CN104925816A - Titanium dioxide modified rod-shaped silicon dioxide nuclear shell material and preparation method thereof - Google Patents
Titanium dioxide modified rod-shaped silicon dioxide nuclear shell material and preparation method thereof Download PDFInfo
- Publication number
- CN104925816A CN104925816A CN201510354844.0A CN201510354844A CN104925816A CN 104925816 A CN104925816 A CN 104925816A CN 201510354844 A CN201510354844 A CN 201510354844A CN 104925816 A CN104925816 A CN 104925816A
- Authority
- CN
- China
- Prior art keywords
- sio
- preparation
- pgma
- tio
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a titanium dioxide modified rod-shaped silicon dioxide nuclear shell material and a preparation method thereof. The preparation method comprises the following steps of performing grafting on amphiphilic polymers poly-glycidyl methacrylate-poly (polycarboxylate based superplasticizer) modified rod-shaped mesoporous materials SiO2 to prepare a sample SiO2-poly- glycidyl methacrylate-poly (polycarboxylate based superplasticizer); performing hydrolysis on tetrabutyl titanate by using the sample SiO2-poly-glycidyl methacrylate-poly (polycarboxylate based superplasticizer) as a template; and performing high-temperature calcinations to remove polymers so as to obtain the titanium dioxide modified rod-shaped silicon dioxide nuclear shell material. The traditional method for preparing a rod-shaped SiO2-TiO2 nuclear shell structure composite material is improved. The titanium dioxide modified rod-shaped silicon dioxide nuclear shell material is easy to operate and is novel; and the problems that TiO2 nano particles are in an auto-agglutination state and surfaces of the mesoporous materials are easy to conglobate in a process of preparing the SiO2-TiO2 composite materials by using the traditional method are solved.
Description
Technical field
The invention belongs to field of material synthesis technology, particularly relate to a kind of titania modified bar-shaped silicon-dioxide (SiO
2-TiO
2) core-shell material and preparation method thereof.
Background technology
Ordered mesoporous material is the novel nano structure material risen rapidly the nineties in last century, has just obtained international physics, chemistry and the great attention of material educational circles since being born, and develops rapidly and become one of study hotspot interdisciplinary.Ordered mesoporous material is because of its orderly pore passage structure, and larger specific surface area and pore volume, have potential application in fields such as catalysis, separation, absorption and functionalization materials.Wherein mesoporous molecular sieve SBA-15 is with neutral surface active agent P123 for template, the mesoporous silicon oxide (SiO of the bar-shaped high-sequential utilizing hydrothermal method to prepare
2) material, by carrying out chemically modified to its surface, its application in every field effectively can be expanded.Wang (J.Phys.Chem.C, 2011,115:22191) etc. use silane coupling agent 3-aminopropyl triethoxysilane (APTES) to the mesoporous SiO of corynebacterium
2material carries out rear graft modification, prepare the mesoporous material of functionalization, its six sides shape meso-hole structure does not change, spacing, unit cell parameters and wall thickness increase all to some extent, there is the trend reduced in specific surface area, pore volume and aperture, and the modified mesoporous material of aminopropyl is all significantly increased to the fixed amount of PPL (porcine pancreatic lipase) with to the catalytic activity of vanay hydrolysis, thermostability, reusing as carrier.
In recent years, titanium dioxide (TiO
2) because of its good semi-conductivity, transmittance, specific refractory power, chemical stability, and the advantage such as inexpensive, toxicological harmless, bio-compatibility, get more and more people's extensive concerning, through being often used as the shell structure of inorganic materials, be mainly used in catalyzer, the solar cell of dye sensitization and sensor aspect.But, TiO
2nanoparticle is easily reunited in reaction system, and effective ratio area also can reduce thereupon, causes the rapid decline of its catalytic activity, limits its application.In order to solve the problem, can by TiO
2nanometer particle load is on the surface of mesoporous material, and the existence of vesicular structure not only effectively can increase TiO
2specific surface area, and be beneficial to TiO
2optical absorption, thus improve photocatalytic activity.
Up to now, about SiO
2-TiO
2the preparation method of core-shell material, that reports in document is a lot, mainly based on template, mainly with SiO
2ball is template, and minority is with SiO
2mesoporous material is template.Utilize the mesoporous and larger specific surface area of the high-sequential of mesoporous material, can TiO be made
2nanoparticle is deposited in mesoporous material surface, the SiO of obtained favorable dispersity
2-TiO
2core-shell material.Qian (J.Phys.Chem.C, 2013,117:19544) etc. are template with SBA-15, make TiO by sol-gel method
2direct load, on mesoporous material surface, obtains SiO
2-TiO
2core-shell material, like this by TiO
2shell is directly coated on mesoporous material SiO
2core surface, is easy to cause TiO in preparation process
2nanoparticle autohemagglutination or at SiO
2core surface forms local and reunites, thus affects its photocatalysis effect.For solving the problem, first can carry out modification to mesoporous material, obtained new template, as SiO
2-polymkeric substance.
At present, ARGET ATRP method grafting amphipathic nature polyalcohol modification rod-like mesoporous material SiO is utilized
2obtained sample SiO
2-PGMA-POEOMA, and as template hydrolysis tetrabutyl titanate (TBT), then high-temperature calcination removing polymer, prepare bar-shaped SiO
2-TiO
2core-shell composite material, TBT hydrolysis is acted on by hydrogen bond action and amphiphilic polymer poly (glycidyl methacrylate)-poly-(Methylacrylic acid polyethylene glycol single armor ether ester) (PGMA-POEOMA).With the bar-shaped SiO of ARGET ATRP method grafting amphipathic nature polyalcohol modification
2for template prepares SiO
2-TiO
2the matrix material of nucleocapsid is not also in the news.
Summary of the invention
Technical problem underlying to be solved by this invention improves the bar-shaped SiO of tradition preparation exactly
2-TiO
2the method of composite material of core-shell structure, simple to operate, method is novel, solves traditional method and prepares bar-shaped SiO
2-TiO
2tiO in composite material
2nanoparticle autohemagglutination and the problem of easily reuniting on mesoporous material surface.
