CN109607544A - A kind of method of synthesizing flaky nano elementary silicon - Google Patents
A kind of method of synthesizing flaky nano elementary silicon Download PDFInfo
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- CN109607544A CN109607544A CN201811612838.0A CN201811612838A CN109607544A CN 109607544 A CN109607544 A CN 109607544A CN 201811612838 A CN201811612838 A CN 201811612838A CN 109607544 A CN109607544 A CN 109607544A
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- elementary silicon
- silicon
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- nano elementary
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
Abstract
The invention discloses a kind of method of synthesizing flaky nano elementary silicon, preparation method is as follows: using quaternary ammonium salt modification Schistose kaolinite, adds pillared object and be modified, after drying, calcining, adds aluminium powder heating reduction, filtered, washing obtains flake nano elementary silicon.The flake nano elementary silicon have it is laminar structured, product have the characteristics that stability height, reactivity it is good；Present invention process is easy to operate and safe, low in cost, mild condition, the rate of output are high, improves product stability, is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the preparation technical field of synthesis elementary silicon, more particularly to a kind of synthesizing flaky nano silicon
The method of simple substance.
Background technique
As China's science and technology continues to develop, silicon is in photoelectric field, and semicon industry is using more and more, to the need of elementary silicon
The amount of asking is continuously increased, and the synthesis of elementary silicon has become research hotspot.Elementary silicon because of its unique structure and characteristic of semiconductor,
The fields such as light, electricity, magnetic are widely used.But the preparation method of the elementary silicon prior art has at high cost, condition harshness
The shortcomings that.
Silicon nanocrystal is often referred to size in nanoscale silicon crystal.Silicon nanostructure due to quantum confined effect effect and
A variety of new features different from body silicon materials are produced, such as: fluorescent effect is significant, optical band gap is adjustable, optical absorption enhancing
It is obvious etc. with more exciton effects under high-energy photon effect.Since silicon materials are most important at present and most widely used semiconductor materials
Material, silicon nano material has the application field for being conducive to expand traditional silicon device, thus nano-silicon is taken seriously.Currently, sharp
With silane decomposition method, laser bombardment silicon target method, low temperature plasma method prepares nano silicon spheres or particle, and cost of material is high, operation
Condition is harsh.Some methods prepare sheet nanometer elementary silicon, need to be collectively formed with graphene or other matrix, graphene is not
The characteristics of easily removing, limits the production application of lamella silicon.Using the pillared effect of pillared object, by modified sheet silica
Dispersion, then restores, obtains sheet nanometer elementary silicon.This method is easy to operate, is easy to go into operation on a large scale.
Therefore, in conjunction with the above problem, a kind of synthesizing flaky nano silicon low in cost, easy to operate, mild condition is provided
The problem of method of simple substance is those skilled in the art's urgent need to resolve.
Summary of the invention
In view of this, this method raw material sources are wide the present invention provides a kind of method of synthesizing flaky nano elementary silicon, produce
Object stability is high, it can be achieved that largely preparing flake nano elementary silicon.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of method of synthesizing flaky nano elementary silicon, comprising the following steps:
S1 is stirred for 24 hours under the conditions of 600r/min with quaternary ammonium salt modification Schistose kaolinite；
S2 adds pillared object to step S1 products therefrom, and 12~36h, mixing speed 600r/min, ultrasound is mixed
5~6h is handled, supersonic frequency 40KHz, heating, drying, natural cooling after calcining obtains pillared layered kaolin intermediate；
S3, the pillared layered kaolin intermediate that step S2 is obtained are mixed with aluminium powder, are uniformly mixed and are placed on sintering furnace
In, it is warming up to 400~700 DEG C of reactions under an inert atmosphere, calcines 1~5h, collects product in reaction after natural cooling；
S4, into reaction obtained by step S3, the dilute sulfuric acid of 1mol/L is added in product, and reaction to no aluminium ion generates, centrifugation point
Sediment is separated out, is washed with deionized 3-5 times, the hydrofluoric acid reaction of 0.1mol/L, after centrifuge separation, deionized water are added
Washing 3-5 times is dried, obtains flake nano elementary silicon.
Preferably, quaternary ammonium salt is hexadecyltrimethylammonium chloride, cetyl trimethylammonium bromide in the step S1
One of.
