CN106629745A - Method for preparing cellulose supported hollow SiO2 microsphere catalytic carrier - Google Patents
Method for preparing cellulose supported hollow SiO2 microsphere catalytic carrier Download PDFInfo
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- CN106629745A CN106629745A CN201710014898.1A CN201710014898A CN106629745A CN 106629745 A CN106629745 A CN 106629745A CN 201710014898 A CN201710014898 A CN 201710014898A CN 106629745 A CN106629745 A CN 106629745A
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- microballoon
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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
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- B01J32/00—
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention discloses a method for preparing cellulose supported hollow SiO2 microsphere catalytic carrier. The method mainly comprises the steps of using the microsphere aggregates formed by polyelectrolyte polyacrylic acid in a poor solvent thereof as the mold, using ethyl silicate as the precursor, conducting hydrolysis and polymerization to obtain SiO2/PAA core-shell microsphere, centrifuging and washing the product to remove the polyelectrolyte polymer to form hollow SiO2 microspheres, and loading the hollow SiO2 microspheres onto cellulose to obtain cellulose supported hollow SiO2 microsphere catalytic carriers. The method for preparing cellulose supported hollow SiO2 microsphere catalytic carrier has the advantages that the method is simple and fast; the hollow SiO2 microspheres are scattered with uniform particle size; the preparation cost is low; the application value is high. The method uses natural cellulose as the support carrier, thus not only the degradable green materials are utilized, the environmental pollution is mitigated, but also at the same time, the cellulose macromolecule has good adsorbing function with good support performance.
Description
Technical field
The present invention relates to a kind of preparation method of cellulose catalytic carrier, more particularly to a kind of cellulose loads hollow SiO2
The preparation method of microballoon catalytic carrier, belongs to field of material engineering technology.
Background technology
Silica (SiO2), because it has good mechanical strength, heat endurance and chemical inertness, in scientific research and life
Product field suffers from important effect.Again because SiO2Colloid has high stability, nano core-shell knot in liquid medium
The controllability of structure precipitation process and thickness of the shell is good.In addition, the SiO prepared by sol-gel process2Surface is with substantial amounts of
Silanol base, the often place of Polymer adsorption, it is many in polarity, highly polar homopolymers and copolymers can pass through hydrogen bond
It is attracted to its surface.So, SiO2It is very handy core-shell type cladding medium.
Hollow SiO2Micro-sphere material has in the field such as catalysis, the loading of medicine and dyestuff and release, absorption potentially answers
With value, the extensive concern of people is caused.Although existing SiO2The preparation method of hollow ball has many reports, but exists mostly
The time spends the deficiencies such as longer, laboratory strength is excessive.And great majority prepare the method for hollow microsphere and need to remove template, one
As need to select appropriate chemical solvent to dissolve or combustion decomposition template can obtain hollow-core construction at a high temperature of certain.Porous material
Material has pore passage structure size adjustable and queueing discipline due to it, the features such as high specific surface area and big adsorption capacity, is urging
The field such as change, separation, absorption, biomaterial, sensor advanced composite material (ACM) and photoelectronics, electromagnetism, materialogy, environmentology
Have a wide range of applications.
