temperature bake obtains mesoporous silicon carbide.Hard template method is relatively costly and the step of increased removing template.Soft template such as patent
CN201210146069 obtains silicon carbide precursor with resorcinol, formaldehyde, tetraethyl orthosilicate as raw material with sol-gel process
Body, through carbon thermal reduction mesoporous silicon carbide is generated.Both of which needs high-temperature roasting, high energy consumption.
The content of the invention
The present invention in order to solve prior art in the problems such as prepare mesoporous silicon carbide and take tediously long, high energy consumption, there is provided one
Plant the preparation method of order mesoporous carborundum.
The present invention is achieved by the following technical solutions：A kind of preparation method of order mesoporous carborundum, its step is：
(i) order mesoporous SiO is prepared2/ C composite
(ii) microwave reduction prepares order mesoporous carborundum
Order mesoporous SiO2/ C composite is placed in micro-wave oven zone line, adjustment position, until infrared temperature probe is surveyed
Obtain the maximum temperature point of composite；It is 0.09MPa to be evacuated to vacuum, and it is 0.03MPa to be passed through nitrogen to vacuum, takes out true
Empty, logical nitrogen steps are repeated twice, after be evacuated to vacuum again for 0.09MPa, be passed through nitrogen is to vacuum
0.07MPa；Micro-wave oven cooling water circulating device is opened, microwave control switch is opened, microwave power is adjusted and is caused to be warming up in stove
1300 DEG C ± 10 DEG C, isothermal reaction 20min；Microwave control switch is closed, stops heating, it is 0.09MPa to be evacuated to vacuum,
Naturally cool in stove after room temperature, close recirculated water；Open atmospheric valve, when microwave furnace pressure reaches atmospheric pressure, fire door
Automatically open up, take out, obtain the order mesoporous carborundum of powder.
The micro-wave oven adopted during practical operation of the present invention is the production of Nanjing Jie Quan microwave equipments Co., Ltd, its model
NJZ4-3。
The present invention in the preparation of carborundum, is brought rapidly up microwave technique application in the short time, significantly shorten preparation time,
Reducing energy consumption, greatly reduces traditional preparation methods and prepares time-consuming long shortcoming, prepare take shorter, reasonable raw material proportioning,
Product is stablized, and is to prepare a kind of very good method of order mesoporous carborundum.
In addition, the order mesoporous carborundum powder that (ii) step of the present invention obtains subsequently has carried out removal of impurities process, should remove and live together
Reason includes high temperature carbon removal treatment and pickling except silicon process.
When being embodied as, it is the step of the high temperature carbon removal treatment：Order mesoporous carborundum powder is placed in Muffle furnace,
700 DEG C of roasting 2h, remove unreacted carbon.The pickling except being the step of silicon is processed：Order mesoporous carborundum powder is placed in
In the hydrofluoric acid solution of 50% volume fraction, 24h is stood；Supernatant is outwelled in centrifugation afterwards, is cleaned, and is dried, and removes unreacted silicon.
Further, the present invention does template with triblock copolymer body structure directing agent F127, and with tetraethyl orthosilicate silicon source is done,
Carbon source is done with phenol resin oligomer；And prepare order mesoporous SiO2The step of/C composite is：
1. F127 is dissolved in absolute ethyl alcohol, adds hydrochloric acid solution, 40 DEG C of constant temperature to stir 1h；After sequentially add positive silicic acid second
The ethanol solution of ester and phenol resin oligomer, 40 DEG C of constant temperature stir 2h, obtain mixed solution；
2. mixed solution is placed in container, and 5～8h is placed under room temperature, is subsequently placed in 24h in 100 DEG C of constant temperature ovens, container
Interior formation yellow film, scraping wears into fine powder；
3. the fine powder is placed in tube furnace, is warming up to 350 DEG C with 1 DEG C/min and is incubated 3h, then be warming up to 1 DEG C/min
600 DEG C, subsequently it is warming up to 900 DEG C with 5 DEG C/min and is incubated 2h, obtains the order mesoporous SiO of black2/ C composite.
Said method is first obtained order mesoporous SiO using soft template method2The composite of/C, then using microwave calcining carbon heat
Reduction is quickly obtained order mesoporous carborundum, and obtained carborundum aperture is concentrated, and specific surface area is big.
Description of the drawings
Fig. 1 is the transmission electron microscope enlarged drawing of order mesoporous carborundum of the present invention.In figure：It can be seen that in order
Regular mesoporous presence.