For solving the problem, the present invention realizes by the following technical solutions:
A kind of titania modified bar-shaped silica core shell material, long for 0.8-1.2 μm, wide for 350-450nm, aperture be 5-10nm, use the monomer OEOMA of different amount to regulate and control SiO by regulating
2-TiO
2the TiO of core-shell material
2thickness of the shell, has prepared the bar-shaped SiO that thickness of the shell is 15-24nm
2-TiO
2core-shell material, has especially successfully prepared thickness of the shell and has been respectively 18nm, the bar-shaped SiO of 24nm and 20nm
2-TiO
2core-shell material.
The preparation method of described titania modified bar-shaped silica core shell material, adopts ARGET ATRP method grafting amphipathic nature polyalcohol PGMA-POEOMA modification rod-like mesoporous material SiO
2obtained sample SiO
2-PGMA-POEOMA, and as template hydrolysis tetrabutyl titanate (TBT), then high-temperature calcination removing polymer, prepare titania modified bar-shaped silica core shell material.
Comprise the following steps:
(1) bar-shaped SiO
2preparation: with tetraethyl orthosilicate (TEOS) for raw material, with polyoxyethylene glycol (PEG, Mn=4000 ~ 10000g/moL, be preferably 6000g/moL) and polyoxyethylene-poly-oxypropylene polyoxyethylene (P123, Mn=4000 ~ 10000g/moL, be preferably 5800g/moL) be template, reaction prepare long for 0.8-1.2 μm (being preferably 1 μm), wide for 350-450nm, aperture be the mesoporous SiO of corynebacterium of 5-10nm
2;
(2) SiO
2-NH
2preparation: with 3-aminopropyl triethoxysilane (APTES) for coupling agent, with the mesoporous SiO of corynebacterium obtained in step (1)
2for raw material, prepare amino modified SiO
2-NH
2;
(3) SiO
2the preparation of-Br: with the SiO obtained in dibromo-isobutyl acylbromide (BiB) and step (2)
2-NH
2for raw material, prepare the successful SiO of bromine modification
2-Br;
(4) SiO
2the preparation of-PGMA-Br: with GMA (glycidyl methacrylate), FeCL
36H
2o, PPh
3the SiO that (triphenylphosphine), vitamins C (VC), EBiB (2-isobutyl ethyl bromide) and step (3) obtain
2-Br is raw material, take DMF as solvent, adopts ARGET ATRP method, reacts 20-24h at 55-65 DEG C, dry, prepares SiO
2-PGMA-Br;
Wherein, described raw material GMA, FeCL
36H
2o, PPh
3, injection Vitamin B_6 BiB, initiator SiO
2the adding proportion of-Br and solvent DMF is 5mL:0.0045g:(0.0350-0.0524) g:(0.0203-0.0377) g:24 μ L:(0.08-0.12) g:15mL;
(5) SiO
2the 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), FeCl
36H
2o, PPh
3, VC and EBiB be raw material, take DMF as solvent, adopts ARGETATRP method, under 85-95 DEG C of condition, react 13-17h, dry, prepares SiO
2-PGMA-POEOMA;
Wherein, described raw material OEOMA, FeCL
36H
2o, PPh
3, VC, EBiB, initiator SiO
2the adding proportion of-PGMA-Br and solvent DMF is (18-23) mL:0.015g:(0.1-0.125) g:(0.24-0.28) g:22.5 μ L:(0.03-0.06) g:10mL;
(6) bar-shaped SiO
2-TiO
2the preparation of core-shell material:
The amphipathic SiO obtained in step (5) is added in reactor
2-PGMA-POEOMA, with TBT, ethanol, ammoniacal liquor, reacts 22-26h at 35-40 DEG C, dry, obtained SiO
2-PGMA-POEOMA-TiO
2;
Wherein, SiO
2the 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 above-mentioned obtained SiO
2-PGMA-POEOMA-TiO
2, at 440-490 DEG C of calcining 5-7h, obtain SiO
2-TiO
2core-shell material.
In step (1), described bar-shaped SiO
2preparation method be specially:
Template polyoxyethylene glycol (PEG) and polyoxyethylene-poly-oxypropylene polyoxyethylene (P123) are dissolved in the mixing solutions of water and hydrochloric acid, be stirred to PEG and P123 all to dissolve, stir and dropwise add tetraethyl orthosilicate (TEOS), TEOS, P123, PEG, HCl and H
2the mol ratio of O is 1:0.017:0.0088:5.71:192, leaves standstill, transferred to by mixture in autoclave after after stirring and evenly mixing, cooling after reaction.The white mixture suction filtration of above-mentioned gained is precipitated thing, washing, dry, then at 450-550 DEG C of calcining 4h, prepare long for 0.8-1.2 μm (being preferably 1 μm), wide be 350-450nm, the mesoporous SiO of aperture 5-10nm corynebacterium
2;
In step (1), washing, dry detailed process are: use distilled water repetitive scrubbing 3-5 time, by the throw out vacuum-drying of gained.The time of stirring and evenly mixing is 5min.
In step (1), the temperature of reaction left standstill is 35 DEG C, and the reaction times is 24h, and the temperature of reaction in autoclave is 130 DEG C, and the reaction times is 24h.
In step (2), SiO
2-NH
2preparation method be specially:
The SiO that corynebacterium is mesoporous is added in reactor
2and toluene, after being uniformly mixed, in reactor, dropwise add 1.884-2.826g APTES, N
2under condition after stirring reaction, eccentric cleaning, dry, obtain amino modified SiO
2-NH
2;
Wherein, described SiO
2, toluene and APTES adding proportion be: (0.60-0.80) g:20mL:(1.884-2.826) g.
In step (2), temperature of reaction is 70-80 DEG C (preferably 75 DEG C), and the reaction times is 18h.
In step (3), SiO
2the preparation method of-Br is specially:
SiO is added in reactor
2-NH
2, toluene, triethylamine, ultrasonic; After ultrasonic, above-mentioned reactor is placed in low-temp reaction bath (-5-25 DEG C), after mixing, stirs at low temperatures and logical N
2, dropwise add dibromo-isobutyl acylbromide, rise to room temperature afterwards, after having reacted, separation, cleaning, drying, obtain the successful SiO of bromine modification
2-Br;
Wherein, described SiO
2-NH
2, toluene, triethylamine and dibromo-isobutyl acylbromide adding proportion 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 times is 3h; 12h is reacted under room temperature.
