CN105217676B - Titania aerogel with nanometer sheet and nano-porous structure and preparation method thereof - Google Patents
Titania aerogel with nanometer sheet and nano-porous structure and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of titania aerogel with nanometer sheet and nano-porous structure and preparation method thereof, the titania aerogel has nanometer sheet and nano-porous structure, and the BET specific surface area of the titania aerogel is 50-300 m2/g。
Description
Technical field
The invention belongs to new chemical materialses field, and in particular to a kind of titanium oxide with nanometer sheet and nano-porous structure
Aeroge and preparation method thereof.
Background technology
Aeroge is known most light solid in the world at present, and its porosity may be up to 99.8%, bore hole size 1~
100nm, specific surface area may be up to 1000m2/ g, bulk density can be in 3~500kg/m3Between change, be a kind of high-tech, green
It is minimum up to 0.015W/ (mK) under environmentally friendly, efficient energy-saving and heat-insulating material, its thermal conductivity normal temperature and pressure), it is current known solid
Minimum one kind of thermal conductivity in state material.Due to the unique texture and performance of aeroge, the material is expected in Aeronautics and Astronautics, work
There is huge application prospect in industry energy-conservation, building energy conservation and the extensive field such as sound insulation, damping, explosion-proof, environmentally friendly, energy storage.2007
On August 19, Britain《The Sunday Times》Publish an article title, " aeroge will be the material that changes the world ".
Titanium dioxide (TiO2) it is a kind of broad-band gap oxide semiconductor material, generally there are two kinds of crystalline substances of anatase and rutile
Type, serves not only as titanium dioxide and delustering agent, has substantial amounts of application in fields such as paint, enamel, and touch as semiconductor and light
Catalytic material, the field such as air cleaning indoors, waste water treatment, PM2.5 improvement, cosmetics, solar cell is widely used.
Titania aerogel is a kind of low-density, high porosity, the nano-porous materials of high-specific surface area, its unique hole
Structure and semiconductor light it is electroactive make its have in fields such as catalysis, catalyst carrier, electrode, absorption, insulations widely should
Use prospect.Such as, in terms of electrode, titania aerogel can be used as the light anode of DSSC, due to its height ratio
Surface area, can load more dyestuffs, so as to improve photo-excited electron density and battery efficiency；In terms of catalysis, titanium oxide gas
Gel can be widely used for photocatalytic air, water extraction is pure and other are based on the fields such as photochemical catalytic oxidation and organic pollutant degradation.
The preparation of titania aerogel is typically prepared using collosol and gel combination supercritical drying process, complex process, danger
Dangerous larger, cost is high.But it is extremely difficult to prepare pure titania aerogel using constant pressure and dry technique, because Titanium alkoxides are active
A variety of factors such as height, Titanium alkoxides gelatinization complexity, using constant pressure and dry method be difficult to obtain with good microstructure and compared with
The titania aerogel material of low-density.The preparation on titania aerogel has some reports both at home and abroad.Chinese patent
200610024301.3 a kind of preparation method of the titania aerogel available for catalysis material is disclosed, using non-titanium alcohol
Salt and aqueous solvent are made into presoma, then mixs with epoxides, can be as short as obtaining the block alcohol of titanium oxide in several minutes solidifying
Glue, and through aging, the means such as supercritical drying, calcination process obtain titania aerogel powder or block.Chinese patent
201310012851.3 disclose one kind in precursor solution while adding surfactant, chelating agent and drying control agent
Method to prepare titania aerogel.Chinese patent 201310459800.5 discloses a kind of aniline-acetone in-situ preparation water
Method control sol-gel process prepares titanium oxide gel, then by aging, solvent is replaced and supercritical drying process, obtains high
The method of the good block titania aerogel of specific surface area, controllability.Chinese patent 201310755307.8 discloses a kind of normal
The method that pressure prepares hydrophobic titania aeroge, is characterized in, after titanium oxide gel carries out exchange of solvent, then in hexamethyl
Hydrophobically modified is carried out in the cyclohexane solvent of disilazane, so as to obtain Hydrophobic silica aeroge after drying box is cooled down.
