CN1448371A - Synthetic method of mesopore metallic oxide, mixed metallic oxide and metallic phosphate serial microballons using mesopore carbon microballons as form - Google Patents
Synthetic method of mesopore metallic oxide, mixed metallic oxide and metallic phosphate serial microballons using mesopore carbon microballons as form Download PDFInfo
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Abstract
The present invention the method of forming mesoporous metal oxide, mixed metal oxide and metal phosphate microballoon through synthesizing small mesoporous carbon ball with mesoporous silicon microballoon as mother body, perfusing the mixture of metal alkoxide, metal chloride and phaophate, drying and roasting. The mesoporous metal oxide, phosphate, etc. have important uses in catalysis, adsorption and other fields owing to their high specific surface area, nanometer level pores, great amount of active components on the pore wall and other features. Through said process, serial mesoporous microballoons including titania, zirconia, alumina, mixed titanium-zirconium oxide, mixed titanium-silicon oxide, zirconium phosphate, titanium phosphate, aluminum phosphate, tin phosphate and ferric phosphate may be synthesized.
Description
Technical field
The present invention be a kind of be that parent synthetic mesoporous carbon bead carries out the perfusion of metal alkoxide, metal chloride-phosphate mixture with the mesopore silicon oxide bead, by forming the method for mesopore metal oxide, metal phosphate microballoon after dry, the roasting.Mesopore oxide, phosphoric acid salt microballoon are a kind of type materials with high-ratio surface, nano pore, better thermostability, in conjunction with oxide compound, phosphoric acid salt inherent character, will have wide practical use in fields such as catalysis, absorption, novel light, electricity, magnetic materials.
Background technology
Mesoporous microsphere is a kind of type material with high-ratio surface, nanometer range internal orifice dimension, ball size distribution homogeneous in micrometer range.But its skeleton of mesoporous ball of having reported now is made up of the inert silicon oxide, further expand its application in catalysis and must adopt the aftertreatment load to go into the method for active ingredient, thereby limit the application of such mesoporous ball to a certain extent.And for non-silicon skeleton mesoporous material synthetic, traditional sol-gel process institute synthetic oxide compound or the phosphoric acid salt general thermostability relatively poor (some need add thermostability that rare earth element improve its skeleton) of tensio-active agent under inducing of passing through, and synthesis condition complexity, controllability is relatively poor, and the regulation and control of the pattern of such material also are difficult to realize.
Summary of the invention
The objective of the invention is to study the method for the mesoporous microsphere of the stronger preparation mesopore metal oxide of a kind of universality, mixed metal oxide, the non-silicon skeleton of metal phosphate series,
The mesoporous carbon spheres of related employing can be used as template, guarantees the microballoon pattern of the material that obtains.The different metal alkoxy compound, metal chloride-phosphoric acid ester presoma mother liquor can optionally obtain the skeleton of material requested and form, perfusion in mesoporous carbon microballoon duct and in addition the exsiccant method can make mother liquor hydrolytic crosslinking in the mesoporous carbon spheres duct, begin to take shape the skeleton of non-silicon mesoporous microsphere, it is reasonable crosslinked that roasting under nitrogen atmosphere can make this skeleton further obtain, and make the skeleton crystallization of part material, the roasting that further switches under the air atmosphere then can be removed the carbon template, really obtains required mesopore oxide, mixed oxide or phosphatic microballoon.Should go for oxide compound and the phosphate material that great majority have potential catalytic applications as the method for template with mesoporous carbon spheres.
The method of technology of the present invention is as follows:
1. raw material mesoporous carbon microballoon is synthetic: a certain amount of mesopore silicon oxide spheres adds the dilution heat of sulfuric acid of the sucrose of aequum, at room temperature stirs centrifugal after drying, charing in nitrogen atmosphere subsequently then.This stirring, drying, charing step repeat once.Carbon/silicon the compound ball that obtains is soaked back water, washed with isopropyl alcohol several respectively in the hydrofluoric acid of 40wt% mass percent concentration, dry back obtains raw material mesoporous carbon microballoon.