Fig. 2 is the X-ray small-angle diffraction intensity collection of illustrative plates of order mesoporous carborundum of the present invention.Ordinate is to spread out in figure
Intensity is penetrated, abscissa is the θ of the angle of diffraction 2, and little angle XRD peak occurs, illustrates to be ordered into meso-hole structure at 0.8 °.
Fig. 3 is the X-ray full-shape diffracted intensity collection of illustrative plates of order mesoporous carborundum of the present invention.35.579 in figure,
41.383rd, 59.977,71.777,75.492 is carborundum standard diffraction peak, is kissed completely with standard card PDF#29-1129
Close, illustrate that the product for synthesizing is carborundum.
Fig. 4 is the suction-desorption isothermal curve figure of order mesoporous carborundum of the present invention.The curve generation that figure orbicular spot is located
Table adsorption curve figure, the curve that side's point is located represents desorption curve figure.As seen from the figure, suction-desorption isotherm meet H1 types return it is stagnant
Ring, what H1 types returned stagnant ring reflection is the cylindrical hole of even aperture distribution, and specific surface area is 446.55m2/g。
Fig. 5 is the pore size distribution curve figure of order mesoporous carborundum of the present invention.Understand in figure, pore size distribution curve can
To find out that aperture concentrates on 6.3nm or so.
Specific embodiment
The chemical substance material that the present invention is used is：Structure directing agent F127, phenol, formaldehyde, tetraethyl orthosilicate, anhydrous second
Alcohol, NaOH, hydrochloric acid, hydrofluoric acid, deionized water, nitrogen, it prepares consumption with gram, milliliter, centimetre3For measurement unit
F127：Polyoxyethylene-poly-oxypropylene polyoxyethylene 16.00g ± 0.01g
Phenol：C6H5OH 18.30g±0.01g
Formaldehyde：HCHO 28.50ml±0.01ml
Tetraethyl orthosilicate：Si(OC2H5)4 4.40ml±0.01ml
Absolute ethyl alcohol：C2H5OH 180.00mL±0.01mL
NaOH：NaOH 25.065g±0.001g
Hydrochloric acid：HCl 10.00mL±0.01mL
Hydrofluoric acid：HF 15.00mL±0.01 mL
Deionized water：H2O 3000ml±50ml
Nitrogen：N2 10000cm3±100cm3
Preparation method is as follows：
(1) solution is prepared
1. 20wt.% sodium hydroxide solutions are configured
NaOH 25.065g ± 0.001g are weighed, in being dissolved in beaker, the volumetric flask of 100mL is poured into, beaker is repeatedly washed
And pour water into volumetric flask, and 100ml is titrated to, the fully dissolving that teetertotters is formed：20wt.% sodium hydroxide solutions.
2. 2mol/L, 0.2mol/L hydrochloric acid solution is configured
Graduated cylinder measures 8.33 ml ± 0.01ml concentrated hydrochloric acids, pours the volumetric flask of 50ml into, repeatedly washs graduated cylinder and pours in water
Volumetric flask, is titrated to 50ml, teetertotters and is thoroughly mixed to form：2mol/L hydrochloric acid solutions.
Graduated cylinder measures 1.66 ml ± 0.01ml concentrated hydrochloric acids, pours the volumetric flask of 50ml into, repeatedly washs graduated cylinder and pours in water
Volumetric flask, is titrated to 50ml, teetertotters and is thoroughly mixed to form：0.2mol/L hydrochloric acid solutions.
(2) formulated phenolic resin oligomer solution
1. weigh phenol 18.30g ± 0.01g to place in beaker, beaker is in 40 DEG C of heating water bath states of constant temperature, makes phenol
Melt completely.
2. the 20wt.% sodium hydroxide solutions of pre-configured 3.20ml ± 0.01ml are added, 10min is stirred.
3. under 40 DEG C of temperature constant states, it is added dropwise over the formalin of 28.50ml ± 0.01ml.
4. 72 DEG C are warming up to, constant temperature stirring 1h, mixture solution is cooled to 20 DEG C of room temperature.
5. the pH of mixture solution is adjusted to into 7 with 2mol/L hydrochloric acid solutions.
6. the solution rotary vacuum evaporator for obtaining rotary evaporation 2h in the case where vacuum is 0.09MPa temperature 50 Cs, obtains
To phenol resin oligomer, closed preservation.
7. phenol resin oligomer 29.625g ± 0.001g are measured, then measures 150ml absolute ethyl alcohols, be sufficiently mixed, be made into
20wt% phenol resin oligomer solution.