Although the existing numerous studies of preparation technology on titania aerogel, current people can not be also realized same
The multilevel hierarchy aeroge of different morphologies is obtained in titania aerogel simultaneously.No matter such multistage material aeroge is than surface
All it is significantly increased in terms of product and Electronic Transport of Two Benzene than conventional oxidation titanium aeroge, so as in dye sensitization of solar electricity
It is used widely in the fields such as pond, lithium ion battery electrode material, photocatalysis.Therefore, exploitation prepares the new technology of such material
With important scientific meaning and wide market prospects.
The content of the invention
It is contemplated that filling up prior art can not realize in same titania aerogel while obtaining different morphologies
Blank, the invention provides a kind of titania aerogel with nanometer sheet and nano-porous structure and preparation method thereof.
The invention provides a kind of titania aerogel, the titania aerogel has nanometer sheet and nanoporous knot
Structure, the BET specific surface area of the titania aerogel is 50-300m2/g。
It is preferred that in the titania aerogel, the thickness of nanometer sheet is 3-50nm, the aperture of nano-pore for 1-
100nm, the porosity of aeroge is 50-98%.
It is preferred that the density of the titania aerogel is 0.3-1.5g/cm3。
Present invention also offers a kind of method for preparing above-mentioned titania aerogel, methods described includes：
1) organic titanium source, alcohol are mixed and obtains A liquid with acid for adjusting pH to 1~5；
2) alcohol, water, amino agents are mixed and obtains B liquid with acid for adjusting pH to 1~5；
3) by step 1) prepare A liquid and step 2) prepare B liquid mixing, stirring to sediment disappear after stand, obtain
Titania gel；
4) by step 3) in prepare titania gel under aging；
5) by step 4) after the titania gel through aging for preparing is broken, aging after being mixed with alcohol obtains titanium dioxide
Titanium alcogel；
6) by step 5) the titanium dioxide alcogel for preparing, to obtain titanium dioxide alkane solidifying for aging after mix with alkane solvent
Glue；And
7) by step 6) made from after titanium dioxide alkane gel drying, calcining is produced with nanometer sheet and nanoporous shape
The titania aerogel of looks.
It is preferred that step 1) in, the organic titanium source contains at least one O-Ti key, the preferred fourth of metatitanic acid four of organic titanium source
Ester, tetraethyl titanate, isopropyl titanate.
It is preferred that step 1) in, the volume ratio of organic titanium source and alcohol is 1:(1-5).
It is preferred that step 1) and step 2) in, acid is hydrochloric acid, acetic acid, sulfuric acid or nitric acid；Alcohol is to contain a hydroxyl-functional
The low-boiling point alcohol of group, preferably methanol, ethanol, propyl alcohol, isopropanol.
It is preferred that step 2) in, amino agents are to be selected from-NH containing at least one3、-NH2With the chemical combination of-NH group
Thing, preferably urea, hexa, ammoniacal liquor, ethylenediamine, triethanolamine.
It is preferred that step 3) in, titanium source, water, alcohol, the mol ratio of amino agents are 1 in TiO 2 sol：(10-
100)：(8-20)：(0.1-5).
It is preferred that step 4) in, aging 1-72 hours, preferably 4-8 hours at 50-99 DEG C.
It is preferred that step 5) in, by step 4) TiO 2 sol of aging for preparing smashed to pieces to the full-size of fragment
Less than 5mm, it is that its 1-10 times alcohol is mixed with volume, aging 1-72 hours at 50-78 DEG C, obtains titanium dioxide alcosol,
Wherein, alcohol preferred alcohol, methanol, isopropanol.
It is preferred that step 6) in, titanium dioxide alcosol is that its 1-10 times alkyl solvents is mixed with volume, in 50-78
Obtain titanium dioxide alkane gel within aging 1-72 hours at DEG C, wherein, the preferred surface tension of alkyl solvents is less than 25N/m alkane, special
Not preferred hexamethylene, normal heptane, n-hexane.
