CN104925816B - A kind of titania modified bar-shaped silica core shell material and preparation method thereof - Google Patents
A kind of titania modified bar-shaped silica core shell material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of titania modified bar-shaped silica core shell material and preparation method thereof, the method is using the modified rod-like mesoporous material SiO of ARGET ATRP methods grafting amphipathic nature polyalcohol poly (glycidyl methacrylate) poly- (Methylacrylic acid polyethylene glycol single armor ether ester)2Prepared sample SiO2Poly (glycidyl methacrylate) poly- (Methylacrylic acid polyethylene glycol single armor ether ester), and as template hydrolysis butyl titanate, then high-temperature calcination removing polymer, prepares titania modified bar-shaped silica core shell material.Present invention improves over tradition prepares bar-shaped SiO2‑TiO2The method of composite material of core-shell structure, simple to operate, method is novel, solves conventional method and prepares bar-shaped SiO2‑TiO2TiO in composite material2Nano-particle autohemagglutination and the problem easily reunited on mesoporous material surface.
Description
Technical field
The invention belongs to field of material synthesis technology, more particularly to a kind of titania modified bar-shaped silica (SiO2-
TiO2) core-shell material and preparation method thereof.
Background technology
Ordered mesoporous material is the rapidly growing novel nano structure material nineties in last century, has just been obtained since the birth
International physics, chemistry and the great attention of material educational circles, and develop rapidly and become one of study hotspot interdisciplinary.It is situated between in order
Porous materials in catalysis, are separated, are adsorbed and functionalization material because of its orderly pore passage structure, larger specific surface area and pore volume
There is potential application in field.Wherein mesoporous molecular sieve SBA-15 is with neutral surface active agent P123 as template, using hydro-thermal
Mesoporous silicon oxide (the SiO of bar-shaped high-sequential prepared by method2) material, by being chemically modified to its surface, Ke Yiyou
Its application in every field is expanded on effect ground.Wang(J.Phys.Chem.C,2011,115：Etc. 22191) use silane coupler
3- aminopropyl triethoxysilanes (APTES) SiO mesoporous to corynebacterium2Material carries out rear graft modification, prepares functionalization
Mesoporous material, its six sides shape meso-hole structure do not change, and interplanar distance, cell parameter and wall thickness increased, specific surface
There is the trend for reducing in product, pore volume and aperture, and the modified mesoporous material of aminopropyl as carrier to PPL (pig pancreas fat
Enzyme) fixed amount and the catalysis activity to glyceryl triacetate hydrolysis, heat endurance, reusing be significantly increased.
In recent years, titanium dioxide (TiO2) because of its good semiconduction, light transmittance, refractive index, chemical stability, and
The advantages of inexpensive, nonhazardous, bio-compatibility, get more and more people's extensive concerning, be often used as the shell of inorganic material
Rotating fields, are mainly used in the aspects such as catalyst, the solar cell of dye sensitization and sensor.But, TiO2Nano-particle
Easily reunite in reaction system, effective ratio area also can reduce therewith, cause the rapid decline of its catalysis activity, limit which
Using.In order to solve the above problems, can be by TiO2, on the surface of mesoporous material, the presence of loose structure is or not nanometer particle load
TiO can be only effectively increased2Specific surface area, and be beneficial to TiO2Optical absorption, so as to improve photocatalytic activity.
So far, with regard to SiO2-TiO2The preparation method of core-shell material, what is reported in document are a lot, mainly with template
Based on, more with SiO2Ball is template, and minority is with SiO2Mesoporous material is template.Using mesoporous material high-sequential it is mesoporous with
And larger specific surface area, TiO can be made2Nano-particle is deposited in mesoporous material surface, and the SiO of favorable dispersibility is obtained2-
TiO2Core-shell material.Qian(J.Phys.Chem.C,2013,117：Etc. 19544) with SBA-15 as template, by sol-gel
Method makes TiO2Mesoporous material surface is directly loaded in, SiO is obtained2-TiO2Core-shell material, so by TiO2Shell is directly coated on Jie
Porous materials SiO2Core surface, easily causes TiO in preparation process2Nano-particle autohemagglutination or in SiO2Core surface formation office
Portion reunites, so as to affect its photocatalysis effect.To solve the above problems, first mesoporous material can be modified, be obtained new
Template, such as SiO2- polymer.
At present, using the modified rod-like mesoporous material SiO of ARGET ATRP methods grafting amphipathic nature polyalcohol2Prepared sample
SiO2- PGMA-POEOMA, and as template hydrolysis butyl titanate (TBT), then high-temperature calcination removing polymer, prepares
Go out bar-shaped SiO2-TiO2Core-shell composite material, TBT hydrolysis shrink sweet by hydrogen bond action and amphipathic polymer polymethylacrylic acid
Grease-poly- (Methylacrylic acid polyethylene glycol single armor ether ester) (PGMA-POEOMA) is acted on.It is grafted with ARGET ATRP methods amphipathic
The bar-shaped SiO of polymer modification2SiO is prepared for template2-TiO2The composite of nucleocapsid is not also reported.
The content of the invention
Technical problem underlying to be solved by this invention is exactly to improve tradition to prepare bar-shaped SiO2-TiO2Core shell structure is combined
The method of material, simple to operate, method is novel, solves conventional method and prepares bar-shaped SiO2-TiO2TiO in composite material2Receive
Rice corpuscles autohemagglutination and the problem easily reunited on mesoporous material surface.
To solve the above problems, the present invention employs the following technical solutions realization：
A kind of titania modified bar-shaped silica core shell material, a length of 0.8-1.2 μm, a width of 350-450nm, aperture
For 5-10nm, regulate and control SiO using different amounts of monomer OEOMA by adjusting2-TiO2The TiO of core-shell material2Thickness of the shell, is prepared for
Bar-shaped SiO of the thickness of the shell for 15-24nm2-TiO2Core-shell material, is especially successfully prepared thickness of the shell and is respectively 18nm, 24nm and
The bar-shaped SiO of 20nm2-TiO2Core-shell material.
