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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- CN107746074B CN107746074B CN201711096104.7A CN201711096104A CN107746074B CN 107746074 B CN107746074 B CN 107746074B CN 201711096104 A CN201711096104 A CN 201711096104A CN 107746074 B CN107746074 B CN 107746074B
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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- 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
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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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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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