CN107746074B - A kind of titanium dioxide of core-shell structure mesoporous material and preparation method thereof with cavity - Google Patents
A kind of titanium dioxide of core-shell structure mesoporous material and preparation method thereof with cavity Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011258 core-shell material Substances 0.000 title claims abstract description 37
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 33
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000009825 accumulation Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 12
- -1 titanium sulfate ethanol Chemical compound 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- 230000001147 anti-toxic effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000036314 physical performance Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000011257 shell material Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/30—Particle morphology extending in three dimensions
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- Chemical Kinetics & Catalysis (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
A kind of titanium dioxide of core-shell structure mesoporous material and preparation method thereof with cavity belongs to field of material technology, and for material grains having a size of 10~30nm, accumulation, which is constituted, has mesoporous core-shell structure, including shell mechanism and inner core；Method are as follows: (1) second alcohol and water is mixed into ethanol water；(2) titanium sulfate is added；(3) ammonium chloride powder is added and stirs into colorless and transparent mixed solution；(4) it is put into reaction kettle, is reacted 1~10 hour at 150~220 DEG C, natural cooling isolates solid phase as presoma；(5) roasting after presoma is washed and dried, is made the titanium dioxide of core-shell structure mesoporous material with cavity.The advantages that product of the invention has large specific surface area, and adsorption capacity is strong, and reactant/product diffusion transport is easy to carry out, good antitoxin physical performance and circulation and stress；The problem of method is easy to operate, avoids production cost and Environmental costs raising.
Description
Technical field
The invention belongs to metal oxide materials technical field, in particular to a kind of core-shell structure titanium dioxide with cavity
Titanium mesoporous material and preparation method thereof.
Background technique
The water pollution got worse promotes the research of photocatalytic degradation material, nanocrystalline TiO2It is high with catalytic activity,
Chemical stability is good, and low energy consumption, non-toxic and safe, lower-price characteristic, is a kind of ideal conductor photocatalysis degradable material.
The main problem for hindering its application at present is, and its catalytic stability and circulation not high to the absorption efficiency of visible light
Reclaiming ability also needs further to be promoted；TiO2Mesoporous material porosity is high, and specific surface area and activity are big, can adsorb more
Organic pollutant, and using between the internal grain of duct multiple reflections effect enhance its absorption efficiency to sunlight, from
And effectively improve photocatalytic degradation efficiency；And possess the titanium dioxide mesoporous material of core-shell structure, have unique semi-enclosed
It is steady also to show brilliant photostability and catalysis while keeping above-mentioned mesoporous material high reaction activity for micro- reaction environment
It is qualitative, it is easy to circulation and stress regenerative operation.
The common method about the preparation of titanium dioxide of core-shell structure material is template at present, is divided into soft template and hard template
Two classes.Soft template is usually that surfactant is utilized to form micella or vesica etc., and hollow or core-shell structure answer is obtained after roasting
Condensation material, affecting parameters are numerous, are unfavorable for industrialization；Hard template rule is mostly with organic polymeric microspheres, silicon dioxide microsphere, carbon
Ball etc. is carrier, and nano-titanium dioxide is evenly distributed on carrier surface, institute's carried titanium dioxide shell knot in a manner of shell
It is insufficient to close intensity, load capacity is not high.Also the titanium dioxide for preparing core-shell structure using hydro-thermal method using Titanium alkoxides as titanium source is had been reported that
Material, but the unstable facile hydrolysis of Titanium alkoxides, reaction speed are difficult to control；Chinese patent CN201010201801.6 discloses one kind
The preparation method of titanium dioxide nano material with core-shell structure, this method using trivalent titanium salt and glucose as initial feed,
The titanium dioxide nano material with core-shell structure has been made by solvent heat and calcining.This method need to comprehensively consider in presoma
The removal degree and core-shell structure of residual carbon are sintered destroyed overall degree, increase calcining link production cost and
The control difficulty of structure repeatability.