The preparation method of the titania modified bar-shaped silica core shell material, is grafted using ARGET ATRP methods
The modified rod-like mesoporous material SiO of amphipathic nature polyalcohol PGMA-POEOMA2Prepared sample SiO2- PGMA-POEOMA, and as mould
Plate hydrolysis of tetrabutyl titanate (TBT), then high-temperature calcination removing polymer, prepares titania modified bar-shaped silica core
Shell material.
Comprise the following steps：
(1) bar-shaped SiO2Preparation：With tetraethyl orthosilicate (TEOS) as raw material, with polyethylene glycol (PEG, Mn=4000
～10000g/moL, preferably 6000g/moL) and polyoxyethylene-poly-oxypropylene polyoxyethylene (P123, Mn=4000～
10000g/moL, preferably 5800g/moL) for template, reaction prepares a length of 0.8-1.2 μm (preferably 1 μm), a width of
350-450nm, the mesoporous SiO of corynebacterium that aperture is 5-10nm2；
(2)SiO2-NH2Preparation：With 3- aminopropyl triethoxysilanes (APTES) as coupling agent, to obtain in step (1)
The mesoporous SiO of corynebacterium for arriving2For raw material, amino modified SiO is prepared2-NH2；
(3)SiO2The preparation of-Br：With the SiO obtained in dibromo-isobutyl acylbromide (BiB) and step (2)2-NH2For raw material, system
The standby bromine that obtains is modified successful SiO2-Br；
(4)SiO2The preparation of-PGMA-Br：With GMA (GMA), FeCL3·6H2O、PPh3(three
Phenylphosphine), the SiO that obtains of vitamin C (VC), EBiB (2- isobutyl ethyl bromides) and step (3)2- Br is raw material, with DMF is
Solvent, using ARGET ATRP methods, reacts 20-24h at 55-65 DEG C, be dried, prepare SiO2-PGMA-Br；
Wherein, described raw material GMA, FeCL3·6H2O、PPh3, injection Vitamin B_6 BiB, initiator SiO2- Br and solvent
The adding proportion of DMF is 5mL：0.0045g：(0.0350-0.0524)g：(0.0203-0.0377)g：24μL：(0.08-0.12)
g：15mL；
(5)SiO2The preparation of-PGMA-POEOMA：
With SiO in step (4)2- PGMA-Br is initiator, with OEOMA (Methylacrylic acid polyethylene glycol single armor ether ester, Mn
=500g/moL), FeCl3·6H2O、PPh3, VC and EBiB be raw material, with DMF as solvent, using ARGET ATRP methods,
13-17h is reacted under the conditions of 85-95 DEG C, is dried, is prepared SiO2-PGMA-POEOMA；
Wherein, described raw material OEOMA, FeCL3·6H2O、PPh3, VC, EBiB, initiator SiO2- PGMA-Br and solvent
The adding proportion of DMF is (18-23) mL：0.015g：(0.1-0.125)g：(0.24-0.28)g：22.5μL：(0.03-0.06)
g：10mL；
(6) bar-shaped SiO2-TiO2The preparation of core-shell material：
The amphipathic SiO obtained in step (5) is added in reactor2- PGMA-POEOMA, and TBT, ethanol, ammoniacal liquor,
22-26h is reacted at 35-40 DEG C, is dried, SiO is obtained2-PGMA-POEOMA-TiO2；
Wherein, SiO2The adding proportion of-PGMA-POEOMA, TBT, ethanol and ammoniacal liquor is：(0.007-0.016)g：
(0.45-0.60)g：50mL：(0.36-0.56)mL；
By SiO obtained above2-PGMA-POEOMA-TiO2, 5-7h is calcined at 440-490 DEG C, obtain SiO2-TiO2Core
Shell material.
In step (1), the bar-shaped SiO2Preparation method be specially：
Template polyethylene glycol (PEG) and polyoxyethylene-poly-oxypropylene polyoxyethylene (P123) are dissolved in into water and hydrochloric acid
Mixed solution in, stir to PEG and P123 and all dissolve, stirring is added dropwise over tetraethyl orthosilicate (TEOS), TEOS,
P123, PEG, HCl and H2The mol ratio of O is 1：0.017：0.0088：5.71：192, it is rear after stirring and evenly mixing to stand, by mixture
It is transferred in autoclave, cools down after reaction.The white mixture suction filtration of above-mentioned gained is precipitated into thing, is washed, is dried,
Then 4h is calcined at 450-550 DEG C, prepare a length of 0.8-1.2 μm (preferably 1 μm), a width of 350-450nm, aperture 5-
The mesoporous SiO of 10nm corynebacteriums2；
In step (1), washing, the detailed process being dried are：With distilled water cyclic washing 3-5 time, by the sediment of gained
Vacuum drying.The time for stirring and evenly mixing is 5min.
In step (1), the reaction temperature of standing is 35 DEG C, and the reaction time is 24h, and the reaction temperature in autoclave is
130 DEG C, the reaction time is 24h.
In step (2), SiO2-NH2Preparation method be specially：
The SiO in reactor adding corynebacterium mesoporous2And toluene, after being uniformly mixed, dropwise add toward reactor
Enter 1.884-2.826g APTES, N2Under the conditions of after stirring reaction, eccentric cleaning is dried, obtains amino modified SiO2-NH2；
Wherein, the SiO2, toluene and APTES adding proportion be：(0.60-0.80)g：20mL：(1.884-2.826)
g。
In step (2), reaction temperature is 70-80 DEG C (preferably 75 DEG C), and the reaction time is 18h.