2. metal oxide, the preparation of mixed metal oxide, metal phosphate mother liquor: with a certain amount of certain metal alkyl oxide as single metal oxide mother liquor; Or two kinds of metal alkyl oxides or a kind of metal alkoxide compound are mixed the mother liquor that obtains mixed metal oxide with another kind of metal anhydrous chloride; Or a certain amount of metal chloride, phosphoric acid ester be dissolved in the mother liquor that is made into metal phosphate in the alcohol compound (as methyl alcohol, ethanol, Virahol, the trimethyl carbinol etc.).
3. the mother liquor of mesoporous carbon microsphere template perfusion: a certain amount of mesoporous carbon microballoon is dispersed in a certain amount of this organic solvent that is used for washing after with washings such as aromatics derivative or hydrocarbon compound several, introduce a certain amount of mother liquor, be closed in and be placed in the container under the exsiccant environment, the quality percentage composition of dabbling mother liquor in organic solvent is 2-80wt%, and infusion time is 2-24h.Centrifugation, product organic solvent washing after drying.Obtain the mesoporous microsphere of carbon-non-silicon materials skeleton.
4. the removal of mesoporous carbon microsphere template: with mesoporous microsphere roasting under certain temperature in nitrogen atmosphere of a certain amount of carbon-non-silicon materials skeleton, switch to air atmosphere subsequently, roasting once more under certain temperature finally obtains mesopore oxide, phosphoric acid salt micro-sphere material.
Actual conditions is as follows:
The mass percent concentration of sucrose dilution heat of sulfuric acid is 1-50wt% in 1, stirs charing.Can repeat once, add hydrofluoric acid dips, washing, drying.
Metal alkyl oxide such as titanium ethanolate in 2, isopropyl titanate, tetrabutyl titanate, zirconic acid ethyl ester, zirconic acid isopropyl ester, the aluminic acid tert-butyl ester, tetraethoxy; Two kinds of metal alkyl oxide mixtures such as triethoxy aminopropyl estersil and titanium ethanolate, isopropyl titanate, the mixture of any one in the tetrabutyl titanate; A kind of metal alkoxide compound and another kind of metal anhydrous chloride such as titanium ethanolate, isopropyl titanate, the mixture of any one in the tetrabutyl titanate and zirconium tetrachloride; The mother liquor of metal phosphate such as a certain amount of zirconium tetrachloride, aluminum trichloride (anhydrous), titanium tetrachloride, chlorization high tin or anhydrous chlorides of rase high ferro a kind of and a certain amount of triethyl phosphate or trimethyl phosphite 99 wherein is dissolved in alcohol compound (comprising methyl alcohol, ethanol, Virahol, the trimethyl carbinol etc.) after mixing and is made into the solution that mass percent is 2-80wt%.
Before the mesoporous carbosphere perfusion, use organic solvent washing in 3.After the perfusion, centrifugation, washing, drying temperature is 60-150 ℃, be 1-48h time of drying.
Maturing temperature in 4 under nitrogen atmosphere is 100-1500 ℃, and roasting time is 0.5-100h, switch to air atmosphere after, maturing temperature is 100-1500 ℃, roasting time is 0.5-100h.
The sucrose of mesopore silicon oxide microballoon of the present invention-dilute sulphuric acid dipping can carry out in following condition:
Adding concentration in the mesopore silicon oxide microballoon is the dilution heat of sulfuric acid of the sucrose of 1-50wt%, stirs under the room temperature, and general churning time is 1-72h, and is centrifugal, drying; Charing 1-24h under 200-1200 ℃ of temperature in nitrogen atmosphere then.Can repeat once.The hydrofluoric acid dips 1-24h that adds 40wt% then thoroughly cleans, dry getting final product under 60-150 ℃.
The mesoporous carbon microballoon of above-mentioned acquisition need wash thoroughly, general 1-10 time, reunites otherwise easily produce.