In porous material preparation field, Chinese patent (CN201610244127.7) is " with a kind of nonionic/anion binding
Type surfactant for soft template silicon dioxide microsphere preparation " disclose reversible addion-fragmentation chain transfer method polymerization
The star amphiphilic block copolymer with cagelike silsesquioxane as core is obtained, it contains hydrophilic polymethoxy polyethylene glycol propylene
Acid esters section, hydrophobic polymethyl methacrylate section, hydrophobic polystyrene section, and cagelike silsesquioxane core；Mesoporous dioxy
Silicon nitride material is prepared and is mainly star amphiphilic block copolymer for soft template, and tetraethyl orthosilicate is silicon source, and tetrahydrofuran/hydrochloric acid is molten
Liquid is mixed solvent, and selectivity volatilization tetrahydrofuran is realized.A kind of Chinese patent (CN201610094136.2) " controllable water suction two
The controllable water suction earth silicon material of the preparation method of silicon oxide microsphere ", macroscopic view has micro-sphere structure, and microcosmic has meso-hole structure,
Simultaneously synthesizing hybridisation silica gel has a high activity surface, narrow pore-size distribution and excellent mechanical stability, the controllable water suction
The preparation method of silicon dioxide microsphere material can be quick, and simplicity prepares the silicon dioxide microsphere with controllable water imbibition performance.In
State's patent (CN201610108385.2) " a kind of monitoring of near infrared light, the mesoporous silicon dioxide micro-sphere of controlled drug release and its
The mesoporous silicon dioxide micro-sphere that synthetic method " is related to is sandwich construction：Most kernel is a smooth nano SiO 2 particle,
For adjusting microspherulite diameter and load near-infrared nanocrystalline body, these near-infrared nanocrystalline bodies are excited in certain wavelength near infrared light
Under, lower transformation can occur, that is, send the near infrared light of specific wavelength；Secondary outer layer is one layer of smooth silica shell,
For fixing and protecting the near-infrared nanocrystalline body of internal layer；Outermost layer is mesoporous silicon oxide shell, for load target medicine
With the quencher molecule of near infrared light nanocrystal and it is connected or coats responsive polymer, to realize that controlled drug discharges.The U.S. is special
Sharp (US4132560) " Pigmented microporous silica microspheres " provides a kind of by acidifying water
The method that bag oil emu prepares microballoon, the silicon dioxide microsphere after coloring can be used for coating composition as opacifier and conduct is filled out
Expect the manufacture for paper.United States Patent (USP) (US4011096) " Vesiculated silica microspheres " provides one kind
The method that the double emulsions of acidification oil bag oil-in-water prepare microballoon, the silicon dioxide microsphere of bubbles can be used for coating group as opacifier
Compound and applying filler are in papermaking.Up to now, yet there are no cellulose as skeleton, loaded by Moist chemical synthesis cellulose
Hollow SiO2The related process technologies of microballoon catalytic carrier occur.
The cellulose that the present invention is provided loads hollow SiO2Microballoon catalytic carrier, is by polyelectrolyte polyacrylic acid (PAA)
The sphere aggregates formed in its poor solvent are template, and tetraethyl orthosilicate (TEOS) is silicon source predecessor, and Jing is hydrolyzed, polymerization
After obtain SiO2/ PAA core-shell particles, product Jing centrifugation washings, can remove polyelectrolyte polymers so as to form SiO2It is hollow micro-
Ball, is then loaded to and the hollow SiO of cellulose load is obtained on cellulose2Microballoon catalytic carrier.The method is fast and convenient,
SiO2Tiny balloon disperses and uniform particle diameter, low production cost, and using value is high.The present invention is carried using native cellulose as load
Body, had both taken full advantage of biodegradable green material, had reduced environmental pollution, while cellulose macromolecule itself is with good
Good adsorption function, the cellulose of generation loads hollow SiO2Microballoon catalytic carrier loading functional is good, application it is wide and
Prospect is huge.The cellulose of preparation loads hollow SiO2Microballoon catalytic carrier is applied to catalysis, medical and magnetic, photoelectric material etc.
The application in field, the production meaning with reality.
The content of the invention
To overcome traditional Si O2The defect such as preparation process present in tiny balloon synthetic method is loaded down with trivial details, time-consuming, while changing
Kind SiO2Tiny balloon reunite serious, particle diameter heterogeneity the problems such as, prepare fast and convenient method of operating, dispersion and particle diameter be equal
First, low production cost, the high SiO of using value2Tiny balloon, it is an object of the invention to provide a kind of load of cellulose is hollow
SiO2The preparation method of microballoon catalytic carrier.
For achieving the above object, the technical scheme is that and adopt following steps：
1) polyacrylic acid of 0.1-0.2g is placed in conical flask, at ambient temperature, adds 1-2mL concentration to be 25%
Polyacrylic acid is dissolved into transparent settled solution by ammoniacal liquor, and stirring simultaneously pours rapidly the ethanol that 20-40mL concentration is 99.7%, solution into
It is changed into milky, then divides 0.5-1mL tetraethyl orthosilicates 4 times, each interval time 1-3h, in injection reactant liquor, continues to stir
3-5h is mixed, is centrifuged and is obtained hollow SiO with distillation 5 post-dryings of water washing2Microballoon；
2) by step 1) the hollow SiO that obtains2Microballoon adds Cyanuric Chloride, and 3-5h is reacted under condition of ice bath, then will
Cellulose powder is dissolved in DMF, by the hollow SiO of load2Microballoon is added and passed through in 70-90 DEG C of shaking bath
The cellulose powder reaction 1-3h of DMF dissolving, product washing suction filtration 5 times is simultaneously dried, that is, obtains having loaded
Into cellulose load hollow SiO2Microballoon catalytic carrier.