Preferably, kaolin in the step S1: quaternary ammonium salt: the mass ratio of deionized water is 1:1.44~1.66:2.
Preferably, pillared object includes but is not limited to sodium chloride, potassium chloride in the step S2.
Preferably, the molar ratio of kaolin and pillared object is 1:5~10 in the step S2.
Preferably, 3-5h is calcined under the conditions of 300~350 DEG C of temperature in the step S2.
Preferably, the molar ratio of silica and aluminium powder is 1:2~5 in pillared modified kaolin in the step S3.
Preferably, in the step S3 under an inert atmosphere with heat up per minute 20 DEG C speed heating.
Preferably, in the step S4 controlled at being dried for 24 hours under the conditions of 100 DEG C.
As can be seen from the above technical solutions, compared with prior art, beneficial effects of the present invention are as follows:
Present invention quaternary ammonium salt modification Schistose kaolinite, quaternary ammonium salts make lamella kaolin structure in piece interlayer
It is loose, it is easy to subsequent pillared modification and aluminum reduction reaction, highly shortened the pillared object modified time；Utilize pillared object
Pillared effect is modified, and separates lamella, and reaction is not easy to be formed spherical or particle, and lamella is not easy to gather blocking, increases ratio
Surface area improves the activity of flake nano elementary silicon, dispersibility and loading；Utilize aluminum reduction, dilute sulfuric acid, hydrofluoric acid
Filtration washing removes the impurity such as aluminium oxide, the silica generated in raw material and reaction process, improves the rate of output of product.It adopts
With technical solution of the present invention, the rate of output is up to 80% or more, and final product can be easily separated with raw material, reacts in normal temperature condition
Lower progress, it is mild condition, easy to operate, low in cost, it can be achieved that heavy industrialization prepares flake nano elementary silicon.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1:
The embodiment of the present invention 1 discloses a kind of method of synthesizing flaky nano elementary silicon, the technical solution adopted is as follows:
A kind of method of the synthesizing flaky nano elementary silicon, comprising the following steps:
S1, in 1000mL beaker, be added 50g Schistose kaolinite, 72g hexadecyltrimethylammonium chloride, 100mL go from
Sub- water stirs for 24 hours under the conditions of 600r/min；
250g sodium chloride is added into step S1 by S2, and 12h, mixing speed 600r/min, 40KHz ultrasound is mixed
5h is handled, heating, drying controls 300 DEG C of temperature, calcines 3h, and natural cooling obtains pillared layered kaolin intermediate；
S3 is added 26g aluminium powder and mixes with the pillared layered kaolin intermediate that step S2 is obtained, is uniformly mixed and is placed on burning
In freezing of a furnace, 700 DEG C of reactions are warming up to 20 DEG C of the speed of heating up per minute under an inert atmosphere, 1h is calcined, is received after natural cooling
Product in collection reaction；
S4, into reaction obtained by step S3, the dilute sulfuric acid of the 1mol/L of 3L is added in product, and reaction to no aluminium ion generates, from
The heart isolates sediment, is washed with deionized 3-5 times, adds the hydrofluoric acid reaction 0.5h of the 0.1mol/L of 50mL, centrifugation
After separation, deionized water is washed 3-5 times, controlled at being dried for 24 hours under the conditions of 100 DEG C, obtains flake nano elementary silicon,
It is 87% that experiment, which measures yield,.
Embodiment 2:
The embodiment of the present invention 2 discloses a kind of method of synthesizing flaky nano elementary silicon, the technical solution adopted is as follows:
A kind of method of the synthesizing flaky nano elementary silicon, comprising the following steps:
S1, in 1000mL beaker, be added 50g Schistose kaolinite, 72g hexadecyltrimethylammonium chloride, 100mL go from
Sub- water stirs for 24 hours under the conditions of 600r/min；
300g sodium chloride is added into step S1 by S2, and 36h, mixing speed 600r/min, 40KHz ultrasound is mixed
5.5h is handled, heating, drying controls 330 DEG C of temperature, calcines 5h, and natural cooling obtains pillared layered kaolin intermediate；
S3 is added 40g aluminium powder and mixes with the pillared layered kaolin intermediate that step S2 is obtained, is uniformly mixed and is placed on burning
In freezing of a furnace, 550 DEG C of reactions are warming up to 20 DEG C of the speed of heating up per minute under an inert atmosphere, 5h is calcined, is received after natural cooling
Product in collection reaction；
S4, into reaction obtained by step S3, the dilute sulfuric acid of the 1mol/L of 2.5L is added in product, and reaction to no aluminium ion generates,
It is centrifugated out sediment, is washed with deionized 3-5 times, the hydrofluoric acid reaction 0.5h of the 0.1mol/L of 60mL is added, from
After heart separation, deionized water is washed 3-5 times, controlled at being dried for 24 hours under the conditions of 100 DEG C, obtains flake nano silicon list
Matter, it is 86% that experiment, which measures yield,.