(3) order mesoporous SiO is prepared2/ C composite
Triblock copolymer body structure directing agent F127 does template, and tetraethyl orthosilicate does silicon source, and phenol resin solution does carbon
Source.
1. the F127 for weighing 3.2g ± 0.01g is dissolved in 20.50ml ± 0.01ml absolute ethyl alcohols, and addition 2.20ml ±
The hydrochloric acid solution of the 0.2mol/L of 0.01ml, at 40 DEG C of constant temperature 1h is stirred.
2. the tetraethyl orthosilicate of 4.40ml ± 0.01ml and the 20wt% phenolic resin of 12.80ml ± 0.01ml are sequentially added
Solution, constant temperature stirring 2h.
3. the solution for obtaining is poured in evaporating dish, and room temperature keeps 5-8h, is then placed in baking oven, 100 DEG C of constant temperature 24h, evaporation
One layer of yellow film is left on ware, is scraped and is worn into fine powder.
4. powder is put in quartz boat, is placed in tube furnace center, 20 DEG C are warming up to 350 DEG C with 1 DEG C/min from room temperature
3h is kept, then 600 DEG C are warming up to 1 DEG C/min, with 5 DEG C/min 900 DEG C are warming up to, in 900 DEG C of constant temperature 2h, obtain black has
The mesoporous SiO of sequence2/ C composite.
(4) carbon thermal reduction prepares order mesoporous carborundum
1. the SiO of 3.00g ± 0.01g is weighed2/ C composite is put in corundum crucible, and corundum crucible is put into into insulating brick
Center groove, is placed in the zone line of micro-wave oven furnace chamber, adjusting position, until infrared temperature probe measures the maximum temperature of sample
Degree point.
2. it is 0.09MPa to be evacuated to vacuum, and it is 0.03MPa to be passed through nitrogen to vacuum, vacuumizes, leads to nitrogen steps
Be repeated twice, after be evacuated to vacuum again for 0.09MPa, it is 0.07MPa to be passed through nitrogen to vacuum.
3. open micro-wave oven circulating water cooling device, then open microwave, adjust microwave power make in-furnace temperature by 25 DEG C by
Edge up to 1300 DEG C ± 10 DEG C, constant temperature 20min makes solid-phase mixture fully be reacted；
SiO2+ 3C=2CO ↑+SiC
In formula：SiO2：Silica, C：Carbon, CO：Carbon monoxide, SiC：Carborundum.
4. microwave is closed after the completion of reacting, 0.09MPa is evacuated to, treats that cavity temperature slowly cools to 25 with cooling water
After DEG C, recirculated water is closed.
5. product is taken out
Atmospheric valve is opened, when microwave furnace pressure reaches atmospheric pressure, fire door is automatically opened up, and the powder in corundum crucible is
For the order mesoporous carborundum of non-removal of impurities.
(5) dedoping step
1. high temperature removes carbon
Upper step is obtained into powder to be put in quartz boat, is placed in Muffle furnace, the lower 700 DEG C of roasting 2h of air atmosphere are removed not
The carbon of reaction.
2. pickling removes silicon
Hydrofluoric acid 15mL is measured, 30mL is diluted to, will be impregnated in a solution of hydrofluoric acid except the sample after carbon, stand 24h.
3. centrifugation
Mixed liquor is placed in centrifuge tube, 6min is centrifuged with the rotating speed of 12000 turns/min, outwell supernatant liquor, clean to
Supernatant liquor pH close 7, retains the solid sample in centrifuge tube.
4. kept dry
After the sample for obtaining is dried into 24h in 80 DEG C of baking ovens, in being fitted into sample sack, label is posted, is placed in drier,
Closed preservation.
(6) detect, analyze, characterize
Use transmission electron microscope observation sample topography；
Crystal phase analysis and order mesoporous identification are carried out with X-ray powder diffraction instrument；
The measure of order mesoporous carborundum is carried out with specific surface and Porosimetry.
