CN101215003A - Method for preparing integral macropore titanium oxide - Google Patents
Method for preparing integral macropore titanium oxide Download PDFInfo
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- CN101215003A CN101215003A CNA2008100520208A CN200810052020A CN101215003A CN 101215003 A CN101215003 A CN 101215003A CN A2008100520208 A CNA2008100520208 A CN A2008100520208A CN 200810052020 A CN200810052020 A CN 200810052020A CN 101215003 A CN101215003 A CN 101215003A
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Abstract
The invention discloses a process for preparing macroporous titanium oxide of integral type, belonging to the preparative technique of porous inorganic oxide of integral type. The process is to employ phenylethene and divinylbenzens as monomer to prepare macroporous organic framework of integral type by reversing concentrated emulsions, employ butyl titanate to prepare TiO2 hydrosol and fill the TiO2 hydrosol into the large-hole organic framework of integral type, the filled organic or inorganic compounds of integral type is dried and calcined at temperature of 500-600 DEG C and the framework is deprivated, and then, the macroporous titanium oxide of integral type is obtained. The process has the advantages that the preparation process is simple and easy to be operated, the obtained macroporous titanium oxide of integral type is provided with micron-sized pore passages which are communicated with each other, the bore diameter of macroporous titanium oxide of integral type is 500 nm-20 mu m, further, the macroporous titanium oxide of integral type is applicable to be employed as catalyst carriers, sorbing materials and parting materials.
Description
Technical field
The present invention relates to a kind of preparation method of integral macropore titanium oxide, belong to the technology of preparing of monolithic devices porous inorganic oxide.
Background technology
The integral macropore oxide compound receives much concern owing to it has the micron-sized macropore of hundreds of nanometer to tens duct, high-specific surface area, high damping properties, good thermostability, lower characteristics such as specific inductivity, is widely used in support of the catalyst, sorbing material, parting material, chromatograph packing material, sound-absorbing and fields such as cushioning material, opticfiber communication.
The preparation method of integral macropore oxide compound mainly is a template, and template comprises: tensio-active agent, polyalcohol stephanoporate ball, porous membrane, cellulose acetate permeable membrane etc.Wherein, C.Solans etc.
[1,2]Adopt phase reversion letex polymerization (PIT) preparation polystyrene cellular material, and prepared the porous metal oxide materials as template with this material.The polymkeric substance cellular material of PIT emulsion process preparation is compared with traditional method, its aperture littler (＜1um), the aperture dispersiveness is also better, therefore prepared its structure of metal oxide porous material is rule and have higher compressed capability more.Du Zhongjie etc.
[3]Adopt the super-thick emulsion legal system to be equipped with polystyrene porous material and polyacrylamide porous material, and prepared monolithic porous titania meterial as template with this material, its aperture is between hundreds of nanometer and several microns, and the duct connects, gas by the time pressure drop little, this material has application prospect widely.
Adopt template to prepare the integral macropore material, preparation process mainly comprises: the preparation of (1) monolithic devices organic formwork; (2) preparation of target product precursor liquid; (3) in template, fill the target precursor liquid; (4) remove organic formwork.About the preparation of target product precursor liquid in the step (2), all adopted the solution of target product or alcosol to fill in the document in the past.This method is bigger owing to grain diameter after filling roasting with solution on the one hand, causes the aperture obviously to reduce; Alcosol and organic formwork wettability are good on the other hand, cause filling excessive, thereby cause the duct not to be communicated with, and pore volume reduces.
Reference:
[1]SolansC.E?squenaJ.A?zemarN.Highly?concentrated(gel)e?mulsions，versatileReaction?media，Current?Opinion?in?Colloid?and?Interface?Science，2003(8)，156-163
[2]Jordi?E.GSR?Ravi?S.Conxita?S.H?ighly?Concentrated?W/O?Emulsions?Preparedby?the?PIT?Method?as?Templates?for?Solid?Foams，Langmuir，2003(19)，2983-2988
[3] Du Zhongjie etc. SCI, 2002,23 (8): 1614～1618
Summary of the invention
The object of the present invention is to provide a kind of preparation method of integral macropore titanium oxide, this method is simple, and the integral macropore titanium oxide that makes has the macropore duct that micron order interconnects.