Summary of the invention
The present invention is intended to provide a kind of titanium dioxide of core-shell structure mesoporous material and preparation method thereof with cavity, uses
Titanium sulfate and ammonium chloride are primary raw material, obtain the method that presoma roasts again by low-temp reaction, obtained hud typed mesoporous
Structure can dramatically increase the catalytic activity of material and the adsorbance to organic pollutant, and have good antitoxin physical performance and follow
Ring recyclability.
The crystallite dimension of titanium dioxide of core-shell structure mesoporous material with cavity of the invention is 10~30nm, crystal grain heap
Product constitutes the core-shell structure for having 10~20nm mesoporous, including shell mechanism and inner core；There is cavity inside shell mechanism, outside
The mean outside diameter of shell structure having a size of 1~4 μm, shell mechanism with a thickness of 50~100nm；Also there is kernel inside shell mechanism
Structure, the mean outside diameter of inner core is having a size of 0.5~2 μm.
The specific surface area of the above-mentioned titanium dioxide of core-shell structure mesoporous material with cavity is 102~125m2/g。
The crystal form of the above-mentioned titanium dioxide of core-shell structure mesoporous material with cavity is anatase nanometer crystal.
The preparation method of titanium dioxide of core-shell structure mesoporous material with cavity of the invention sequentially includes the following steps:
(1) by second alcohol and water according to volume ratio 1:(1~5) ratio mix, obtain ethanol water；
(2) titanium sulfate is added in ethanol water, is stirred evenly, form titanium sulfate ethanol water；Wherein titanium sulfate
Molar ratio with ethyl alcohol is 1:(50~100)；
(3) ammonium chloride powder is added in titanium sulfate ethanol water, stirs evenly and colorless and transparent mixed solution is made；
Wherein the molar ratio of titanium sulfate and ammonium chloride is 1:(1~3)；
(4) mixed solution is put into reaction kettle, is reacted 1~10 hour in 150~220 DEG C, naturally cools to room temperature, so
After isolate solid phase as presoma；
(5) by presoma it is washed and dried after, roasted 3~8 hours under the conditions of 450~650 DEG C, be made have cavity
Titanium dioxide of core-shell structure mesoporous material.
In above-mentioned steps (5), presoma washing, which refers to, is washed with deionized removal acid ion, and drying refers to 100
It is dried 2~4 hours under the conditions of ± 3 DEG C.
Meso-hole structure with 10~20nm is prepared for the invention has the following beneficial effects: (1) and with cavity
Titanium dioxide of core-shell structure nanocrystalline material；(2) spherical shell of titanium dioxide of core-shell structure mesoporous material and kernel be all by 10~
The titanium dioxide nanocrystalline grain of 30nm is accumulated, and crystal grain accumulation hole is interlaced, transports and load sky there are secondary between nucleocapsid
Chamber has large specific surface area, and adsorption capacity is strong, and reactant/product diffusion transport is easy to carry out, and good antitoxin physical performance and follows
The advantages that ring recyclability；(3) method is without complex device, easy to operate, when existing template can be overcome to prepare core-shell material
The disadvantages of template synthesis cost height, complex process, also it is avoided that other methods are unstable using Titanium alkoxides or titanium tetrachloride etc.
Production cost caused by titanium source and Environmental costs improve problem.
Detailed description of the invention
Fig. 1 is the XRD diagram of the titanium dioxide of core-shell structure mesoporous material with cavity of embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of the titanium dioxide of core-shell structure mesoporous material with cavity of embodiment 1；
Fig. 3 is the pore-size distribution and adsorption desorption song of the titanium dioxide of core-shell structure mesoporous material with cavity of embodiment 2
Line chart.
Specific embodiment
The reaction kettle used in the embodiment of the present invention is the reaction kettle of inner liner polytetrafluoroethylene.
When mixed solution is put into reaction kettle in the embodiment of the present invention, material packing ratio in reaction kettle is 70~85%.
Ethyl alcohol, titanium sulfate and the ammonium chloride used in the embodiment of the present invention is market analytical pure reagents.
The water used in the embodiment of the present invention is deionized water.
It is using centrifuge separation that solid phase is isolated in the embodiment of the present invention.