In step (3), SiO2The preparation method of-Br is specially：
SiO is added in reactor2-NH2, toluene, triethylamine, ultrasound；Above-mentioned reactor is placed in into low-temp reaction after ultrasound
In bath (- 5-25 DEG C), after being well mixed, stir at low temperature and logical N2, dibromo-isobutyl acylbromide is added dropwise over, room is risen to afterwards
Temperature, after the completion of reaction, separates, cleaning, is dried, obtain bromine and be modified successful SiO2-Br；
Wherein, described SiO2-NH2, toluene, the adding proportion of triethylamine and dibromo-isobutyl acylbromide be (0.40-0.60) g：
20mL：(1.20-1.70)mL：(1.0-3.0)mL.
In step (3), low-temp reaction temperature is 0 DEG C, and the reaction time is 3h；12h is reacted under room temperature.
In step (4), preferable reaction temperature is 60 DEG C, and the reaction time is 22h.
In step (5), preferable reaction temperature is 90 DEG C, and the reaction time is 15h.
In step (6), preferable reaction temperature is 40 DEG C, and the reaction time is 24h.
The step (1), (2), (3), (4), (5), the drying in (6) are vacuum drying, temperature be 50-70 DEG C (preferably
60 DEG C), vacuum drying time is 10-15h (preferred 12h).
SiO is prepared by this method2-TiO2Core-shell material has the advantages that：
Method has a novelty, and operation equipment is simple, improves in conventional method directly by TiO2Nanoparticle coating is arrived
The method on mesoporous material surface, it is to avoid TiO2The phenomenon that nano-particle is easily reunited.The invention provides one kind is with amphipathic polymerization
The bar-shaped SiO of thing PGMA-POEOMA graft modifications2SiO is prepared for template hydrolysis TBT2-TiO2Method, polymer pass through hydrogen bond
Interact with TBT, finally obtain the adjustable core-shell material of thickness of the shell, the method is easy to operate, reaction condition is gentle, belongs to one
The method for planting universality, it is adaptable to prepare the adjustable core-shell material of various thickness of the shells, have great in terms of the preparation of new material
Scientific research meaning.
The present invention regulates and controls SiO using different amounts of monomer OEOMA simply by regulation2-TiO2The TiO of core-shell material2Shell
Thickness, when molar ratio is respectively OEOMA：FeCl3·6H2O：PPh3：VC：EBiB=(890,940,990)：1：8：30：When 3
It is successfully prepared the bar-shaped SiO that thickness of the shell is respectively 18nm, 24nm and 20nm2-TiO2Core-shell material.
Description of the drawings
Fig. 1 is the SiO that the embodiment of the present invention 2 is prepared2-TiO2TEM；
Fig. 2 is the SiO that the embodiment of the present invention 2 is prepared2-TiO2Lattice fringe figure；
Fig. 3 is the SiO that the embodiment of the present invention 2 is prepared2-TiO2Electron diffraction diagram；
Fig. 4 is the SiO that the embodiment of the present invention 2 is prepared2-TiO2X-ray diffraction pattern, shows preparation in figure
TiO2The characteristic diffraction peak of Detitanium-ore-type.
Specific embodiment
Further illustrate with reference to specific embodiment.
Embodiment 1
1g P123 and 0.5355g PEG are dissolved in 7.5g water and 30g 2M hydrochloric acid, are stirred until solution at 35 DEG C
It is transparent.2.125g TEOS are added dropwise in the case where being stirred continuously, are continued stirring 5min, at 35 DEG C, is stood 24h.Then
Resulting mixed solution is transferred in inner liner polytetrafluoroethylene autoclave, hydro-thermal reaction 24h at 130 DEG C.To obtain
Product vacuum suction filtration, washing, be dried 12h at 60 DEG C.Then the white powder for obtaining is placed in tube furnace, 550 DEG C of sky
5h is calcined in gas atmosphere, obtains being about 1 μm, a width of 350-450nm, the mesoporous SiO of corynebacterium of aperture about 6nm2。
By corynebacterium 0.35g obtained above mesoporous SiO2, 20mL toluene is in the there-necked flask of 100mL and by this three mouthfuls
Bottle is placed in oil bath pan, after magnetic agitation is uniform, 0.942g APTES, N is added dropwise over toward flask2Under the conditions of, 75 DEG C of stirrings
Reaction 18h, eccentric cleaning are dried, and obtain amino modified SiO2-NH2。
0.25g SiO are added in the there-necked flask of 100mL2-NH2, 20mL toluene, 0.5mL triethylamines, ultrasonic 10min,
Flask is placed in low-temp reaction bath, is well mixed, stirred at 0 DEG C and logical N2, it is added dropwise over 1mL dibromo-isobutyl acylbromides, 0 DEG C
Lower reaction 3h, to rise to afterwards and react 12h under 25 DEG C of room temperatures, obtains bromine and is modified successful SiO2-Br。
The there-necked flask of 100mL is placed in oil bath pan, 15mL DMFs (DMF), 0.10g is added
SiO2-Br、0.0045g FeCl3·6H2O、0.0437g PPh3After stirring, lead to N20.5h, adds in the mixed solution
5mL GMA and 24 μ L 2- isobutyl ethyl bromide EBiB, after stirring, add 0.0290g vitamin Cs (VC), seal three mouthfuls
Bottle, is warmed up to 60 DEG C of reaction 22h, obtains SiO2- PGMA-Br, eccentric cleaning are dried.