The present invention is realized that by following technical proposals a kind of preparation method of integral macropore titanium oxide is characterized in that comprising following process:
(1) preparation of template
The vinylbenzene (styrene) and the divinylbenzene (DVB) that will be V (divinylbenzene)/V (vinylbenzene)=1: 3.8～4.4 with the volume ratio are monomer, adding quality is the class of tensio-active agent department 80 of total monomer quality 2%～20%, and quality is to be oil phase behind initiator Diisopropyl azodicarboxylate (AIBN) uniform mixing of total monomer quality 0.1%～2%.Under agitation add in oil phase and remove ionized water, the volume fraction that makes water obtains anti-phase concentrated emulsion 75%～90%.Concentrated emulsion is poured in the mould, 50～65 ℃ of sealing polymerization 24～48h, 60～90 ℃ of drying 24～48h obtain the organic macropore template of monolithic devices.
(2) TiO
2The preparation of the water-sol
With the butyl (tetra) titanate is raw material, be the ratio of n (butyl (tetra) titanate)/n (dehydrated alcohol)/n (deionized water)/n (nitric acid)=1/9/3/0.3 in molar ratio, butyl (tetra) titanate is added in the dehydrated alcohol, add deionized water and nitric acid again, after stirring, wore out 1 day, add deionized water once more for the ratio of v (butyl (tetra) titanate)/v (deionized water)=1/1 by volume then at 20-25 ℃, 20-25 ℃ was worn out 2～3 days, and obtained TiO
2The water-sol.
(3) TiO
2The filling of the water-sol
The TiO that filling step (2) makes in the organic macropore template of the monolithic devices that step (1) makes
2The water-sol is filled the back and is removed the unnecessary colloidal sol of template surface, and this monolithic devices organic/inorganic composite at 60～90 ℃ of forced air drying 12～24h, is repeated filling and drying process 2～6 times.
(4) template removes
The monolithic devices organic/inorganic composite that step (3) is made is that 0.1～5 ℃/min is warming up to 500～700 ℃ of roasting 1～8h with temperature rise rate, obtains integral macropore titanium oxide.
The present invention has the following advantages: preparation process is simple.Anti-phase concentrated emulsion legal system is equipped with the integral macropore polystyrene moulding, and the raw material cheapness is simple to operate.Precursor liquid adopts TiO
2The water-sol, the integral macropore titanium oxide that makes has the macropore duct that micron order interconnects, the aperture is 1～50 μ m, existing the aperture on the hole wall is the mesoporous of 2～50nm.So the integral macropore titanium oxide of structure is applicable to as support of the catalyst, sorbing material and parting material.Can be as required, design prepares the monolithic devices organic formwork of different shapes size and duct size, thereby is prepared into the integral macropore oxide compound of different shapes size and duct size.
Description of drawings
The SEM figure of the integral macropore template that Fig. 1 makes for the embodiment of the invention 1
The integral macropore TiO that Fig. 2 makes for the embodiment of the invention 1
2SEM figure
Embodiment
Embodiment 1
(1) anti-phase concentrated emulsion legal system is equipped with the integral macropore polystyrene moulding
Vinylbenzene and divinylbenzene monomer be with the NaOH solution washing of equal-volume 0.2mol/L 4 times, uses equal-volume deionized water wash 4 times standby again.Accurately take by weighing washed vinylbenzene 6mL and divinylbenzene 1.5mL, put into the 100mL there-necked flask.To wherein adding class of 0.062g initiator Diisopropyl azodicarboxylate and 0.54g tensio-active agent department 80, stirring it is mixed.Under agitation dropwise slowly drip deionized water 33.9mL in there-necked flask, the dropping time is controlled at 60min, forms anti-phase concentrated emulsion.After continuing to stir 30min, concentrated emulsion is moved in the mould, put into 60 ℃ of thermostat container polymerization 24h.Template after the polymerization obtains the integral macropore polystyrene moulding at 60 ℃ of dry 48h.
(2) TiO
2The colloidal sol preparation
Get the 20mL butyl (tetra) titanate and be dissolved in the 30.84mL dehydrated alcohol, add the 3.173mL deionized water while stir, butyl (tetra) titanate begins hydrolysis, adds 1.22mL nitric acid peptization again.25 ℃ were worn out 1 day, added the deionized water of 20mL again, and 25 ℃ were worn out 2 days, and obtained transparent TiO
2Colloidal sol.
(3) TiO
2The filling of colloidal sol
The TiO that in the template that step (1) makes, makes in the filling step (2)
2Colloidal sol.Fill the back and absorb the unnecessary colloidal sol of template surface with filter paper, again with this monolithic devices organic/inorganic composite at 70 ℃ of dry 12h.Repeat filling and drying process 4 times.