Described hollow SiO2Microballoon is 1-3 with the mass ratio of Cyanuric Chloride:1.
Described cellulose powder is 1-3 with the mass ratio of N,N-dimethylformamide:2.
Described hollow SiO2Microballoon is 2-3 with the mass ratio of cellulose powder:10.
Described cellulose is the one kind in rice straw, straw and bagasse source fiber element.
Compared with background technology, the invention has the advantages that：
Present invention improves traditional Si O2Preparation process present in tiny balloon synthetic method is loaded down with trivial details and time-consuming, SiO2It is empty
Heart microballoon reunite serious, particle diameter heterogeneity the problems such as, prepared fast and convenient method of operating, dispersion and uniform particle diameter, production
Low cost, the high SiO of using value2Tiny balloon, with long chain cellulose as skeleton adulteration SiO2Tiny balloon is not only increased
SiO2The overall adsorptivity of tiny balloon carrier, while also improve the added value of plant cellulose and do not cause environmental pressure,
Have important practical significance.
Description of the drawings
Fig. 1 is that cellulose prepared by embodiment 1 loads hollow SiO2The SiO of microballoon catalytic carrier2The transmitted electron of microballoon shows
Micro mirror figure (left figure：Amplify 20000 times；Right figure amplifies 40000 times)；
Fig. 2 is that cellulose prepared by embodiment 1 loads hollow SiO2The N of microballoon catalytic carrier2Adsorption-desorption curve.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1:
1) polyacrylic acid of 0.1g is placed in conical flask, at ambient temperature, addition 2mL concentration is that 25% ammoniacal liquor will
Polyacrylic acid is dissolved into transparent settled solution, and stirring simultaneously pours rapidly the ethanol that 25mL concentration is 99.7% into, and solution is changed into milky white
Color, then divides the tetraethyl orthosilicate of 0.5mL 4 times, per minor tick in corresponding time 2h injections reactant liquor.Continue to stir 5h,
It is centrifuged and uses after 5 drying of distillation water washing and obtains hollow SiO2Microballoon；
2) by step 1) the hollow SiO that obtains2Microballoon presses hollow SiO2Microballoon and Cyanuric Chloride 1:1 reaction mass ratio adds
Enter Cyanuric Chloride and 4h is reacted under condition of ice bath, then rice straw cellulose powder is pressed into rice straw cellulose powder and N, N- dimethyl formyl
Amine 1:2 mass ratio is dissolved in DMF, by the hollow SiO of load2Microballoon presses hollow SiO2Microballoon and cellulose powder
2:10 reaction mass ratio adds the cellulose powder reaction through N,N-dimethylformamide dissolving in 80 DEG C of shaking bath
2h, product washing suction filtration 5 times is simultaneously dried, that is, obtain loading the hollow SiO of cellulose load for completing2Microballoon catalytic carrier
(a)。
Embodiment 2:
1) polyacrylic acid of 0.15g is placed in conical flask, at ambient temperature, adds the ammonia that 1.5mL concentration is 25%
Polyacrylic acid is dissolved into transparent settled solution by water, and stirring simultaneously pours rapidly the ethanol that 20mL concentration is 99.7% into, and solution is changed into
Milky, then divides the tetraethyl orthosilicate of 0.5mL 4 times, per minor tick in corresponding time 3h injections reactant liquor.Continue to stir
3h, is centrifuged and obtains hollow SiO after being dried for 5 times with distillation water washing2Microballoon；
2) by step 1) the hollow SiO that obtains2Microballoon presses hollow SiO2Microballoon and Cyanuric Chloride 2:1 reaction mass ratio adds
Enter Cyanuric Chloride and 3h is reacted under condition of ice bath, then Wheat straw fiber element powder is pressed into Wheat straw fiber element powder and N, N- dimethyl formyl
Amine 3:2 mass ratio is dissolved in DMF, by the hollow SiO of load2Microballoon presses hollow SiO2Microballoon and cellulose powder