With the SiO for preparing2- PGMA-Br makees macromole evocating agent, and the there-necked flask of 100mL is placed in oil bath pan, adds
The mol ratio of each material is as follows：OEOMA：FeCl3·6H2O：PPh3：VC：EBiB=890：1：8：30：3, using ARGET ATRP
Method, sequentially adds 10mL DMF, 0.05g SiO2-PGMA-Br、0.015g FeCl3·6H2O、0.1g PPh3Ultrasound, stirring are equal
After even, lead to N20.5h, adds molecular weight to be 500g mol in the mixed solution-1OEOMA monomers 18.4mL and 22.5 μ L 2- bromines
Ethyl isobutyrate EBiB, after stirring, is injected into 0.26g VC, seals there-necked flask, is warmed up to 90 DEG C of reaction 15h, and centrifugation is clear
Wash the SiO for obtaining POEOMA graft modifications2, at 60 DEG C, it is vacuum dried 12h.
The there-necked flask of 100mL is placed in oil bath pan, 50mL ethanol, 0.008g SiO is added2-PGMA-POEOMA、
After 0.46mL ammoniacal liquor stirs, temperature rises to 40 DEG C, adds 0.5005g TBT, react 24h toward the mixed solution, will
The white precipitate solution centrifugal for arriving, the sediment distilled water that centrifugation is obtained and absolute ethyl alcohol centrifuge washing, obtain SiO2-
PGMA-POEOMA-TiO2,60 DEG C of vacuum drying 12h.
By above-mentioned gained SiO2-PGMA-POEOMA-TiO2Sample is placed in calcining furnace, and 6h, PGMA- are calcined at 450 DEG C
POEOMA amphipathic nature polyalcohols are pyrolyzed at high temperature, obtain final product TiO2Bar-shaped SiO of the thickness of the shell for 18nm2-TiO2Core-shell material.
Embodiment 2：
The PEG of the P123 and 0.5355g of 1g is dissolved in the hydrochloric acid of 7.5g water and 30g 2M, stir at 35 DEG C until
Solution is transparent.2.125g TEOS are added dropwise in the case where being stirred continuously, are continued stirring 5min, at 35 DEG C, is stood 24h.So
Afterwards resulting mixed solution is transferred in inner liner polytetrafluoroethylene autoclave, hydro-thermal reaction 24h at 130 DEG C.Will
The product vacuum suction filtration that obtains, washing, are dried 12h at 60 DEG C.Then the white powder for obtaining is placed in tube furnace, 550 DEG C
Air atmosphere in calcine 5h, obtain being about 1 μm, a width of 350-450nm, the mesoporous SiO of corynebacterium of aperture about 6nm2。
By corynebacterium 0.35g obtained above mesoporous SiO2, 20mL toluene is in the there-necked flask of 100mL and by this three mouthfuls
Bottle is placed in oil bath pan, after magnetic agitation is uniform, 0.942g APTES, N is added dropwise over toward flask2Under the conditions of, 75 DEG C of stirrings
Reaction 18h, eccentric cleaning are dried, and obtain amino modified SiO2-NH2。
0.25g SiO are added in the there-necked flask of 100mL2-NH2, 20mL toluene, 0.5mL triethylamines, ultrasonic 10min,
Flask is placed in low-temp reaction bath, is well mixed, stirred at 0 DEG C and logical N2, 1mL BiB are added dropwise over, are reacted at 0 DEG C
3h, to rise to afterwards and react 12h under 25 DEG C of room temperatures, obtains bromine and is modified successful SiO2-Br。
The there-necked flask of 100mL is placed in oil bath pan, 15mL DMF, 0.10g SiO is added2-Br、0.0045g
FeCl3·6H2O、0.0437g PPh3After stirring, lead to N20.5h, adds 5mL GMA and 24 μ L in the mixed solution
EBiB, after stirring, adds 0.0290g VC, seals there-necked flask, is warmed up to 60 DEG C of reaction 22h, obtains SiO2- PGMA-Br,
Eccentric cleaning is dried.
With the SiO for preparing2- PGMA-Br makees macromole evocating agent, and the there-necked flask of 100mL is placed in oil bath pan, adds
The mol ratio of each material is as follows：OEOMA：FeCl3·6H2O：PPh3：VC：EBiB=940：1：8：30：3, using ARGET ATRP
Method, sequentially adds 10mL DMF, 0.05g SiO2-PGMA-Br、0.015g FeCl3·6H2O、0.1g PPh3Ultrasound, stirring are equal
After even, lead to N20.5h, adds molecular weight to be 500g mol in the mixed solution-1OEOMA monomers 20.6mL and 22.5 μ L
EBiB, after stirring, is injected into 0.26g VC, seals there-necked flask, is warmed up to 90 DEG C of reaction 15h, and eccentric cleaning is obtained
The SiO of POEOMA graft modifications2, at 60 DEG C, it is vacuum dried 12h.
The there-necked flask of 100mL is placed in oil bath pan, 50mL ethanol, 0.008g SiO is added2-PGMA-POEOMA、
After 0.46mL ammoniacal liquor stirs, temperature rises to 40 DEG C, adds 0.5005g TBT, react 24h toward the mixed solution, will
The white precipitate solution centrifugal for arriving, the sediment distilled water that centrifugation is obtained and absolute ethyl alcohol centrifuge washing, obtain SiO2-
PGMA-POEOMA-TiO2, 60 DEG C of vacuum drying 12h.
By above-mentioned gained SiO2-PGMA-POEOMA-TiO2Sample is placed in calcining furnace, and 6h, PGMA- are calcined at 450 DEG C
POEOMA amphipathic nature polyalcohols are pyrolyzed at high temperature, obtain final product SiO2-TiO2Core-shell material such as Fig. 1.
Fig. 1 is preparation SiO2-TiO2TEM, prepared material nucleocapsid thickness is about 24nm, nanocrystalline TiO2The crystalline substance of particle
Away from for 0.35nm, this corresponds to anatase TiO to compartment2101 faces such as Fig. 2, in the SEAD figure (SAED) from Fig. 3
TiO can be clearly visible2In (101), (004), (200), (105), the presence of (211) and (204) concentric diffraction ring, this shows
TiO2The polycrystalline property of particle.