The cleaning solvent of the mesoporous carbon microballoon that obtains by above-mentioned steps is aromatic solvent or varsol, as benzene, and toluene, normal hexane, hexanaphthene etc.
The dabbling better condition of mother liquor of the present invention is:
The mixed metal alkoxide compound is any one mixture in triethoxy third amino estersil and the titanic acid ester, and both mol ratios are 0.1-10.
The mixture of metal alkoxide compound and metal anhydrous chloride, both mol ratios are 0.2-12.
The mixture of metal anhydrous chloride and phosphoric acid ester, both mol ratios are 0.3-15.
The invention provides with the mesopore silicon oxide spheres is that raw material synthetic carbosphere is a template, and then by synthesising mesoporous oxide compound, mixed oxide and phosphatic method after metal alkane sample oxygen compound, hybrid metal alkyl oxide and the perfusion of metal phosphate mother liquor, the roasting.This preparation method is easy and simple to handle, and is applied widely, and modulation leeway is big, can synthesize the material of multiple composition, and the mesoporous non-silicon microballoon that is obtained has the pattern of high specific surface area and good ball, has a good application prospect.
Description of drawings
Fig. 1 is the XRD figure with meso-porous titanium oxide microspheres product of anatase crystal.The diffraction peak of other crystalline phases among the figure beyond the no tangible anatase octahedrite shows that product is the meso-porous titanium oxide microballoon of more purified anatase crystal.
Fig. 2 is the XRD figure with meso-porous titanium oxide microspheres product of rutile-anatase octahedrite mixing crystal formation.
Fig. 3 is the SEM figure of example 5, shows that the product major part is the microballoon pattern.
Fig. 4 is the SEM figure as the mesoporous carbon microballoon of template, shows that the mesoporous non-silicon skeleton series microballoon of this method synthetic has duplicated the pattern of template well.
Embodiment
Below example be to provided by the present invention be further specifying of being done of template synthetic mesopore oxide, mixed oxide, phosphoric acid salt microballoon with the mesoporous carbon microballoon.
Example 1
Adding concentration in the mesopore silicon oxide microballoon is the sucrose dilution heat of sulfuric acid of 1wt%.Stir 24h under the room temperature, centrifugal after drying.In nitrogen atmosphere,, obtain carbon silicon complex microsphere, it is soaked in the hydrofluoric acid of 40wt%, wash successively with a large amount of water and Virahol in 900 ℃ of following charings 5 hours, dry down in 100 ℃.Obtain the mesoporous carbon microballoon.
Example 2
Press the method for embodiment 1 and handle, the concentration of the sucrose dilution heat of sulfuric acid of adding is 50wt%, obtains the mesoporous carbon microballoon.
Example 3
Press the method for embodiment 1 and handle, the temperature of charing is 200 ℃, and 8 hours time, the mesoporous carbon microballoon pattern of acquisition changes.
Example 4
Press the method for embodiment 1 and handle, the temperature of charing is 1200 ℃, 2 hours time, the mesoporous carbon microballoon of acquisition.
Example 5
A) add hexanaphthene in the container that holds the mesoporous carbon microballoon that obtains in 1, make the liquid-solid ratio 50 of hexanaphthene and mesoporous carbon microballoon, jolting is 5 minutes behind the ultra-sonic dispersion, and is centrifugal, pours out hexanaphthene.Add hexanaphthene subsequently once more, repeat above-mentioned washing step 3 times.B) pouring into subsequently with mesoporous carbon microballoon liquid-solid ratio is 30 hexanaphthene.The quality percentage composition that is introduced in behind the ultra-sonic dispersion in the solvent is the isopropyl titanate of 10wt%, places glove box to place 12h under 25 ℃ of room temperatures behind the ultra-sonic dispersion once more.C) centrifugation goes out solid, and adding and initial mesoporous carbon microballoon liquid-solid ratio are 50 hexanaphthene washing, and the same a of method is with the solid dry 10h under 100 ℃ that obtains.