In step (4), preferable reaction temperature is 60 DEG C, and the reaction times is 22h.
In step (5), preferable reaction temperature is 90 DEG C, and the reaction times is 15h.
In step (6), preferable reaction temperature is 40 DEG C, and the reaction times is 24h.
Drying in described step (1), (2), (3), (4), (5), (6) is vacuum-drying, temperature is 50-70 DEG C (preferably 60 DEG C), and the vacuum-drying time is 10-15h (preferred 12h).
SiO is prepared by present method
2-TiO
2core-shell material has following beneficial effect:
Method has novelty, and operating equipment is simple, improves in traditional method directly by TiO
2nanoparticle coating, to the method on mesoporous material surface, avoids TiO
2the phenomenon that nanoparticle is easily reunited.The invention provides a kind of with the bar-shaped SiO of amphipathic nature polyalcohol PGMA-POEOMA graft modification
2for template hydrolysis TBT prepares SiO
2-TiO
2method, polymkeric substance is interacted by hydrogen bond and TBT, finally obtain the core-shell material that thickness of the shell is adjustable, the method is easy and simple to handle, reaction conditions is gentle, belong to a kind of method of universality, be applicable to prepare the adjustable core-shell material of various thickness of the shell, in the preparation of type material, have great scientific research meaning.
The present invention uses the monomer OEOMA of different amount to regulate and control SiO simply by regulating
2-TiO
2the TiO of core-shell material
2thickness of the shell, when molar ratio is respectively OEOMA:FeCl
36H
2o:PPh
3: VC:EBiB=(890,940,990): successfully prepared thickness of the shell during 1:8:30:3 and be respectively 18nm, the bar-shaped SiO of 24nm and 20nm
2-TiO
2core-shell material.
Accompanying drawing explanation
Fig. 1 is the SiO that the embodiment of the present invention 2 prepares
2-TiO
2tEM;
Fig. 2 is the SiO that the embodiment of the present invention 2 prepares
2-TiO
2lattice fringe figure;
Fig. 3 is the SiO that the embodiment of the present invention 2 prepares
2-TiO
2electron-diffraction diagram;
Fig. 4 is the SiO that the embodiment of the present invention 2 prepares
2-TiO
2x-ray diffraction pattern, shows the TiO of preparation in figure
2the characteristic diffraction peak of Detitanium-ore-type.
Embodiment
Further illustrate below in conjunction with specific embodiment.
Embodiment 1
1g P123 and 0.5355g PEG is dissolved in 7.5g water and 30g 2M hydrochloric acid, stirs until solution is transparent at 35 DEG C.Dropwise adding 2.125g TEOS when constantly stirring, continuing to stir 5min, at 35 DEG C, leaving standstill 24h.Then obtained mixing solutions is transferred in inner liner polytetrafluoroethylene autoclave, hydro-thermal reaction 24h at 130 DEG C.By obtain product vacuum suction filtration, washing, dry 12h at 60 DEG C.Then the white powder obtained is placed in tube furnace, calcines 5h in the air atmosphere of 550 DEG C, obtain being about 1 μm, wide is 350-450nm, and aperture is about the mesoporous SiO of corynebacterium of 6nm
2.
By the mesoporous SiO of above-mentioned for 0.35g obtained corynebacterium
2, 20mL toluene is in the there-necked flask of 100mL and this there-necked flask is placed in oil bath pan, magnetic agitation evenly after, in flask, dropwise add 0.942g APTES, N
2under condition, 75 DEG C of stirring reaction 18h, eccentric cleaning is dry, obtains amino modified SiO
2-NH
2.
0.25g SiO is added in the there-necked flask of 100mL
2-NH
2, 20mL toluene, 0.5mL triethylamine, ultrasonic 10min, is placed in low-temp reaction bath, mixes by flask, stir and logical N at 0 DEG C
2, dropwise add 1mL dibromo-isobutyl acylbromide, at 0 DEG C, react 3h, under rising to 25 DEG C of room temperatures afterwards, react 12h, obtain the successful SiO of bromine modification
2-Br.
The there-necked flask of 100mL is placed in oil bath pan, adds 15mL DMF (DMF), 0.10gSiO
2-Br, 0.0045g FeCl
36H
2o, 0.0437g PPh
3after stirring, logical N
20.5h, adds 5mL GMA and 24 μ L 2-isobutyl ethyl bromide EBiB, after stirring, adds 0.0290g vitamins C (VC) in this mixing solutions, sealing there-necked flask, is warmed up to 60 DEG C of reaction 22h, obtains SiO
2-PGMA-Br, eccentric cleaning is dry.
With the SiO of preparation
2-PGMA-Br makes macromole evocating agent, and the there-necked flask of 100mL is placed in oil bath pan, and the mol ratio adding each material is as follows: OEOMA:FeCl
36H
2o:PPh
3: VC:EBiB=890:1:8:30:3, adopts ARGET ATRP method, adds 10mL DMF, 0.05g SiO successively
2-PGMA-Br, 0.015g FeCl
36H
2o, 0.1g PPh
3ultrasonic, after stirring, logical N
20.5h, in this mixing solutions, add molecular weight is 500g mol
-1oEOMA monomer 18.4mL and 22.5 μ L 2-isobutyl ethyl bromide EBiB, after stirring, is injected into 0.26g VC, sealing there-necked flask, and be warmed up to 90 DEG C of reaction 15h, eccentric cleaning obtains the SiO of POEOMA graft modification
2, vacuum-drying 12h at 60 DEG C.
The there-necked flask of 100mL is placed in oil bath pan, adds 50mL ethanol, 0.008g SiO
2after-PGMA-POEOMA, 0.46mL ammoniacal liquor stir, temperature rises to 40 DEG C, in this mixing solutions, add 0.5005g TBT, reaction 24h, by the white precipitate solution centrifugal obtained, by the centrifugal throw out distilled water that obtains and dehydrated alcohol centrifuge washing, obtain SiO
2-PGMA-POEOMA-TiO2,60 DEG C of vacuum-drying 12h.