Fig. 4 is shown SiO2-TiO2XRD, as can be seen from the figure all of sample is all Anatase, 2 θ=
25.4 ° (101), 37.9 ° (004), 48.0 ° (200), 54.0 ° (105), 54.9 ° (211) and 62.8 ° of (204) places are anatase
The characteristic diffraction peak of phase, this is consistent with the SAED in Fig. 3.
Embodiment 3：
The PEG of the P123 and 0.5355g of 1g is dissolved in the hydrochloric acid of 7.5g water and 30g 2M, stir at 35 DEG C until
Solution is transparent.2.125g TEOS are added dropwise in the case where being stirred continuously, are continued stirring 5min, at 35 DEG C, is stood 24h.So
Afterwards resulting mixed solution is transferred in inner liner polytetrafluoroethylene autoclave, hydro-thermal reaction 24h at 130 DEG C.Will
The product vacuum suction filtration that obtains, washing, are dried 12h at 60 DEG C.Then the white powder for obtaining is placed in tube furnace, 550 DEG C
Air atmosphere in calcine 5h, obtain being about 1 μm, a width of 350-450nm, the mesoporous SiO of corynebacterium of aperture about 6nm2。
By corynebacterium 0.35g obtained above mesoporous SiO2, 20mL toluene is in the there-necked flask of 100mL and by this three mouthfuls
Bottle is placed in oil bath pan, after magnetic agitation is uniform, 0.942g APTES, N is added dropwise over toward flask2Under the conditions of, 75 DEG C of stirrings
Reaction 18h, eccentric cleaning are dried, and obtain amino modified SiO2-NH2。
0.25g SiO are added in the there-necked flask of 100mL2-NH2, 20mL toluene, 0.5mL triethylamines, ultrasonic 10min,
Flask is placed in low-temp reaction bath, is well mixed, stirred at 0 DEG C and logical N2, 1mL BiB are added dropwise over, are reacted at 0 DEG C
3h, to rise to afterwards and react 12h under 25 DEG C of room temperatures, obtains bromine and is modified successful SiO2-Br。
The there-necked flask of 100mL is placed in oil bath pan, 15mL DMF, 0.10g SiO is added2-Br、0.0045g
FeCl3·6H2O、0.0437g PPh3After stirring, lead to N20.5h, adds 5mL GMA and 24 μ L in the mixed solution
EBiB, after stirring, adds 0.0290g VC, seals there-necked flask, is warmed up to 60 DEG C of reaction 22h, obtains SiO2- PGMA-Br,
Eccentric cleaning is dried.
With the SiO for preparing2- PGMA-Br makees macromole evocating agent, and the there-necked flask of 100mL is placed in oil bath pan, adds
The mol ratio of each material is as follows：OEOMA：FeCl3·6H2O：PPh3：VC：EBiB=990：1：8：30：3, using ARGET ATRP
Method, sequentially adds 10mL DMF, 0.05g SiO2-PGMA-Br、0.015g FeCl3·6H2O、0.1g PPh3Ultrasound, stirring are equal
After even, lead to N20.5h, adds molecular weight to be 500g mol in the mixed solution-1OEOMA monomers 22.8mL and 22.5 μ L
EBiB, after stirring, is injected into 0.26g VC, seals there-necked flask, is warmed up to 90 DEG C of reaction 15h, and eccentric cleaning is obtained
The SiO of POEOMA graft modifications2, 60 DEG C of vacuum drying 12h.
The there-necked flask of 100mL is placed in oil bath pan, 50mL ethanol, 0.008g SiO is added2-PGMA-POEOMA、
After 0.46mL ammoniacal liquor stirs, temperature rises to 40 DEG C, adds 0.5005g TBT, react 24h toward the mixed solution, will
The white precipitate solution centrifugal for arriving, the sediment distilled water that centrifugation is obtained and absolute ethyl alcohol centrifuge washing, obtain SiO2-
PGMA-POEOMA-TiO2, at 60 DEG C, it is vacuum dried 12h.
By SiO obtained above2-PGMA-POEOMA-TiO2Sample is placed in calcining furnace, and 6h, PGMA- are calcined at 450 DEG C
POEOMA amphipathic nature polyalcohols are pyrolyzed at high temperature, obtain final product TiO2SiO of the thickness of the shell for 20nm2-TiO2Core-shell material.
Embodiment 4
1g P123 and 0.5355g PEG are dissolved in 7.5g water and 30g 2M hydrochloric acid, are stirred until solution at 35 DEG C
It is transparent.2.125g TEOS are added dropwise in the case where being stirred continuously, are continued stirring 5min, at 35 DEG C, is stood 24h.Then
Resulting mixed solution is transferred in inner liner polytetrafluoroethylene autoclave, hydro-thermal reaction 24h at 130 DEG C.To obtain
Product vacuum suction filtration, washing, be dried 12h at 60 DEG C.Then the white powder for obtaining is placed in tube furnace, 450 DEG C of sky
5h is calcined in gas atmosphere, obtains being about 1 μm, a width of 350-450nm, the mesoporous SiO of corynebacterium of aperture about 6nm2。
By corynebacterium 0.35g obtained above mesoporous SiO2, 20mL toluene is in the there-necked flask of 100mL and by this three mouthfuls
Bottle is placed in oil bath pan, after magnetic agitation is uniform, 0.942g APTES, N is added dropwise over toward flask2Under the conditions of, 70 DEG C of stirrings
Reaction 18h, eccentric cleaning are dried, and obtain amino modified SiO2-NH2。
0.25g SiO are added in the there-necked flask of 100mL2-NH2, 20mL toluene, 0.5mL triethylamines, ultrasonic 10min,
Flask is placed in low-temp reaction bath, is well mixed, stirred at 0 DEG C and logical N2, it is added dropwise over 1mL dibromo-isobutyl acylbromides, 0 DEG C
Lower reaction 3h, to rise to afterwards and react 12h under 25 DEG C of room temperatures, obtains bromine and is modified successful SiO2-Br。
The there-necked flask of 100mL is placed in oil bath pan, 15mL DMFs (DMF), 0.10g is added
SiO2-Br、0.0045g FeCl3·6H2O、0.0437g PPh3After stirring, lead to N20.5h, adds in the mixed solution
5mL GMA and 24 μ L 2- isobutyl ethyl bromide EBiB, after stirring, add 0.0290g vitamin Cs (VC), seal three mouthfuls
Bottle, is warmed up to 55 DEG C of reaction 22h, obtains SiO2- PGMA-Br, eccentric cleaning are dried.