D) get the 0.5g solid and add in the magnetic boat, under nitrogen atmosphere, be warming up to 600 ℃ with the temperature rise rate of 10 ℃/min, and keep 6h from room temperature, reduce to room temperature after, switch to air atmosphere, be warming up to 600 ℃ with the temperature rise rate of 10 ℃/min, keep 6h.The cooling back obtains product, through XRD (Rigaku D/max-IIA x ray powder diffraction instrument), nitrogen absorption representation under the 77K, SEM (Philips XL 30 scanning electronic microscope) characterizes detection, for having the meso-porous titanium oxide microballoon of anatase crystal, the XRD spectrum, the specific surface and the pore volume distributed data of SEM figure and sample are seen accompanying drawing.
Embodiment 6
Press the method for example 5 and handle, the temperature of handling in nitrogen atmosphere is 900 ℃, and other experimental procedure is the same, obtains sample and detects to having rutile through XRD, and anatase octahedrite mixes the meso-porous titanium oxide microballoon of crystalline phase.Its XRD spectrum, the specific surface and the pore volume distributed data of SEM figure and sample are seen accompanying drawing.
Example 7
Press the method for example 5 and handle, introduce the aluminic acid tert-butyl ester in the b step, other experimental procedure is the same, obtains the meso-porous alumina microballoon.The specific surface of sample and pore volume distributed data are seen accompanying drawing.
Example 8
Press the method for example 5 and handle, introduce the zirconic acid isopropyl ester in the b step, other experimental procedure is the same, obtains the mesoporous zircite microballoon.The specific surface of sample and pore volume distributed data are seen accompanying drawing.
Example 9
Press the method for example 5 and handle, introduce the mixed solution of triethoxy aminopropyl estersil and isopropyl titanate in the b step, other experimental procedure is the same, obtains mesoporous titanium-titanium-silicon mixed oxide microballoon.The specific surface of the sample of sample and pore volume distributed data are seen accompanying drawing.
Example 10
Press the method for example 5 and handle, introduce the mixed solution of isopropyl titanate and zirconium tetrachloride in the b step, other experimental procedure is the same, obtains mesoporous titanium-Zr mixed oxide microballoon.Sample specific surface and pore volume distributed data are seen accompanying drawing.
Example 11
Press the method for example 5 and handle, introduce the mixed solution of titanium tetrachloride and triethyl phosphate in the b step, other experimental procedure is the same, obtains mesoporous titanium phosphate microballoon.The specific surface of sample and pore volume distributed data see Table 1.
| The sample name | Specific surface area (m 2/g) | Mean pore size (nm) | Pore volume (cm 3/g) |
| ????TiO(T) | ????158 | ????6 | ????0.30 |
| ????TiO(R) | ????143 | ????7 | ????0.34 |
| ????AlO | ????96 | ????6 | ????0.14 |
| ????ZrO | ????442 | ????4 | ????0.61 |
| ????Ti/Si | ????455 | ????4 | ????0.33 |
| ????Ti/Zr | ????117 | ????4 | ????0.14 |
| ????TiP | ????330 | ????3.5 | ????0.36 |
Table 1
Table 1 is example 5-11 specific surface and pore volume distributed data figure, shows that product has relative higher specific surface area.
In the table: TiO (T) is for having the meso-porous titanium oxide microballoon of anatase crystal;
TiO (R) is for having the meso-porous titanium oxide microballoon of rutile-anatase octahedrite mixing crystal formation;
AlO is the meso-porous alumina microballoon;
ZrO is the mesoporous zircite microballoon;
Ti/Si is a meso titanium silica mixed oxide microballoon;
Ti/Zr is mesoporous titanium Zr mixed oxide microballoon;
TiP is mesoporous titanium phosphate microballoon;
Example 12-15
Press the method for example 5 and handle, in the b step, introduce zirconium tetrachloride, aluminum trichloride (anhydrous), chlorization high tin, the mixed solution of anhydrous trichlorine high ferro and triethyl phosphate, other experimental procedure is the same, obtains the microballoon of mesoporous zirconium phosphate, aluminum phosphate, phosphoric acid tin, tertiary iron phosphate.