By above-mentioned gained SiO
2-PGMA-POEOMA-TiO
2sample is placed in calcining furnace, calcines 6h at 450 DEG C, and the at high temperature pyrolysis of PGMA-POEOMA amphipathic nature polyalcohol, obtains TiO
2thickness of the shell is the bar-shaped SiO of 18nm
2-TiO
2core-shell material.
Embodiment 2:
The PEG of P123 and 0.5355g of 1g is dissolved in the hydrochloric acid of 7.5g water and 30g 2M, stirs until solution is transparent at 35 DEG C.Dropwise adding 2.125g TEOS when constantly stirring, continuing to stir 5min, at 35 DEG C, leaving standstill 24h.Then obtained mixing solutions is transferred in inner liner polytetrafluoroethylene autoclave, hydro-thermal reaction 24h at 130 DEG C.By obtain product vacuum suction filtration, washing, dry 12h at 60 DEG C.Then the white powder obtained is placed in tube furnace, calcines 5h in the air atmosphere of 550 DEG C, obtain being about 1 μm, wide is 350-450nm, and aperture is about the mesoporous SiO of corynebacterium of 6nm
2.
By the mesoporous SiO of above-mentioned for 0.35g obtained corynebacterium
2, 20mL toluene is in the there-necked flask of 100mL and this there-necked flask is placed in oil bath pan, magnetic agitation evenly after, in flask, dropwise add 0.942g APTES, N
2under condition, 75 DEG C of stirring reaction 18h, eccentric cleaning is dry, obtains amino modified SiO
2-NH
2.
0.25g SiO is added in the there-necked flask of 100mL
2-NH
2, 20mL toluene, 0.5mL triethylamine, ultrasonic 10min, is placed in low-temp reaction bath, mixes by flask, stir and logical N at 0 DEG C
2, dropwise add 1mL BiB, at 0 DEG C, react 3h, under rising to 25 DEG C of room temperatures afterwards, react 12h, obtain the successful SiO of bromine modification
2-Br.
The there-necked flask of 100mL is placed in oil bath pan, adds 15mL DMF, 0.10g SiO
2-Br, 0.0045gFeCl
36H
2o, 0.0437g PPh
3after stirring, logical N
20.5h, adds 5mL GMA and 24 μ L EBiB, after stirring, adds 0.0290g VC in this mixing solutions, sealing there-necked flask, is warmed up to 60 DEG C of reaction 22h, obtains SiO
2-PGMA-Br, eccentric cleaning is dry.
With the SiO of preparation
2-PGMA-Br makes macromole evocating agent, and the there-necked flask of 100mL is placed in oil bath pan, and the mol ratio adding each material is as follows: OEOMA:FeCl
36H
2o:PPh
3: VC:EBiB=940:1:8:30:3, adopts ARGET ATRP method, adds 10mL DMF, 0.05g SiO successively
2-PGMA-Br, 0.015g FeCl
36H
2o, 0.1g PPh
3ultrasonic, after stirring, logical N
20.5h, in this mixing solutions, add molecular weight is 500g mol
-1oEOMA monomer 20.6mL and 22.5 μ L EBiB, after stirring, is injected into 0.26g VC, sealing there-necked flask, and be warmed up to 90 DEG C of reaction 15h, eccentric cleaning obtains the SiO of POEOMA graft modification
2, vacuum-drying 12h at 60 DEG C.
The there-necked flask of 100mL is placed in oil bath pan, adds 50mL ethanol, 0.008g SiO
2after-PGMA-POEOMA, 0.46mL ammoniacal liquor stir, temperature rises to 40 DEG C, in this mixing solutions, add 0.5005g TBT, reaction 24h, by the white precipitate solution centrifugal obtained, by the centrifugal throw out distilled water that obtains and dehydrated alcohol centrifuge washing, obtain SiO
2-PGMA-POEOMA-TiO
2, 60 DEG C of vacuum-drying 12h.
By above-mentioned gained SiO
2-PGMA-POEOMA-TiO
2sample is placed in calcining furnace, calcines 6h at 450 DEG C, and the at high temperature pyrolysis of PGMA-POEOMA amphipathic nature polyalcohol, obtains SiO
2-TiO
2core-shell material is as Fig. 1.
Fig. 1 is preparation SiO
2-TiO
2tEM, prepared material nucleocapsid thickness is about 24nm, nanocrystalline TiO
2the spacing of lattice of particle is 0.35nm, and this corresponds to anatase octahedrite TiO
2101 look like Fig. 2, obviously can see TiO from the selected area electron diffraction figure (SAED) Fig. 3
2in (101), (004), (200), (105), the existence of (211) and (204) concentric diffraction ring, this shows TiO
2the polycrystalline character of particle.
That Fig. 4 shows is SiO
2-TiO
2xRD figure, as can be seen from the figure all samples are all Anatase, in 2 θ=25.4 ° (101), 37.9 ° (004), 48.0 ° (200), 54.0 ° (105), 54.9 ° (211) and 62.8 ° of (204) places are the characteristic diffraction peak of Anatase, and this is consistent with the SAED in Fig. 3.
Embodiment 3:
The PEG of P123 and 0.5355g of 1g is dissolved in the hydrochloric acid of 7.5g water and 30g 2M, stirs until solution is transparent at 35 DEG C.Dropwise adding 2.125g TEOS when constantly stirring, continuing to stir 5min, at 35 DEG C, leaving standstill 24h.Then obtained mixing solutions is transferred in inner liner polytetrafluoroethylene autoclave, hydro-thermal reaction 24h at 130 DEG C.By obtain product vacuum suction filtration, washing, dry 12h at 60 DEG C.Then the white powder obtained is placed in tube furnace, calcines 5h in the air atmosphere of 550 DEG C, obtain being about 1 μm, wide is 350-450nm, and aperture is about the mesoporous SiO of corynebacterium of 6nm
2.
By the mesoporous SiO of above-mentioned for 0.35g obtained corynebacterium
2, 20mL toluene is in the there-necked flask of 100mL and this there-necked flask is placed in oil bath pan, magnetic agitation evenly after, in flask, dropwise add 0.942g APTES, N
2under condition, 75 DEG C of stirring reaction 18h, eccentric cleaning is dry, obtains amino modified SiO
2-NH
2.