3:10 reaction mass ratio adds the cellulose powder reaction through N,N-dimethylformamide dissolving in 80 DEG C of shaking bath
1h, product washing suction filtration 5 times is simultaneously dried, that is, obtain loading the hollow SiO of cellulose load for completing2Microballoon catalytic carrier
(b)。
Embodiment 3:
1) polyacrylic acid of 0.2g is placed in conical flask, at ambient temperature, addition 1mL concentration is that 25% ammoniacal liquor will
Polyacrylic acid is dissolved into transparent settled solution, and stirring simultaneously pours rapidly the ethanol that 40mL concentration is 99.7% into, and solution is changed into milky white
Color, then divides the tetraethyl orthosilicate of 0.75mL 4 times, per minor tick in corresponding time 1h injections reactant liquor.Continue to stir 5h,
It is centrifuged and uses after 5 drying of distillation water washing and obtains hollow SiO2Microballoon；
2) by step 1) the hollow SiO that obtains2Microballoon presses hollow SiO2Microballoon and Cyanuric Chloride 3:1 reaction mass ratio adds
Enter Cyanuric Chloride and 4h is reacted under condition of ice bath, then Bagasse-cellulose powder is pressed into Bagasse-cellulose powder and N, N- dimethyl
Formamide 1:2 mass ratio is dissolved in DMF, by the hollow SiO of load2Microballoon presses hollow SiO2Microballoon and fiber
Plain powder 2:10 reaction mass ratio adds the cellulose powder through N,N-dimethylformamide dissolving in 70 DEG C of shaking bath
Reaction 2h, product washing suction filtration 5 times is simultaneously dried, that is, obtain loading the hollow SiO of cellulose load for completing2Microballoon catalysis is carried
Body (c).
Embodiment 4:
1) polyacrylic acid of 0.1g is placed in conical flask, at ambient temperature, addition 2mL concentration is that 25% ammoniacal liquor will
Polyacrylic acid is dissolved into transparent settled solution, and stirring simultaneously pours rapidly the ethanol that 30mL concentration is 99.7% into, and solution is changed into milky white
Color, then divides the tetraethyl orthosilicate of 1mL 4 times, per minor tick in corresponding time 2h injections reactant liquor.Continue to stir 4h, from
The heart simultaneously obtain hollow SiO after 5 drying of water washing with distilling2Microballoon；
2) by step 1) the hollow SiO that obtains2Microballoon presses hollow SiO2Microballoon and Cyanuric Chloride 1:1 reaction mass ratio adds
Enter Cyanuric Chloride and 5h is reacted under condition of ice bath, then rice straw cellulose powder is pressed into rice straw cellulose powder and N, N- dimethyl formyl
Amine 2:2 mass ratio is dissolved in DMF, by the hollow SiO of load2Microballoon presses hollow SiO2Microballoon and cellulose powder
3:10 reaction mass ratio adds the cellulose powder reaction through N,N-dimethylformamide dissolving in 90 DEG C of shaking bath
3h, product washing suction filtration 5 times is simultaneously dried, that is, obtain loading the hollow SiO of cellulose load for completing2Microballoon catalytic carrier
(d)。
Determine four kinds of hollow SiO prepared by embodiment 1,2,3,42The particle size of microballoon, while tester calculates it bearing
The load factor being loaded onto on cellulose.Table 1 is four kinds of hollow SiO prepared by embodiment 1,2,3,42The particle size of microballoon determines knot
Fruit and the load factor result being loaded on cellulose.From data in table 1, obtained using preparation method of the present invention
Cellulose loads hollow SiO2Microballoon catalytic carrier (a), cellulose load hollow SiO2Microballoon catalytic carrier (b), cellulose load
Hollow SiO2Microballoon catalytic carrier (c), cellulose load hollow SiO2The SiO of microballoon catalytic carrier (d)2Microsphere average grain diameter exists
248-356nm, is loaded to the load factor on cellulose in 11.5-15.3%, illustrates hollow SiO prepared by the method2It is micro-
Ball is loaded on cellulose and has synthesized the hollow SiO of cellulose load really2Microballoon catalytic carrier and with preferable load effect.