Example 16-19
Press the method for example 5 and handle, in the b step, introduce zirconium tetrachloride, aluminum trichloride (anhydrous), chlorization high tin, the mixed solution of anhydrous trichlorine high ferro and trimethyl phosphite 99, other experimental procedure is the same, obtains the microballoon of mesoporous zirconium phosphate, aluminum phosphate, phosphoric acid tin, tertiary iron phosphate.
Example 20
Press the method for example 5 and handle, maturing temperature is 200 ℃ under the nitrogen atmosphere in the d step, and other experimental procedure is the same, and the meso-porous titanium oxide microballoon of acquisition is amorphous.
Example 21
Press the method for example 5 and handle, maturing temperature is 400 ℃ under the air atmosphere in the d step, and other experimental procedure is the same, in the meso-porous titanium oxide microballoon of acquisition.
Example 22
Press the method for example 5 and handle, washing times is 1 time in a step, and other experimental procedure is the same, and the meso-porous titanium oxide microballoon of acquisition is reunited.
Example 23
Press the method for example 5 and handle, washing times is 10 times in a step, and other experimental procedure is the same, the meso-porous titanium oxide microballoon with anatase crystal of acquisition.
Example 24
Press the method for example 5 and handle, the quality percentage composition of dabbling mother liquor in solvent is 2wt% in the b step, and other experimental procedure is the same, and the meso-porous titanium oxide microballoon of acquisition can not keep good pattern.
Example 25
Press the method for example 5 and handle, the quality percentage composition of dabbling mother liquor in solvent is 80wt% in the b step, and other experimental procedure is the same, can not obtain the meso-porous titanium oxide microballoon.
Example 26
Press the method for example 5 and handle, placed 2 hours behind the dabbling mother liquor in the b step, other experimental procedure is the same, can not obtain the meso-porous titanium oxide microballoon.
Example 27
Press the method for example 5 and handle, placed 24 hours behind the dabbling mother liquor in the b step, other experimental procedure is the same, obtains to have the meso-porous titanium oxide microballoon of anatase crystal.
Example 28
Press the method for example 5 and handle, maturing temperature is 100 ℃ under the nitrogen atmosphere in the d step, and other experimental procedure is the same, and the meso-porous titanium oxide microballoon of acquisition is amorphous.
Example 29
Press the method for example 5 and handle, maturing temperature is 1500 ℃ under the nitrogen atmosphere in the d step, and other experimental procedure is the same, obtains to have the meso-porous titanium oxide microballoon of anatase crystal, but its specific surface area and porosity descend.
Example 30
Press the method for example 5 and handle, roasting time is 0.5 hour under the nitrogen atmosphere in the d step, and other experimental procedure is the same, and the meso-porous titanium oxide microballoon of acquisition is amorphous.
Example 31
Press the method for example 5 and handle, roasting time is 100 hours under the nitrogen atmosphere in the d step, and other experimental procedure is the same, obtains to have the meso-porous titanium oxide microballoon of anatase crystal.
Example 32
Press the method for example 5 and handle, maturing temperature is 100 ℃ under the air atmosphere in the d step, and other experimental procedure is the same, can not obtain the meso-porous titanium oxide microballoon.
Example 33
Press the method for example 5 and handle, maturing temperature is 1500 ℃ under the air atmosphere in the d step, and other experimental procedure is the same, obtains to have the meso-porous titanium oxide microballoon of anatase octahedrite-rutile mixing crystal formation, but its specific surface area and porosity descend.
Example 34
Press the method for example 5 and handle, roasting time is 0.5 hour under the air atmosphere in the d step, and other experimental procedure is the same, can not obtain the meso-porous titanium oxide microballoon.