0.25g SiO is added in the there-necked flask of 100mL
2-NH
2, 20mL toluene, 0.5mL triethylamine, ultrasonic 10min, is placed in low-temp reaction bath, mixes by flask, stir and logical N at 0 DEG C
2, dropwise add 1mL BiB, at 0 DEG C, react 3h, under rising to 25 DEG C of room temperatures afterwards, react 12h, obtain the successful SiO of bromine modification
2-Br.
The there-necked flask of 100mL is placed in oil bath pan, adds 15mL DMF, 0.10g SiO
2-Br, 0.0045gFeCl
36H
2o, 0.0437g PPh
3after stirring, logical N
20.5h, adds 5mL GMA and 24 μ L EBiB, after stirring, adds 0.0290g VC in this mixing solutions, sealing there-necked flask, is warmed up to 60 DEG C of reaction 22h, obtains SiO
2-PGMA-Br, eccentric cleaning is dry.
With the SiO of preparation
2-PGMA-Br makes macromole evocating agent, and the there-necked flask of 100mL is placed in oil bath pan, and the mol ratio adding each material is as follows: OEOMA:FeCl
36H
2o:PPh
3: VC:EBiB=990:1:8:30:3, adopts ARGET ATRP method, adds 10mL DMF, 0.05g SiO successively
2-PGMA-Br, 0.015g FeCl
36H
2o, 0.1g PPh
3ultrasonic, after stirring, logical N
20.5h, in this mixing solutions, add molecular weight is 500g mol
-1oEOMA monomer 22.8mL and 22.5 μ L EBiB, after stirring, is injected into 0.26g VC, sealing there-necked flask, and be warmed up to 90 DEG C of reaction 15h, eccentric cleaning obtains the SiO of POEOMA graft modification
2, 60 DEG C of vacuum-drying 12h.
The there-necked flask of 100mL is placed in oil bath pan, adds 50mL ethanol, 0.008g SiO
2after-PGMA-POEOMA, 0.46mL ammoniacal liquor stir, temperature rises to 40 DEG C, in this mixing solutions, add 0.5005g TBT, reaction 24h, by the white precipitate solution centrifugal obtained, by the centrifugal throw out distilled water that obtains and dehydrated alcohol centrifuge washing, obtain SiO
2-PGMA-POEOMA-TiO
2, vacuum-drying 12h at 60 DEG C.
By above-mentioned obtained SiO
2-PGMA-POEOMA-TiO
2sample is placed in calcining furnace, calcines 6h at 450 DEG C, and the at high temperature pyrolysis of PGMA-POEOMA amphipathic nature polyalcohol, obtains TiO
2thickness of the shell is the SiO of 20nm
2-TiO
2core-shell material.
Embodiment 4
1g P123 and 0.5355g PEG is dissolved in 7.5g water and 30g 2M hydrochloric acid, stirs until solution is transparent at 35 DEG C.Dropwise adding 2.125g TEOS when constantly stirring, continuing to stir 5min, at 35 DEG C, leaving standstill 24h.Then obtained mixing solutions is transferred in inner liner polytetrafluoroethylene autoclave, hydro-thermal reaction 24h at 130 DEG C.By obtain product vacuum suction filtration, washing, dry 12h at 60 DEG C.Then the white powder obtained is placed in tube furnace, calcines 5h in the air atmosphere of 450 DEG C, obtain being about 1 μm, wide is 350-450nm, and aperture is about the mesoporous SiO of corynebacterium of 6nm
2.
By the mesoporous SiO of above-mentioned for 0.35g obtained corynebacterium
2, 20mL toluene is in the there-necked flask of 100mL and this there-necked flask is placed in oil bath pan, magnetic agitation evenly after, in flask, dropwise add 0.942g APTES, N
2under condition, 70 DEG C of stirring reaction 18h, eccentric cleaning is dry, obtains amino modified SiO
2-NH
2.
0.25g SiO is added in the there-necked flask of 100mL
2-NH
2, 20mL toluene, 0.5mL triethylamine, ultrasonic 10min, is placed in low-temp reaction bath, mixes by flask, stir and logical N at 0 DEG C
2, dropwise add 1mL dibromo-isobutyl acylbromide, at 0 DEG C, react 3h, under rising to 25 DEG C of room temperatures afterwards, react 12h, obtain the successful SiO of bromine modification
2-Br.
The there-necked flask of 100mL is placed in oil bath pan, adds 15mL DMF (DMF), 0.10gSiO
2-Br, 0.0045g FeCl
36H
2o, 0.0437g PPh
3after stirring, logical N
20.5h, adds 5mL GMA and 24 μ L 2-isobutyl ethyl bromide EBiB, after stirring, adds 0.0290g vitamins C (VC) in this mixing solutions, sealing there-necked flask, is warmed up to 55 DEG C of reaction 22h, obtains SiO
2-PGMA-Br, eccentric cleaning is dry.
With the SiO of preparation
2-PGMA-Br makes macromole evocating agent, and the there-necked flask of 100mL is placed in oil bath pan, and the mol ratio adding each material is as follows: OEOMA:FeCl
36H
2o:PPh
3: VC:EBiB=890:1:8:30:3, adopts ARGET ATRP method, adds 10mL DMF, 0.05g SiO successively
2-PGMA-Br, 0.015g FeCl
36H
2o, 0.1g PPh
3ultrasonic, after stirring, logical N
20.5h, in this mixing solutions, add molecular weight is 500g mol
-1oEOMA monomer 18.4mL and 22.5 μ L 2-isobutyl ethyl bromide EBiB, after stirring, is injected into 0.26g VC, sealing there-necked flask, and be warmed up to 85 DEG C of reaction 15h, eccentric cleaning obtains the SiO of POEOMA graft modification
2, vacuum-drying 15h at 50 DEG C.
The there-necked flask of 100mL is placed in oil bath pan, adds 50mL ethanol, 0.008g SiO
2after-PGMA-POEOMA, 0.46mL ammoniacal liquor stir, temperature rises to 35 DEG C, in this mixing solutions, add 0.5005g TBT, reaction 24h, by the white precipitate solution centrifugal obtained, by the centrifugal throw out distilled water that obtains and dehydrated alcohol centrifuge washing, obtain SiO
2-PGMA-POEOMA-TiO
2, 70 DEG C of vacuum-drying 10h.