(4) roasting removes template
The organic/inorganic composite that step (3) is made adds in the retort furnace, is that 1 ℃/min is warming up to 550 ℃ of roasting 3h with temperature rise rate, obtains integral macropore oxidation TiO
2, mean pore size is 2 μ m.
Embodiment 2
The preparation method is identical with embodiment 1 with process, changes the volume of the deionized water that adds in the step (1) into 24mL by 33.9ml, and the integral macropore polystyrene moulding mean pore size that makes is 1.3 μ m.
Embodiment 3
The preparation method is identical with embodiment 1 with process, changes the volume of the deionized water that adds in the step (1) into 54mL by 33.9ml, and the integral macropore polystyrene moulding mean pore size that makes is 4.2 μ m.
Embodiment 4
The preparation method is identical with embodiment 1 with process, changes the quality of the tensio-active agent department that adds in the step (1) classes 80 into 0.108g by 0.54g, and the monolithic devices polystyrene moulding mean pore size that makes is 0.6 μ m.
Embodiment 5
The preparation method is identical with embodiment 1 with process, changes the quality of the tensio-active agent department that adds in the step (1) classes 80 into 0.3g by 0.54g, the integral macropore TiO that makes
2Mean pore size is 2.6 μ m.
Embodiment 6
The preparation method is identical with embodiment 1 with process, changes the volume that adds butyl (tetra) titanate in the step (2) into 15mL by 20ml, the integral macropore TiO that makes
2Mean pore size is 0.6 μ m.
Embodiment 7
The preparation method is identical with embodiment 1 with process, changes the volume that adds butyl (tetra) titanate in the step (2) into 25mL by 20ml, the integral macropore TiO that makes
2Mean pore size is 3.8 μ m.
Embodiment 8
The preparation method is identical with embodiment 1 with process, changes maturing temperature in the step (4) into 500 ℃ by 550 ℃, the integral macropore TiO that makes
2Mean pore size is 2.1 μ m.
Embodiment 9
The preparation method is identical with embodiment 1 with process, changes maturing temperature in the step (4) into 600 ℃ by 550 ℃, the integral macropore TiO that makes
2Mean pore size is 3.4 μ m.
Claims (1)
1. the preparation method of an integral macropore titanium oxide is characterized in that comprising following process:
(1) preparation of template
With divinylbenzene/volume of styrene ratio is that 1: 3.8～4.4 vinylbenzene and divinylbenzene are monomer, adding quality is the class of tensio-active agent department 80 of total monomer quality 2%～20%, and quality is the initiator Diisopropyl azodicarboxylate of total monomer quality 0.1%～2%, it behind the uniform mixing oil phase, under agitation in oil phase, add deionized water, the volume fraction that makes water is 75%～90%, obtain anti-phase concentrated emulsion, concentrated emulsion is poured in the mould, at 50～65 ℃ of sealing polymerization 24～48h, 60～90 ℃ of drying 24～48h obtain the organic macropore template of monolithic devices;
(2) TiO
2The preparation of the water-sol
With the butyl (tetra) titanate is raw material, in butyl (tetra) titanate/dehydrated alcohol/deionized water/nitric acid mol ratio is 1/9/3/0.3 ratio, butyl (tetra) titanate is added in the dehydrated alcohol, add deionized water and nitric acid again, after stirring, at room temperature aging 1 day is that 1/1 ratio adds deionized water once more in butyl (tetra) titanate/deionized water volume ratio then, 20-25 ℃ was worn out 2～3 days, and obtained TiO
2The water-sol;
(3) TiO
2The filling of the water-sol
The TiO that filling step (2) makes in the organic macropore template of the monolithic devices that step (1) makes
2The water-sol is filled the back and is removed the unnecessary colloidal sol of template surface, and this monolithic devices organic/inorganic composite at 60～90 ℃ of forced air drying 12～24h, is repeated filling and drying process 2～6 times;
(4) template removes
The monolithic devices organic/inorganic composite that step (3) is made is that 0.1～5 ℃/min is warming up to 500～700 ℃ of roasting 1～8h with temperature rise rate, obtains integral macropore titanium oxide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815747A (en) * | 2012-08-09 | 2012-12-12 | 嘉兴优太太阳能有限公司 | Mesoporous ball preparing method for solar batteries |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815747A (en) * | 2012-08-09 | 2012-12-12 | 嘉兴优太太阳能有限公司 | Mesoporous ball preparing method for solar batteries |
| CN102815747B (en) * | 2012-08-09 | 2014-07-30 | 嘉兴优太太阳能有限公司 | Mesoporous ball preparing method for solar batteries |
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