Embodiment 3:
The embodiment of the present invention 3 discloses a kind of method of synthesizing flaky nano elementary silicon, the technical solution adopted is as follows:
A kind of method of the synthesizing flaky nano elementary silicon, comprising the following steps:
S1, in 1000mL beaker, be added 50g Schistose kaolinite, 83g cetyl trimethylammonium bromide, 100mL go from
Sub- water stirs for 24 hours under the conditions of 600r/min；
500g potassium chloride is added into step S1 by S2, and 30h, mixing speed 600r/min, 40KHz ultrasound is mixed
6h is handled, heating, drying controls 350 DEG C of temperature, calcines 4h, and natural cooling obtains pillared layered kaolin intermediate；
S3 is added 51g aluminium powder and mixes with the pillared layered kaolin intermediate that step S2 is obtained, is uniformly mixed and is placed on burning
In freezing of a furnace, 400 DEG C of reactions are warming up to 20 DEG C of the speed of heating up per minute under an inert atmosphere, 3h is calcined, is received after natural cooling
Product in collection reaction；
S4, into reaction obtained by step S3, the dilute sulfuric acid of the 1mol/L of 6L is added in product, and reaction to no aluminium ion generates, from
The heart isolates sediment, is washed with deionized 3-5 times, adds the hydrofluoric acid reaction 0.5h of the 0.1mol/L of 80mL, centrifugation
After separation, deionized water is washed 3-5 times, controlled at being dried for 24 hours under the conditions of 100 DEG C, obtains flake nano elementary silicon,
It is 84% that experiment, which measures yield,.
Comparative example:
Pure silicon dioxide particle is taken, through 100 mesh sieve prescreenings, removes bulky grain, little particle is spare.Silica
Grain 10g is mixed with 10g aluminium powder, is warming up to 500 DEG C of reactions under an inert atmosphere, increases about 20 DEG C of temperature per minute, calcines 5h, from
So product in reaction is collected after cooling；The dilute sulfuric acid of the 1mol/L of 600mL is added, reaction to no aluminium ion generates, centrifuge separation
Sediment out is washed with deionized 3-5 times, and the hydrofluoric acid for adding the 0.1mol/L of 30mL reacts 0.5 hour, centrifuge separation
Afterwards, deionized water is washed 3-5 time, controlled at being dried for 24 hours under the conditions of 100 DEG C, is obtained elementary silicon, is tested and measure yield
It is 114%.
The actual yield of comparative example is greater than theoretical yield and also deposits the reason is that silicon has wrapped up partial oxidation aluminium in reduction process
It is not reduced the possibility being mixed in final product elementary silicon in part of silica.
Embodiment 4:
Performance detection is carried out to synthesis elementary silicon sample prepared by embodiment 1-3 and comparative example, take 5g sample elementary silicon with
The sodium hydroxide solution of enough 2mol/L reacts, and detection release hydrogen volume changes with time, testing result data such as 1 institute of table
Show:
1 sample of table and 2mol/L sodium hydroxide reaction response rate
| Sample | Hydrogen (ml/min) |
| Embodiment 1 | 30 |
| Embodiment 2 | 29 |
| Embodiment 3 | 28 |
| Comparative example | 3 |
By the data comparison of table 1 it is found that embodiment 1-3 is synthetically prepared out sheet nano-silicon simple substance, reduction reaction is carried out
Thoroughly, and be swift in response, illustrate silicon good dispersion, contacted with reactant it is more abundant, so reaction rate is big.Pillared object is modified
Intermediate afterwards has layer structure, is easier to contact with reactant compared to particle, is easy to react progress.