Claims (4)
1. a kind of preparation method of order mesoporous carborundum, it is characterised in that
Its step is：
(i) order mesoporous SiO is prepared2/ C composite
Template is done with triblock copolymer body structure directing agent F127, silicon source is done with tetraethyl orthosilicate, with phenol resin oligomer
Do carbon source；
It is described to prepare order mesoporous SiO2The step of/C composite is：
1. F127 is dissolved in absolute ethyl alcohol, adds hydrochloric acid solution, 40 DEG C of constant temperature to stir 1h；After sequentially add tetraethyl orthosilicate with
And the ethanol solution of phenol resin oligomer, 40 DEG C of constant temperature stirring 2h, obtain mixed solution；
2. mixed solution is placed in container, and 5～8h is placed under room temperature, is subsequently placed in 24h in 100 DEG C of constant temperature ovens, shape in container
Yellowly film, scraping wears into fine powder；
3. the fine powder is placed in tube furnace, is warming up to 350 DEG C with 1 DEG C/min and is incubated 3h, then 600 are warming up to 1 DEG C/min
DEG C, subsequently it is warming up to 900 DEG C with 5 DEG C/min and is incubated 2h, obtain the order mesoporous SiO of black2/ C composite；
(ii) microwave reduction prepares order mesoporous carborundum
Order mesoporous SiO2/ C composite is placed in micro-wave oven zone line, adjustment position, until infrared temperature probe measure it is compound
The maximum temperature point of material；It is 0.09MPa to be evacuated to vacuum, and it is 0.03MPa to be passed through nitrogen to vacuum, vacuumizes, leads to
Nitrogen steps are repeated twice, after be evacuated to vacuum again for 0.09MPa, it is 0.07MPa to be passed through nitrogen to vacuum；
Open micro-wave oven cooling water circulating device, open microwave control switch, adjust microwave power cause to be warming up in stove 1300 DEG C ±
10 DEG C, isothermal reaction 20min；Microwave control switch is closed, stops heating, be evacuated to vacuum for 0.09MPa, nature in stove
After being cooled to room temperature, recirculated water is closed；Atmospheric valve is opened, when microwave furnace pressure reaches atmospheric pressure, fire door is automatically opened up,
Take out, obtain the order mesoporous carborundum of powder.
2. the preparation method of a kind of order mesoporous carborundum according to claim 1, it is characterised in that：With low-angle X-
Ray powder diffraction appearance at 0.8, illustrates that synthetic product is regular orderly mesoporous material.
3. the preparation method of a kind of order mesoporous carborundum according to claim 1, it is characterised in that：With specific surface and
Suction-desorption isotherm that Porosimetry is obtained, suction-desorption isotherm meets H1 types and returns stagnant ring, and what H1 types returned stagnant ring reflection is
The cylindrical hole of even aperture distribution, finds out that aperture concentrates on 6.3nm, suction-desorption isotherm and aperture by pore size distribution curve
Distribution curve illustrates that the carborundum for synthesizing is ordered into meso-hole structure jointly.
4. the preparation method of a kind of order mesoporous carborundum according to claim 1, it is characterised in that what (ii) step obtained
Order mesoporous carborundum powder has subsequently carried out removal of impurities process, and the removal of impurities is processed includes that high temperature carbon removal treatment and pickling are removed at silicon
Reason.
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| CN106540733B (en) * | 2016-10-27 | 2019-04-05 | 太原理工大学 | A method of preparing graphite phase carbon nitride material |
| CN107416837B (en) * | 2017-05-09 | 2019-10-15 | 武汉科技大学 | A method of porous nano silicon carbide is prepared by raw material of silicate glass |
| CN112093801B (en) * | 2020-05-11 | 2022-05-03 | 武汉科技大学 | Rice hull-based nano silicon carbide/carbon composite wave-absorbing material and preparation method thereof |
| CN111729678A (en) * | 2020-06-30 | 2020-10-02 | 同济大学 | Copper-palladium-loaded mesoporous silicon carbide-based catalyst and preparation method and application thereof |
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| CN101177269A (en) * | 2007-12-13 | 2008-05-14 | 复旦大学 | Meso-porous structural high specific surface carborundum material and preparation method thereof |
| CN102674354A (en) * | 2012-05-11 | 2012-09-19 | 南京工业大学 | Preparation method for mesoporous silicon carbide material |
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| JP6230106B2 (en) * | 2013-07-31 | 2017-11-15 | 太平洋セメント株式会社 | Method for producing silicon carbide single crystal |
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| CN101177269A (en) * | 2007-12-13 | 2008-05-14 | 复旦大学 | Meso-porous structural high specific surface carborundum material and preparation method thereof |
| CN102674354A (en) * | 2012-05-11 | 2012-09-19 | 南京工业大学 | Preparation method for mesoporous silicon carbide material |
Non-Patent Citations (2)
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| "Low-Temperature Pseudomorphic Transformation of Ordered Hierarchical Macro-mesoporous SiO2/C Nanocomposite to SiC via Magnesiothermic Reduction";Yifeng Shi et al.;《Journal of the American Chemical Society》;20100401;第132卷(第6期);第5552-5553页 * |
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