By above-mentioned gained SiO
2-PGMA-POEOMA-TiO
2sample is placed in calcining furnace, calcines 7h at 440 DEG C, and the at high temperature pyrolysis of PGMA-POEOMA amphipathic nature polyalcohol, obtains TiO
2thickness of the shell is the bar-shaped SiO of 18nm
2-TiO
2core-shell material.
Embodiment 5
The PEG of P123 and 0.5355g of 1g is dissolved in the hydrochloric acid of 7.5g water and 30g 2M, stirs until solution is transparent at 35 DEG C.Dropwise adding 2.125g TEOS when constantly stirring, continuing to stir 5min, at 35 DEG C, leaving standstill 24h.Then obtained mixing solutions is transferred in inner liner polytetrafluoroethylene autoclave, hydro-thermal reaction 24h at 130 DEG C.By obtain product vacuum suction filtration, washing, dry 12h at 60 DEG C.Then the white powder obtained is placed in tube furnace, calcines 5h in the air atmosphere of 400 DEG C, obtain being about 1 μm, wide is 350-450nm, and aperture is about the mesoporous SiO of corynebacterium of 6nm
2.
By the mesoporous SiO of above-mentioned for 0.35g obtained corynebacterium
2, 20mL toluene is in the there-necked flask of 100mL and this there-necked flask is placed in oil bath pan, magnetic agitation evenly after, in flask, dropwise add 0.942g APTES, N
2under condition, 80 DEG C of stirring reaction 18h, eccentric cleaning is dry, obtains amino modified SiO
2-NH
2.
0.25g SiO is added in the there-necked flask of 100mL
2-NH
2, 20mL toluene, 0.5mL triethylamine, ultrasonic 10min, is placed in low-temp reaction bath, mixes by flask, stir and logical N at 0 DEG C
2, dropwise add 1mL BiB, at 0 DEG C, react 3h, under rising to 25 DEG C of room temperatures afterwards, react 12h, obtain the successful SiO of bromine modification
2-Br.
The there-necked flask of 100mL is placed in oil bath pan, adds 15mL DMF, 0.10g SiO
2-Br, 0.0045gFeCl
36H
2o, 0.0437g PPh
3after stirring, logical N
20.5h, adds 5mL GMA and 24 μ L EBiB, after stirring, adds 0.0290g VC in this mixing solutions, sealing there-necked flask, is warmed up to 65 DEG C of reaction 22h, obtains SiO
2-PGMA-Br, eccentric cleaning is dry.
With the SiO of preparation
2-PGMA-Br makes macromole evocating agent, and the there-necked flask of 100mL is placed in oil bath pan, and the mol ratio adding each material is as follows: OEOMA:FeCl
36H
2o:PPh
3: VC:EBiB=940:1:8:30:3, adopts ARGET ATRP method, adds 10mL DMF, 0.05g SiO successively
2-PGMA-Br, 0.015g FeCl
36H
2o, 0.1g PPh
3ultrasonic, after stirring, logical N
20.5h, in this mixing solutions, add molecular weight is 500g mol
-1oEOMA monomer 20.6mL and 22.5 μ L EBiB, after stirring, is injected into 0.26g VC, sealing there-necked flask, and be warmed up to 95 DEG C of reaction 15h, eccentric cleaning obtains the SiO of POEOMA graft modification
2, vacuum-drying 12h at 65 DEG C.
The there-necked flask of 100mL is placed in oil bath pan, adds 50mL ethanol, 0.008g SiO
2after-PGMA-POEOMA, 0.46mL ammoniacal liquor stir, temperature rises to 45 DEG C, in this mixing solutions, add 0.5005g TBT, reaction 24h, by the white precipitate solution centrifugal obtained, by the centrifugal throw out distilled water that obtains and dehydrated alcohol centrifuge washing, obtain SiO
2-PGMA-POEOMA-TiO
2, 60 DEG C of vacuum-drying 12h.
By above-mentioned gained SiO
2-PGMA-POEOMA-TiO
2sample is placed in calcining furnace, calcines 5h at 490 DEG C, and the at high temperature pyrolysis of PGMA-POEOMA amphipathic nature polyalcohol, obtains TiO
2thickness of the shell is the SiO of 24nm
2-TiO
2core-shell material.
The molecular weight Mn=6000g/moL of the molecular weight Mn=5800g/moL of the P123 of the use of embodiment 1 ~ 5, PEG.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. a titania modified bar-shaped silica core shell material, is characterized in that: its length is 0.8-1.2 μm, wide for 350-450nm, aperture be 5-10nm, use the monomer OEOMA of different amount to regulate and control SiO by regulating
2-TiO
2the TiO of core-shell material
2thickness of the shell, has prepared the bar-shaped SiO that thickness of the shell is 15-24nm
2-TiO
2core-shell material.