Example 35
Press the method for example 5 and handle, roasting time is 100 hours under the air atmosphere in the d step, and other experimental procedure is the same, obtains to have the meso-porous titanium oxide microballoon of anatase crystal.
Claims (7)
1. one kind is the synthesising mesoporous metal oxide of template with the mesoporous carbon microballoon, mixed metal oxide, the method of metal phosphate series microballoon, it is characterized in that the sucrose-dilution heat of sulfuric acid dipping preparation template mesoporous carbon microballoon of this method by the mesopore silicon oxide microballoon, with metal alkoxide compound or mixed metal alkoxide compound, the mixture of the mixture of metal alkoxide compound and metal chloride or metal chloride and phosphoric acid ester is an oxide compound, mixed oxide, phosphatic forerunner's mother liquor, then by the perfusion of mother liquor at the mesoporous carbon microballoon, and the synthetic target product of two steps of carbon is removed in roasting, actual conditions is: (1) used template is the mesoporous carbon microballoon, being used for dabbling forerunner's mother liquor is metal alkoxide compound or mixed metal alkoxide compound, the mixture of the mixture of metal alkoxide compound and metal chloride or metal chloride and phosphoric acid ester is an oxide compound, mixed oxide, phosphatic forerunner's mother liquor, before the perfusion, mesoporous carbon microballoon organic solvent washs 1-10 time; (2) the used organic solvent of perfusion carbosphere is the above-mentioned solvent of mentioning that is used to wash, and the quality percentage composition of dabbling mother liquor in solvent is 2-80wt%, and the time is 2-24h, and perfusion finishes; After the centrifugation, washing; (3) temperature of sample roasting under nitrogen atmosphere is 100-1500 ℃, and roasting time is 0.5-100h, switch to air atmosphere after, maturing temperature is 100-1500 ℃, roasting time is 0.5-100h.
2. according to claim 1 is the method for the synthesising mesoporous metal oxide of template, mixed metal oxide, metal phosphate series microballoon with the mesoporous carbon microballoon, the condition that it is characterized in that the sucrose-dilution heat of sulfuric acid dipping preparation mesoporous carbon microballoon of mesopore silicon oxide microballoon is: adding concentration in the mesopore silicon oxide microballoon is the dilution heat of sulfuric acid of the sucrose of 1-50wt%, stir under the room temperature, centrifugal after drying, charing under 200-1200 ℃ of temperature in nitrogen atmosphere then, obtain carbon silicon compound ball, it is soaked in hydrofluoric acid, and washing is dry to get final product.
3. according to claim 1 is the method for the synthesising mesoporous metal oxide of template, mixed metal oxide, metal phosphate series microballoon with the mesoporous carbon microballoon, it is characterized in that preceding mesoporous carbon microballoon organic solvent washing 1-10 time of forerunner's mother liquor perfusion.
4. according to claim 1 is the method for the synthesising mesoporous metal oxide of template, mixed metal oxide, metal phosphate series microballoon with the mesoporous carbon microballoon, it is characterized in that the organic solvent of mesoporous carbon microballoon washing is aromatic solvents or varsol.
5. according to claim 1 is the method for the synthesising mesoporous metal oxide of template, mixed metal oxide, metal phosphate series microballoon with the mesoporous carbon microballoon, it is characterized in that the mixed metal alkoxide compound is any one mixture in triethoxy third amino estersil and the titanic acid ester, both mol ratios are 0.1-10.
6. according to claim 1 is the method for the synthesising mesoporous metal oxide of template, mixed metal oxide, metal phosphate series microballoon with the mesoporous carbon microballoon, the mixture that it is characterized in that metal alkoxide compound and metal anhydrous chloride, both mol ratios are 0.2-12.
7. according to claim 1 is the method for the synthesising mesoporous metal oxide of template, mixed metal oxide, metal phosphate series microballoon with the mesoporous carbon microballoon, the mixture that it is characterized in that metal anhydrous chloride and phosphoric acid ester, both mol ratios are 0.3-15.
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