With the SiO for preparing2- PGMA-Br makees macromole evocating agent, and the there-necked flask of 100mL is placed in oil bath pan, adds
The mol ratio of each material is as follows：OEOMA：FeCl3·6H2O：PPh3：VC：EBiB=890：1：8：30：3, using ARGET ATRP
Method, sequentially adds 10mL DMF, 0.05g SiO2-PGMA-Br、0.015g FeCl3·6H2O、0.1g PPh3Ultrasound, stirring are equal
After even, lead to N20.5h, adds molecular weight to be 500g mol in the mixed solution-1OEOMA monomers 18.4mL and 22.5 μ L 2- bromines
Ethyl isobutyrate EBiB, after stirring, is injected into 0.26g VC, seals there-necked flask, is warmed up to 85 DEG C of reaction 15h, and centrifugation is clear
Wash the SiO for obtaining POEOMA graft modifications2, at 50 DEG C, it is vacuum dried 15h.
The there-necked flask of 100mL is placed in oil bath pan, 50mL ethanol, 0.008g SiO is added2-PGMA-POEOMA、
After 0.46mL ammoniacal liquor stirs, temperature rises to 35 DEG C, adds 0.5005g TBT, react 24h toward the mixed solution, will
The white precipitate solution centrifugal for arriving, the sediment distilled water that centrifugation is obtained and absolute ethyl alcohol centrifuge washing, obtain SiO2-
PGMA-POEOMA-TiO2, 70 DEG C of vacuum drying 10h.
By above-mentioned gained SiO2-PGMA-POEOMA-TiO2Sample is placed in calcining furnace, and 7h, PGMA- are calcined at 440 DEG C
POEOMA amphipathic nature polyalcohols are pyrolyzed at high temperature, obtain final product TiO2Bar-shaped SiO of the thickness of the shell for 18nm2-TiO2Core-shell material.
Embodiment 5
The PEG of the P123 and 0.5355g of 1g is dissolved in the hydrochloric acid of 7.5g water and 30g 2M, stir at 35 DEG C until
Solution is transparent.2.125g TEOS are added dropwise in the case where being stirred continuously, are continued stirring 5min, at 35 DEG C, is stood 24h.So
Afterwards resulting mixed solution is transferred in inner liner polytetrafluoroethylene autoclave, hydro-thermal reaction 24h at 130 DEG C.Will
The product vacuum suction filtration that obtains, washing, are dried 12h at 60 DEG C.Then the white powder for obtaining is placed in tube furnace, 400 DEG C
Air atmosphere in calcine 5h, obtain being about 1 μm, a width of 350-450nm, the mesoporous SiO of corynebacterium of aperture about 6nm2。
By corynebacterium 0.35g obtained above mesoporous SiO2, 20mL toluene is in the there-necked flask of 100mL and by this three mouthfuls
Bottle is placed in oil bath pan, after magnetic agitation is uniform, 0.942g APTES, N is added dropwise over toward flask2Under the conditions of, 80 DEG C of stirrings
Reaction 18h, eccentric cleaning are dried, and obtain amino modified SiO2-NH2。
0.25g SiO are added in the there-necked flask of 100mL2-NH2, 20mL toluene, 0.5mL triethylamines, ultrasonic 10min,
Flask is placed in low-temp reaction bath, is well mixed, stirred at 0 DEG C and logical N2, 1mL BiB are added dropwise over, are reacted at 0 DEG C
3h, to rise to afterwards and react 12h under 25 DEG C of room temperatures, obtains bromine and is modified successful SiO2-Br。
The there-necked flask of 100mL is placed in oil bath pan, 15mL DMF, 0.10g SiO is added2-Br、0.0045g
FeCl3·6H2O、0.0437g PPh3After stirring, lead to N20.5h, adds 5mL GMA and 24 μ L in the mixed solution
EBiB, after stirring, adds 0.0290g VC, seals there-necked flask, is warmed up to 65 DEG C of reaction 22h, obtains SiO2- PGMA-Br,
Eccentric cleaning is dried.
With the SiO for preparing2- PGMA-Br makees macromole evocating agent, and the there-necked flask of 100mL is placed in oil bath pan, adds
The mol ratio of each material is as follows：OEOMA：FeCl3·6H2O：PPh3：VC：EBiB=940：1：8：30：3, using ARGET ATRP
Method, sequentially adds 10mL DMF, 0.05g SiO2-PGMA-Br、0.015g FeCl3·6H2O、0.1g PPh3Ultrasound, stirring are equal
After even, lead to N20.5h, adds molecular weight to be 500g mol in the mixed solution-1OEOMA monomers 20.6mL and 22.5 μ L
EBiB, after stirring, is injected into 0.26g VC, seals there-necked flask, is warmed up to 95 DEG C of reaction 15h, and eccentric cleaning is obtained
The SiO of POEOMA graft modifications2, at 65 DEG C, it is vacuum dried 12h.