2. the preparation method of titania modified bar-shaped silica core shell material as claimed in claim 1, is characterized in that: adopt ARGET ATRP method grafting amphipathic nature polyalcohol poly (glycidyl methacrylate)-poly-(Methylacrylic acid polyethylene glycol single armor ether ester) modification rod-like mesoporous material SiO
2obtained sample SiO
2-poly (glycidyl methacrylate)-poly-(Methylacrylic acid polyethylene glycol single armor ether ester), and as template hydrolysis tetrabutyl titanate, then high-temperature calcination removing polymer, prepares titania 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 SiO
2preparation: take tetraethyl orthosilicate as raw material, with polyoxyethylene glycol and polyoxyethylene-poly-oxypropylene polyoxyethylene for template, reaction prepare long for 0.8-1.2 μm, wide for 350-450nm, aperture be the mesoporous SiO of corynebacterium of 5-10nm
2;
(2) SiO
2-NH
2preparation: with 3-aminopropyl triethoxysilane for coupling agent, with the mesoporous SiO of corynebacterium obtained in step (1)
2for raw material, reaction prepares amino modified SiO
2-NH
2;
(3) SiO
2the preparation of-Br: with the SiO obtained in dibromo-isobutyl acylbromide and step (2)
2-NH
2for raw material, reaction prepares the successful SiO of bromine modification
2-Br;
(4) SiO
2the preparation of-PGMA-Br: with glycidyl methacrylate, FeCL
36H
2the SiO that O, triphenylphosphine, vitamins C, 2-isobutyl ethyl bromide and step (3) obtain
2-Br is raw material, take DMF as solvent, adopts ARGETATRP method, reacts 20-24h at 55-65 DEG C, dry, prepares SiO
2-PGMA-Br;
Wherein, described raw material GMA, FeCL
36H
2o, PPh
3, injection Vitamin B_6 BiB, initiator SiO
2the adding proportion of-Br and solvent DMF is 5mL:0.0045g:(0.0350-0.0524) g:(0.0203-0.0377) g:24 μ L:(0.08-0.12) g:15mL;
(5) SiO
2the preparation of-PGMA-POEOMA:
With SiO in step (4)
2-PGMA-Br is initiator, with Methylacrylic acid polyethylene glycol single armor ether ester, FeCl
36H
2o, PPh
3, VC and EBiB be raw material, take DMF as solvent, adopts ARGET ATRP method, under 85-95 DEG C of condition, react 13-17h, dry, prepares SiO
2-PGMA-POEOMA;
Wherein, described raw material OEOMA, FeCL
36H
2o, PPh
3, VC, EBiB, initiator SiO
2the adding proportion of-PGMA-Br and solvent DMF is (18-23) mL:0.015g:(0.1-0.125) g:(0.24-0.28) g:22.5 μ L:(0.03-0.06) g:10mL;
(6) bar-shaped SiO
2-TiO
2the preparation of core-shell material:
The amphipathic SiO obtained in step (5) is added in reactor
2-PGMA-POEOMA, with TBT, ethanol, ammoniacal liquor, reacts 22-26h at 35-40 DEG C, dry, obtained SiO
2-PGMA-POEOMA-TiO
2;
Wherein, SiO
2the 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 above-mentioned obtained SiO
2-PGMA-POEOMA-TiO, at 440-490 DEG C of calcining 5-7h, obtains SiO
2-TiO
2core-shell material.
4. preparation method as claimed in claim 2, is characterized in that: in step (1), described bar-shaped SiO
2preparation method be specially:
Template polyoxyethylene glycol and polyoxyethylene-poly-oxypropylene polyoxyethylene are dissolved in the mixing solutions of water and hydrochloric acid, be stirred to PEG and P123 all to dissolve, stir and dropwise add TEOS, leave standstill after after stirring and evenly mixing, mixture is transferred in autoclave, cooling after reaction; The white mixture suction filtration of above-mentioned gained is precipitated thing, washing, dry, then at 450-550 DEG C of calcining 4h, prepare long for 0.8-1.2 μm, wide be 350-450nm, the mesoporous SiO of aperture 5-10nm corynebacterium
2.
5. preparation method as claimed in claim 4, is characterized in that: TEOS, P123, PEG, HCl and H
2the mol ratio of O is 1:0.017:0.0088:5.71:192.
6. preparation method as claimed in claim 4, is characterized in that in step (1), and the temperature of reaction left standstill is 35 DEG C, and the reaction times is 24h, and the temperature of reaction in autoclave is 130 DEG C, and the reaction times is 24h.
7. preparation method as claimed in claim 2, is characterized in that: in step (2), SiO
2-NH
2preparation method be specially:
The mesoporous SiO of corynebacterium is added to reactor
2and toluene, after being uniformly mixed, in reactor, dropwise add APTES, N
2under condition after stirring reaction, eccentric cleaning, dry, obtain amino modified SiO
2-NH
2.
8. preparation method as claimed in claim 7, is characterized in that: described SiO
2, toluene and APTES adding proportion be: (0.60-0.80) g:20ml:(1.884-2.826) g.
9. preparation method as claimed in claim 6, it is characterized in that: in step (2), temperature of reaction is 70-80 DEG C, and the reaction times is 18h.
10. preparation method as claimed in claim 2, is characterized in that: in step (3), SiO
2the preparation method of-Br is specially:
SiO is added in reactor
2-NH
2, toluene, triethylamine, ultrasonic; After ultrasonic, above-mentioned reactor is placed in low-temp reaction bath, after mixing, stirs at low temperatures and logical N
2, dropwise add dibromo-isobutyl acylbromide, rise to room temperature afterwards, after having reacted, be separated, clean and drying, obtain the successful SiO of bromine modification
2-Br;
Wherein, described SiO
2-NH
2, toluene, triethylamine and dibromo-isobutyl acylbromide adding proportion be (0.40-0.60) g:20mL:(1.20-1.70) mL:(1.0-3.0) mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510354844.0A CN104925816B (en) | 2015-06-24 | 2015-06-24 | A kind of titania modified bar-shaped silica core shell material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510354844.0A CN104925816B (en) | 2015-06-24 | 2015-06-24 | A kind of titania modified bar-shaped silica core shell material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104925816A true CN104925816A (en) | 2015-09-23 |
| CN104925816B CN104925816B (en) | 2017-04-05 |
Family
ID=54113290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510354844.0A Active CN104925816B (en) | 2015-06-24 | 2015-06-24 | A kind of titania modified bar-shaped silica core shell material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104925816B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109868054A (en) * | 2019-01-15 | 2019-06-11 | 重庆新久融科技有限公司 | A kind of efficient nano coating and preparation method thereof for aluminum alloy mould plate |
| CN109926034A (en) * | 2019-04-04 | 2019-06-25 | 中国科学院兰州化学物理研究所 | A kind of preparation and application of the silica gel chromatographic column filling material of amphipathic Ionic Liquid Modified |
| CN110628227A (en) * | 2019-09-20 | 2019-12-31 | 江南大学 | Modified emulsified asphalt and preparation method thereof |