Roasting is using Muffle furnace in the embodiment of the present invention.
Material phase analysis test uses Shimadzu XRD-7000 type X-ray diffractometer in the embodiment of the present invention.
Microscopic appearance detection uses Hitachi SU8010 field emission scanning electron microscope in the embodiment of the present invention.
The equipment that the detection of central hole structure of the embodiment of the present invention uses is 4800 specific surface area of V-Sorb and Porosimetry.
The mixing speed of step (2) is 500~1500rpm in the embodiment of the present invention.
Embodiment 1
Second alcohol and water is mixed according to the ratio of volume ratio 1:1, obtains ethanol water；
2g titanium sulfate is added in ethanol water, is stirred evenly, titanium sulfate ethanol water is formed；Wherein titanium sulfate with
The molar ratio of ethyl alcohol is 1:50；
Ammonium chloride powder is added in titanium sulfate ethanol water, stirs evenly and colorless and transparent mixed solution is made；Its
The molar ratio of middle titanium sulfate and ammonium chloride is 1:1；
Mixed solution is put into reaction kettle, is reacted 10 hours in 150 DEG C, naturally cools to room temperature, is then demultiplex out solid
Mutually it is used as presoma；
Removal acid ion is washed with deionized in presoma, then dries 2 hours under the conditions of 100 ± 3 DEG C, finally
It is roasted 7 hours under the conditions of 500 DEG C, the titanium dioxide of core-shell structure mesoporous material with cavity is made；
Object phase composition XRD analysis exists as shown in Figure 1, roasting the titanic oxide material that 7h is obtained as seen from the figure, at 500 DEG C
25.28 °, 37.80 °, 48.05 °, 53.89 °, 55.06 °, 62.69 °, 68.76 °, 70.31 ° and 75.03 ° have characteristic peak, respectively
(101), (004), (200) (105), (211), (204), (116), (220) and (215) of corresponding anatase titania are brilliant
It is consistent in face, with standard card JCPDS:21-1272；
The crystallite dimension of titanium dioxide of core-shell structure mesoporous material with cavity is 10~30nm, and crystal grain accumulation constitutes tool
There are the core-shell structure that 10~20nm is mesoporous, including shell mechanism and inner core；There is cavity inside shell mechanism, shell mechanism
Mean outside diameter having a size of 1~4 μm, shell mechanism with a thickness of 50~100nm；There is inner core, kernel inside shell mechanism
The mean outside diameter of structure is having a size of 0.5~2 μm, specific surface area 116m2/ g, crystal form are anatase nanometer crystal, electron-microscope scanning knot
Fruit is as shown in Figure 2.
Embodiment 2
With embodiment 1, difference is method:
(1) volume ratio of second alcohol and water is 1:2；
(2) molar ratio of titanium sulfate and ethyl alcohol is 1:60；
(3) molar ratio of titanium sulfate and ammonium chloride is 1:2；
(4) mixed solution is put into reaction kettle, is reacted 5 hours in 170 DEG C；
(5) drying time is 3 hours, 450 DEG C of maturing temperature, the time 8 hours；
BJH adsorbs pore size distribution curve and absorption/desorption isotherm as shown in figure 3, the specific surface area that BET is calculated is
125m2/g；As seen from the figure, most probable pore size shows product within the scope of 10~20nm to be situated between on BJH absorption pore size distribution curve
Porous materials；Absorption/desorption isotherm belongs to typical IV type, and has H1 type hysteresis loop, further illustrates that product has aperture
The even mesoporous structure of cylinder of narrow distribution.
Embodiment 3
With embodiment 1, difference is method:
(1) volume ratio of second alcohol and water is 1:3；
(2) molar ratio of titanium sulfate and ethyl alcohol is 1:70；
(3) molar ratio of titanium sulfate and ammonium chloride is 1:2；
(4) mixed solution is put into reaction kettle, is reacted 3 hours in 180 DEG C；
(5) drying time is 2 hours, 520 DEG C of maturing temperature, the time 6 hours；
The specific surface area of titanium dioxide of core-shell structure mesoporous material with cavity is 112m2/ g, crystal form are received for anatase
Meter Jing.