Such as Fig. 1, from embodiment 1 hollow SiO is prepared2The transmission electron microscope figure of microballoon can be seen that, the synthesis of embodiment 1
SiO2Microsphere diameter about 250nm, there is obvious hollow structure, and wall thickness is about 40nm, and hollow wall is smoother, becomes without internal penetration
Gesture.Such as Fig. 2, from the cellulose of the preparation of embodiment 1 hollow SiO is loaded2The N of microballoon catalytic carrier2Can in adsorption-desorption isothermal
To find out, sample maximum is characterized in that absorption is misaligned with desorption, an obvious H3 type hysteresis loop occurs, in showing sample
With the presence of uneven slit-shaped duct.The specific surface area of sample is 26.83m2/g.Pore size distribution curve occurs one in 3.5nm
Individual sharp peak, illustrates that its aperture major part is 3.5nm, that is, illustrate that microballoon is implicitly present in meso-hole structure, is that from now on microballoon is further
Carrier using provide condition.
Table 1
Listed above is only the specific embodiment of the present invention.The invention is not restricted to above example, there can also be many
Deformation.All deformations that one of ordinary skill in the art can directly derive from present disclosure or associate, all should
It is considered protection scope of the present invention.
Claims (5)
1. a kind of cellulose loads hollow SiO2The preparation method of microballoon catalytic carrier, it is characterised in that comprise the following steps：
1) polyacrylic acid of 0.1-0.2g is placed in conical flask, at ambient temperature, adds the ammoniacal liquor that 1-2mL concentration is 25%
Polyacrylic acid is dissolved into transparent settled solution, stirring simultaneously pours rapidly the ethanol that 20-40mL concentration is 99.7% into, and solution is changed into
Milky, then divides 0.5-1mL tetraethyl orthosilicates 4 times, each interval time 1-3h, in injection reactant liquor, continues to stir 3-
5h, is centrifuged and obtains hollow SiO with distillation 5 post-dryings of water washing2Microballoon；
2) by step 1) the hollow SiO that obtains2Microballoon adds Cyanuric Chloride, 3-5h is reacted under condition of ice bath, then by cellulose
Powder is dissolved in DMF, by the hollow SiO of load2Microballoon is added through N, N- bis- in 70-90 DEG C of shaking bath
The cellulose powder reaction 1-3h of NMF dissolving, product washing suction filtration 5 times is simultaneously dried, that is, obtain loading the fibre for completing
The hollow SiO of dimension element load2Microballoon catalytic carrier.
2. a kind of cellulose according to claim 1 loads hollow SiO2The preparation method of microballoon catalytic carrier, its feature exists
In：Described hollow SiO2Microballoon is 1-3 with the mass ratio of Cyanuric Chloride:1.
3. a kind of cellulose according to claim 1 loads hollow SiO2The preparation method of microballoon catalytic carrier, its feature exists
In：Described cellulose powder is 1-3 with the mass ratio of N,N-dimethylformamide:2.
4. a kind of cellulose according to claim 1 loads hollow SiO2The preparation method of microballoon catalytic carrier, its feature exists
In：Described hollow SiO2Microballoon is 2-3 with the mass ratio of cellulose powder:10.
5. a kind of cellulose according to claim 1 loads hollow SiO2The preparation method of microballoon catalytic carrier, its feature exists
In：Described cellulose is the one kind in rice straw, straw and bagasse source fiber element.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107519149A (en) * | 2017-08-30 | 2017-12-29 | 东华大学 | A kind of preparation method for the silica/CS/PAA nucleocapsid composite nano anti-biotic particles for loading triclosan |
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| CN1223231A (en) * | 1997-11-13 | 1999-07-21 | 德古萨股份公司 | Mouldings based on pyrogenic silicon dioxide |
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| JP2010037137A (en) * | 2008-08-05 | 2010-02-18 | Sony Corp | Hollow particle and method for producing the same |
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