Embodiment 5:
3g sheet silicon and 3g control group particulate Si are taken respectively, are sufficiently mixed with 30g sodium chloride, in air, temperature control
5h is calcined under the conditions of being 300 DEG C, is mixed after cooling with 150mL water, is filtered, washed, dries, and experiment, which measures, respectively obtains 6.3g piece
Stratiform silica and 5.8g particulate silica.
With the methylene blue of 14mg/L, Static Adsorptive capacity test is carried out at room temperature, and absorption test carries out 12h, lamella
Shape silica reaches 450mg/g to methylene blue adsorption number amount, and particulate silica reaches methylene blue adsorption number amount
107mg/g。
Sheet elementary silicon is oxidized to form sheet silica, and due to the effect of pillared object, piece lamellar spacing is larger, piece
Layer can receive adsorbate methylene blue；More accumulation hole is formed between lamella, also functions to the effect for receiving adsorbate.Lamella
Suction-operated performance is abundant.Granular silica does not have these performances, and many silica are not easy contact suction inside particle
Attached matter, suction-operated are difficult to sufficiently show.So sheet silica is big to methylene blue adsorption number amount.Sheet dioxy
SiClx specific surface area reaches 210m2/ g is greater than particulate silica specific surface area 80m2/ g, what large specific surface area had often had
Suction-operated.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (9)
1. a kind of method of synthesizing flaky nano elementary silicon, which comprises the following steps:
S1 is stirred for 24 hours under the conditions of 600r/min with quaternary ammonium salt modification Schistose kaolinite；
S2 adds pillared object to step S1 products therefrom, and 12~36h, mixing speed 600r/min, ultrasonic treatment is mixed
5~6h, supersonic frequency 40KHz, heating, drying, natural cooling after calcining obtain pillared layered kaolin intermediate；
S3, the pillared layered kaolin intermediate that step S2 is obtained are mixed with aluminium powder, are uniformly mixed and are placed in sintering furnace,
It is warming up to 400~700 DEG C of reactions under inert atmosphere, calcines 1~5h, collects product in reaction after natural cooling；
S4, into reaction obtained by step S3, the dilute sulfuric acid of 1mol/L is added in product, and reaction to no aluminium ion is generated, is centrifugated out
Sediment is washed with deionized 3-5 times, adds the hydrofluoric acid reaction of 0.1mol/L, after centrifuge separation, deionized water washing
It 3-5 times, is dried, obtains flake nano elementary silicon.
2. a kind of method of synthesizing flaky nano elementary silicon as described in claim 1, which is characterized in that season in the step S1
Ammonium salt is one of hexadecyltrimethylammonium chloride, cetyl trimethylammonium bromide.
3. a kind of method of synthesizing flaky nano elementary silicon as described in claim 1, which is characterized in that high in the step S1
Ridge soil: quaternary ammonium salt: the mass ratio of deionized water is 1:1.44~1.66:2.
4. a kind of method of synthesizing flaky nano elementary silicon as described in claim 1, which is characterized in that the step S2 center pillar
Supportting object includes but is not limited to sodium chloride, potassium chloride.
5. a kind of method of synthesizing flaky nano elementary silicon as described in claim 1, which is characterized in that high in the step S2
The molar ratio of ridge soil and pillared object is 1:5~10.
6. a kind of method of synthesizing flaky nano elementary silicon as described in claim 1, which is characterized in that in the step S2
3-5h is calcined under the conditions of 300~350 DEG C of temperature.
7. a kind of method of synthesizing flaky nano elementary silicon as described in claim 1, which is characterized in that the step S3 center pillar
Supportting the molar ratio of silica and aluminium powder in modified kaolin is 1:2~5.
8. a kind of method of synthesizing flaky nano elementary silicon as described in claim 1, which is characterized in that in the step S3
Under inert atmosphere with heat up per minute 20 DEG C speed heating.
9. a kind of method of synthesizing flaky nano elementary silicon as described in claim 1, which is characterized in that controlled in the step S4
Temperature processed is dried for 24 hours under the conditions of being 100 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112759662A (en) * | 2021-01-18 | 2021-05-07 | 福建农林大学 | Separation and purification method of tremella polysaccharide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112759662A (en) * | 2021-01-18 | 2021-05-07 | 福建农林大学 | Separation and purification method of tremella polysaccharide |
| CN112759662B (en) * | 2021-01-18 | 2021-12-28 | 福建农林大学 | Separation and purification method of tremella polysaccharide |
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