The there-necked flask of 100mL is placed in oil bath pan, 50mL ethanol, 0.008g SiO is added2-PGMA-POEOMA、
After 0.46mL ammoniacal liquor stirs, temperature rises to 45 DEG C, adds 0.5005g TBT, react 24h toward the mixed solution, will
The white precipitate solution centrifugal for arriving, the sediment distilled water that centrifugation is obtained and absolute ethyl alcohol centrifuge washing, obtain SiO2-
PGMA-POEOMA-TiO2, 60 DEG C of vacuum drying 12h.
By above-mentioned gained SiO2-PGMA-POEOMA-TiO2Sample is placed in calcining furnace, and 5h, PGMA- are calcined at 490 DEG C
POEOMA amphipathic nature polyalcohols are pyrolyzed at high temperature, obtain final product TiO2SiO of the thickness of the shell for 24nm2-TiO2Core-shell material.
The molecular weight Mn=6000g/moL of the molecular weight Mn=5800g/moL of the P123 for using of embodiment 1～5, PEG.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to present invention protection model
The restriction enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not
The various modifications made by needing to pay creative work or deformation are still within protection scope of the present invention.
Claims (9)
1. a kind of titania modified bar-shaped silica core shell material, is characterized in that：It a length of 0.8-1.2 μm, it is a width of
350-450nm, aperture are 5-10nm, regulate and control SiO using different amounts of monomer OEOMA by adjusting2-TiO2Core-shell material
TiO2Thickness of the shell, is prepared for the bar-shaped SiO that thickness of the shell is 15-24nm2-TiO2Core-shell material；
The titania modified bar-shaped silica core shell material is prepared by the following method and obtains：Using ARGET
ATRP methods are grafted amphipathic nature polyalcohol poly (glycidyl methacrylate)-poly- (Methylacrylic acid polyethylene glycol single armor ether ester)
Modified rod-like mesoporous material SiO2Prepared sample SiO2- poly (glycidyl methacrylate)-poly- (metering system acid polyethylene glycol
Monomethyl ether ester), and as template hydrolysis butyl titanate, then high-temperature calcination removing polymer, prepares titanium dioxide and changes
The bar-shaped silica core shell material of property；
Concrete preparation method is as follows：
(1) bar-shaped SiO2Preparation：With tetraethyl orthosilicate as raw material, with polyethylene glycol and PULLRONIC F68-polyoxy
Ethene is template, reaction prepare a length of 0.8-1.2 μm, a width of 350-450nm, aperture for 5-10nm corynebacterium it is mesoporous
SiO2；Template polyethylene glycol and polyoxyethylene-poly-oxypropylene polyoxyethylene are dissolved in the mixed solution of water and hydrochloric acid,
Stir to PEG and P123 and all dissolve, stirring is added dropwise over TEOS, stand after stirring and evenly mixing, mixture is transferred to into high pressure anti-
In answering kettle, cool down after reaction；The white mixture suction filtration of above-mentioned gained is precipitated into thing, is washed, be dried, then in 450-
550 DEG C calcining 4h, prepare a length of 0.8-1.2 μm, a width of 350-450nm, the mesoporous SiO of aperture 5-10nm corynebacteriums2；
(2)SiO2-NH2Preparation：With 3- aminopropyl triethoxysilanes as coupling agent, it is situated between with the corynebacterium obtained in step (1)
Hole SiO2For raw material, react and prepare amino modified SiO2-NH2；
(3)SiO2The preparation of-Br：With the SiO obtained in dibromo-isobutyl acylbromide and step (2)2-NH2For raw material, reaction is prepared into
It is modified successful SiO to bromine2-Br；
(4)SiO2The preparation of-PGMA-Br：With GMA, FeCL3·6H2O, triphenylphosphine, vitamin C,
The SiO that 2- isobutyl ethyl bromides and step (3) are obtained2- Br is raw material, with DMF as solvent, using ARGET ATRP methods, 55-
20-24h is reacted at 65 DEG C, is dried, is prepared SiO2-PGMA-Br；
Wherein, described raw material GMA, FeCL3·6H2O、PPh3, injection Vitamin B_6 BiB, initiator SiO2- Br and solvent DMF add
Plus ratio is 5mL：0.0045g：(0.0350-0.0524)g：(0.0203-0.0377)g：24μL：(0.08-0.12)g：15mL；
(5)SiO2The preparation of-PGMA-POEOMA：
With SiO in step (4)2- PGMA-Br is initiator, with Methylacrylic acid polyethylene glycol single armor ether ester, FeCl3·6H2O、
PPh3, VC and EBiB be raw material, with DMF as solvent, using ARGET ATRP methods, 13-17h is reacted under the conditions of 85-95 DEG C,
It is dried, prepares SiO2-PGMA-POEOMA；
Wherein, described raw material OEOMA, FeCL3·6H2O、PPh3, VC, EBiB, initiator SiO2- PGMA-Br and solvent DMF
Adding proportion is (18-23) mL：0.015g：(0.1-0.125)g：(0.24-0.28)g：22.5μL：(0.03-0.06)g：
10mL；
(6) bar-shaped SiO2-TiO2The preparation of core-shell material：
The amphipathic SiO obtained in step (5) is added in reactor2- PGMA-POEOMA, with TBT, ethanol, ammoniacal liquor, 35-40
22-26h is reacted at DEG C, is dried, SiO is obtained2-PGMA-POEOMA-TiO2；
Wherein, SiO2The adding proportion of-PGMA-POEOMA, TBT, ethanol and ammoniacal liquor is：(0.007-0.016)g：(0.45-
0.60)g：50mL：(0.36-0.56)mL；
By SiO obtained above2-PGMA-POEOMA-TiO2, 5-7h is calcined at 440-490 DEG C, obtain SiO2-TiO2Nucleocapsid material
Material.