Embodiment 4
With embodiment 1, difference is method:
(1) volume ratio of second alcohol and water is 1:4；
(2) molar ratio of titanium sulfate and ethyl alcohol is 1:80；
(3) molar ratio of titanium sulfate and ammonium chloride is 1:3；
(4) mixed solution is put into reaction kettle, is reacted 5 hours in 190 DEG C；
(5) drying time is 4 hours, 550 DEG C of maturing temperature, the time 5 hours；
The specific surface area of titanium dioxide of core-shell structure mesoporous material with cavity is 110m2/ g, crystal form are received for anatase
Meter Jing.
Embodiment 5
With embodiment 1, difference is method:
(1) volume ratio of second alcohol and water is 1:5；
(2) molar ratio of titanium sulfate and ethyl alcohol is 1:90；
(3) molar ratio of titanium sulfate and ammonium chloride is 1:3；
(4) mixed solution is put into reaction kettle, is reacted 3 hours in 200 DEG C；
(5) drying time is 3 hours, 600 DEG C of maturing temperature, the time 4 hours；
The specific surface area of titanium dioxide of core-shell structure mesoporous material with cavity is 107m2/ g, crystal form are received for anatase
Meter Jing.
Embodiment 6
With embodiment 1, difference is method:
(1) volume ratio of second alcohol and water is 1:5；
(2) molar ratio of titanium sulfate and ethyl alcohol is 1:100；
(3) molar ratio of titanium sulfate and ammonium chloride is 1:3；
(4) mixed solution is put into reaction kettle, is reacted 1 hour in 220 DEG C；
(5) drying time is 4 hours, 650 DEG C of maturing temperature, the time 3 hours；
The specific surface area of titanium dioxide of core-shell structure mesoporous material with cavity is 102m2/ g, crystal form are received for anatase
Meter Jing.
Claims (2)
1. a kind of preparation method of the titanium dioxide of core-shell structure mesoporous material with cavity, it is characterised in that according to the following steps into
Row:
(1) by second alcohol and water according to volume ratio 1:(1 ~ 5) ratio mix, obtain ethanol water；
(2) titanium sulfate is added in ethanol water, is stirred evenly, form titanium sulfate ethanol water；Wherein titanium sulfate and second
The molar ratio of alcohol is 1:(50 ~ 100)；
(3) ammonium chloride powder is added in titanium sulfate ethanol water, stirs evenly and colorless and transparent mixed solution is made；Wherein
The molar ratio of titanium sulfate and ammonium chloride is 1:(1 ~ 3)；
(4) mixed solution is put into reaction kettle, is reacted 1 ~ 10 hour in 150 ~ 220 DEG C, naturally cools to room temperature, then separate
Solid phase is as presoma out；
(5) by presoma it is washed and dried after, roasted 3 ~ 8 hours under the conditions of 450 ~ 650 DEG C, be made with cavity nucleocapsid
Structure titanium dioxide mesoporous material；The crystallite dimension of the titanium dioxide of core-shell structure mesoporous material with cavity be 10 ~
30 nm, crystal grain accumulation constitute the core-shell structure for having 10 ~ 20 nm mesoporous, including shell mechanism and inner core；Shell mechanism
There is a cavity in inside, the mean outside diameter of shell mechanism having a size of 1 ~ 4 μm, shell mechanism with a thickness of 50 ~ 100 nm；In shell mechanism
Portion also has inner core, and the mean outside diameter of inner core is having a size of 0.5 ~ 2 μm.
2. the preparation method of the titanium dioxide of core-shell structure mesoporous material according to claim 1 with cavity, feature
It is in step (5), presoma washing, which refers to, is washed with deionized removal acid ion, and drying refers in 100 ± 3 DEG C of conditions
Lower drying 2 ~ 4 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711096104.7A CN107746074B (en) | 2017-11-09 | 2017-11-09 | A kind of titanium dioxide of core-shell structure mesoporous material and preparation method thereof with cavity |
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