| CN111662598A (en) * | 2019-03-08 | 2020-09-15 | 立邦涂料（中国）有限公司 | Water-based paint and preparation and application thereof |
| CN112863799A (en) * | 2020-12-31 | 2021-05-28 | 莱芜职业技术学院 | Iron-based soft magnetic composite material with mesoporous structure coating layer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303885A (en) * | 1999-10-25 | 2001-07-18 | 上海绿纳科技有限公司 | Preparation of nanometer composite particles-organic polymer mixed composite system |
| CN103771424A (en) * | 2014-01-14 | 2014-05-07 | 齐鲁工业大学 | Preparation method of titanium dioxide modified silicon dioxide core-shell material |
| CN104477921A (en) * | 2014-11-04 | 2015-04-01 | 齐鲁工业大学 | Pomegranate-shaped multicore-shell SiO2-TiO2 composite material and preparation method thereof |
-
2015
- 2015-06-24 CN CN201510354844.0A patent/CN104925816B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303885A (en) * | 1999-10-25 | 2001-07-18 | 上海绿纳科技有限公司 | Preparation of nanometer composite particles-organic polymer mixed composite system |
| CN103771424A (en) * | 2014-01-14 | 2014-05-07 | 齐鲁工业大学 | Preparation method of titanium dioxide modified silicon dioxide core-shell material |
| CN104477921A (en) * | 2014-11-04 | 2015-04-01 | 齐鲁工业大学 | Pomegranate-shaped multicore-shell SiO2-TiO2 composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHUNFENG WANG ET AL.: "Porcine pancreatic Lipase Immobilized in Amino-Functionalized Short Rod-Shaped Mesoporous Silica Prepared Using Poly(ethylene glycol) and Triblock Copolymer as Templates", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| LEI ZHANG ET AL.: "Tunable Shell Thickness in Silica Nanospheres Functionalized by a Hydrophobic PMMA-PSt Diblock Copolymer Brush via Activators Generated by Electron Transfer for Atom Transfer Radical Polymerization", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 * |
| MINNAN ZHAO ET AL.: "Fabrication and photoactivity of a tunable-void SiO2–TiO2 core–shell structure on modified SiO2 nanospheres by grafting an amphiphilic diblock copolymer using ARGET ATRP", 《SOFT MATTER》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109868054A (en) * | 2019-01-15 | 2019-06-11 | 重庆新久融科技有限公司 | A kind of efficient nano coating and preparation method thereof for aluminum alloy mould plate |
| CN111662598A (en) * | 2019-03-08 | 2020-09-15 | 立邦涂料（中国）有限公司 | Water-based paint and preparation and application thereof |
| CN111662598B (en) * | 2019-03-08 | 2022-11-01 | 立邦涂料（中国）有限公司 | Water-based paint and preparation and application thereof |
| CN109926034A (en) * | 2019-04-04 | 2019-06-25 | 中国科学院兰州化学物理研究所 | A kind of preparation and application of the silica gel chromatographic column filling material of amphipathic Ionic Liquid Modified |
| CN109926034B (en) * | 2019-04-04 | 2021-08-03 | 中国科学院兰州化学物理研究所 | Preparation and application of silica gel chromatographic packing modified by amphiphilic ionic liquid |
| CN110628227A (en) * | 2019-09-20 | 2019-12-31 | 江南大学 | Modified emulsified asphalt and preparation method thereof |
| CN110628227B (en) * | 2019-09-20 | 2020-07-07 | 江南大学 | Modified emulsified asphalt and preparation method thereof |
| CN112863799A (en) * | 2020-12-31 | 2021-05-28 | 莱芜职业技术学院 | Iron-based soft magnetic composite material with mesoporous structure coating layer and preparation method thereof |
| CN112863799B (en) * | 2020-12-31 | 2022-11-04 | 莱芜职业技术学院 | Iron-based soft magnetic composite material with mesoporous structure coating layer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104925816B (en) | 2017-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101537349B (en) | Preparation of core/shell structural polystyrene/titanium dioxide composite photo catalyst | |
| CN104925816A (en) | Titanium dioxide modified rod-shaped silicon dioxide nuclear shell material and preparation method thereof | |
| CN106582892B (en) | Nano-TiO2Coating structure and its preparation method and application | |
| CN107185515B (en) | A kind of photochemical catalyst and preparation method thereof for sewage disposal | |
| CN106380981B (en) | A kind of modified nano-titanium dioxide self-cleaning coating and preparation method thereof | |
| CN104326507A (en) | Preparation method of hollow titanium dioxide microspheres | |
| CN100424020C (en) | Low temperature method for preparing Nano powder | |
| CN107377006B (en) | A kind of flexibility black TiO2Nano fibrous membrane and preparation method thereof | |
| CN101791547B (en) | Method for preparing TiO2 nanocryatal/nanotube composite photocatalyst | |
| CN105129805B (en) | Preparation method of silicon oxide/tin antimony oxide/zinc oxide ternary composite material | |
| CN105749762A (en) | Macromolecular composite membrane material with photocatalysis activity and preparation method thereof | |
| CN108609649A (en) | A kind of preparation method of sea urchin shape magnetic hollow microsphere | |
| CN104014357B (en) | A kind of nitrogen-doped titanium dioxide raw powder's production technology of reticulated porous structures | |
| CN105887332A (en) | Preparation method of nitrogen-doped flexible TiO2-SiO2 nanofiber membrane with visible light catalytic function | |
| CN105536850B (en) | A kind of high dispersancy nano composite titania material and preparation method thereof | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| CN104923230A (en) | Titanium dioxide/ferroferric oxide nanocomposite and preparation method therefor | |
| CN105709736B (en) | A kind of mosaic Pt@CeO2The preparation method of nano-tube composite catalyst | |
| CN1511630A (en) | Method for preparing porous ceramics supported high activity nano titanium dioxide | |
| CN102286804A (en) | Preparation method of titanium dioxide fibers with photocatalysis function and polycrystalline nanostructure | |
| CN107008240A (en) | Nano crystal titanium dioxide light catalyst of aluminum oxide open celled foam ceramic load Si doping and preparation method thereof | |
| CN106000440A (en) | Preparation method of g-C3N4 quantum dot-loaded titanium dioxide nanoparticles | |
| CN102240561B (en) | Preparation method of CS/TiO2-NTs composite photocatalyst | |
| CN103771424A (en) | Preparation method of titanium dioxide modified silicon dioxide core-shell material | |
| CN103601239A (en) | Preparation method of anatase and brookite mixed crystal TiO2 nanowire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221219 Address after: Room 3115, No. 135, Ward Avenue, Ping'an Street, Changqing District, Jinan, Shandong 250300 Patentee after: Shandong Jiqing Technology Service Co.,Ltd. Address before: 250353 Science Park, West New Town University, Changqing District, Shandong, Ji'nan Patentee before: Qilu University of Technology |