2. the preparation method of titania modified bar-shaped silica core shell material as claimed in claim 1, is characterized in that：Adopt
Amphipathic nature polyalcohol poly (glycidyl methacrylate)-poly- (metering system acid polyethylene glycol is grafted with ARGET ATRP methods
Monomethyl ether ester) modified rod-like mesoporous material SiO2Prepared sample SiO2- poly (glycidyl methacrylate)-poly- (methacrylic acid
Poly glycol monomethyl ether ester), and as template hydrolysis butyl titanate, then high-temperature calcination removing polymer, prepares two
Titanium oxide is modified bar-shaped silica core shell material.
3. preparation method as claimed in claim 2, is characterized in that, comprise the following steps：
(1) bar-shaped SiO2Preparation：Template polyethylene glycol and polyoxyethylene-poly-oxypropylene polyoxyethylene are dissolved in into water and salt
In the mixed solution of acid, stir to PEG and P123 and all dissolve, stirring is added dropwise over TEOS, stand after stirring and evenly mixing, will mixing
Thing is transferred in autoclave, is cooled down after reaction；The white mixture suction filtration of above-mentioned gained is precipitated into thing, is washed, done
It is dry, then 450-550 DEG C calcine 4h, prepare a length of 0.8-1.2 μm, a width of 350-450nm, aperture 5-10nm corynebacteriums
Mesoporous SiO2；
(2)SiO2-NH2Preparation：With 3- aminopropyl triethoxysilanes as coupling agent, it is situated between with the corynebacterium obtained in step (1)
Hole SiO2For raw material, react and prepare amino modified SiO2-NH2；
(3)SiO2The preparation of-Br：With the SiO obtained in dibromo-isobutyl acylbromide and step (2)2-NH2For raw material, reaction is prepared into
It is modified successful SiO to bromine2-Br；
(4)SiO2The preparation of-PGMA-Br：With GMA, FeCL3·6H2O, triphenylphosphine, vitamin C,
The SiO that 2- isobutyl ethyl bromides and step (3) are obtained2- Br is raw material, with DMF as solvent, using ARGET ATRP methods, 55-
20-24h is reacted at 65 DEG C, is dried, is prepared SiO2-PGMA-Br；
Wherein, described raw material GMA, FeCL3·6H2O、PPh3, injection Vitamin B_6 BiB, initiator SiO2- Br and solvent DMF add
Plus ratio is 5mL：0.0045g：(0.0350-0.0524)g：(0.0203-0.0377)g：24μL：(0.08-0.12)g：15mL；
(5)SiO2The preparation of-PGMA-POEOMA：
With SiO in step (4)2- PGMA-Br is initiator, with Methylacrylic acid polyethylene glycol single armor ether ester, FeCl3·6H2O、
PPh3, VC and EBiB be raw material, with DMF as solvent, using ARGET ATRP methods, 13-17h is reacted under the conditions of 85-95 DEG C,
It is dried, prepares SiO2-PGMA-POEOMA；
Wherein, described raw material OEOMA, FeCL3·6H2O、PPh3, VC, EBiB, initiator SiO2- PGMA-Br and solvent DMF
Adding proportion is (18-23) mL：0.015g：(0.1-0.125)g：(0.24-0.28)g：22.5μL：(0.03-0.06)g：
10mL；
(6) bar-shaped SiO2-TiO2The preparation of core-shell material：
The amphipathic SiO obtained in step (5) is added in reactor2- PGMA-POEOMA, with TBT, ethanol, ammoniacal liquor, 35-40
22-26h is reacted at DEG C, is dried, SiO is obtained2-PGMA-POEOMA-TiO2；
Wherein, SiO2The adding proportion of-PGMA-POEOMA, TBT, ethanol and ammoniacal liquor is：(0.007-0.016)g：(0.45-
0.60)g：50mL：(0.36-0.56)mL；
By SiO obtained above2- PGMA-POEOMA-TiO, calcines 5-7h at 440-490 DEG C, obtains SiO2-TiO2Nucleocapsid material
Material.
4. preparation method as claimed in claim 3, is characterized in that：TEOS, P123, PEG, HCl and H2The mol ratio of O is 1：
0.017：0.0088：5.71：192.
5. preparation method as claimed in claim 3, in it is characterized in that step (1), the reaction temperature of standing is 35 DEG C, during reaction
Between be 24h, the reaction temperature in autoclave be 130 DEG C, the reaction time is 24h.
6. preparation method as claimed in claim 3, is characterized in that：In step (2), SiO2-NH2Preparation method be specially：
The mesoporous SiO of corynebacterium is added to reactor2And toluene, after being uniformly mixed, APTES is added dropwise over toward reactor,
N2Under the conditions of after stirring reaction, eccentric cleaning is dried, obtains amino modified SiO2-NH2。
7. preparation method as claimed in claim 6, is characterized in that：The SiO2, toluene and APTES adding proportion be：
(0.60-0.80)g：20mL：(1.884-2.826)g.
8. preparation method as claimed in claim 6, is characterized in that：In step (2), reaction temperature is 70-80 DEG C, the reaction time
For 18h.
9. preparation method as claimed in claim 3, is characterized in that：In step (3), SiO2The preparation method of-Br is specially：
SiO is added in reactor2-NH2, toluene, triethylamine, ultrasound；Above-mentioned reactor is placed in into low-temp reaction bath after ultrasound
In, after being well mixed, stir at low temperature and logical N2, dibromo-isobutyl acylbromide being added dropwise over, is warmed to room temperature afterwards, reaction is completed
Afterwards, separate, cleaning and be dried, obtain bromine and be modified successful SiO2-Br；
Wherein, described SiO2-NH2, toluene, the adding proportion of triethylamine and dibromo-isobutyl acylbromide be (0.40-0.60) g：
20mL：(1.20-1.70)mL：(1.0-3.0)mL.
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