It is preferred that step 7) in, the parameter of drying process is：Drying temperature is 60-200 DEG C, and drying time is 0.5-24
Hour；The technological parameter of high-temperature calcination is：Calcining heat is 300-800 DEG C, and calcination time is 0.5-24 hours.
Beneficial effects of the present invention：
The present invention's is mainly characterized by, and TiO is prepared using Gao Shui-titanium mol ratio2Gel and aeroge, large quantity of moisture are deposited
The aquation of organic titanium source and gelling process can be greatly facilitated, gelling was realized so as to (more than ten seconds) in very short time, so that
Significantly improve production efficiency；
The features of the present invention is also resided in, and the ageing process that amino agents regulate and control titanium oxide wet gel is added in presoma,
The acid that the distinctive alkalescence of amino agents will be neutralized in presoma, it is to avoid inevitable peptization shows in conventional sol gel process
As so as to smoothly obtain the TiO with some strength2Wet gel；
The features of the present invention is also resided in, and the amino agents added in precursor solution can release NH2Group, can be directed to
It is adsorbed in TiO2Nanocrystalline high energy crystal face.When in high-temperature roasting stage, NH2Group is removed, and will promote TiO2Nanocrystal from
Assembling, so as to form flaky nanometer structure；
The features of the present invention is also resided in, the TiO prepared using above-mentioned technique2Aeroge is only by size under nanoscale
5-30nm TiO2Crystal grain is constituted, under micron, submicron-scale, while having two kinds of shapes of nanometer sheet and nanoporous aggregation
Looks.Before not thermally treated, titania aerogel powder has good crystallinity, but in the single porous of nanoscale presentation
Looks；After high-temperature roasting, the crystallinity of titania aerogel powder is greatly improved, and two kinds of shapes are showed on nanoscale
Looks：Fine and close nano flake and porous nanocrystal aggregates；
The features of the present invention is also resided in, and gained titania aerogel powder has higher specific surface area, the powder of preparation
BET specific surface area is up to 170m2/ g, far above conventional Ti O2Nano-powder (such as goldschmidt chemical corporation P25 types TiO2Powder surface area per unit volume
Product is 55m2/ g), so as to increase considerably the load capacity of electrode pair dyestuff and in various catalytic reactions activity and urge
Change efficiency.
Brief description of the drawings
Fig. 1 is the titanium oxide airsetting with nanometer sheet and nano-porous structure prepared in an embodiment of the invention
Rubber powder body microstructure schematic diagram, wherein 1-TiO2Nano-particle, 2-TiO2Nanometer sheet, 3-TiO2Nano-porous structure；
Fig. 2 is the X ray diffracting spectrum of the titania aerogel powder prepared in an embodiment of the invention；
The transmission electron microscope of titania aerogel powders of the Fig. 3 to be prepared in an embodiment of the invention shines
White dashed line marks region for nanometer sheet in piece, figure；
Fig. 4 is the transmission of the titania aerogel powder without high-temperature roasting prepared in an embodiment of the invention
Electron micrograph.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments
The present invention is merely to illustrate, is not intended to limit the present invention.
The invention discloses a kind of titania aerogel powder with nanometer sheet and nano-porous structure and its preparation skill
Art.The purpose of the present invention is：By introducing " amino agents " in precursor solution, regulate and control gelling, the aging of titanium oxide sol
Process and high temperature sintering behavior, and the means such as exchange of solvent, constant pressure and dry, high-temperature roasting are combined, prepare under micro/nano-scale
There is the multilevel hierarchy titania aerogel powder of nanometer sheet and nanoporous pattern simultaneously.The present invention prepares titania aerogel
The technical characterstic of powder is：Prevent titanium oxide gel distinctive in ageing process by adding amino agents in presoma
" peptization " phenomenon, improves aeroge frame strength and crystallization property；Pass through-NH under high temperature2The burn off of group induces TiO2It is nanocrystalline
Grain self assembly, obtains the multilevel hierarchy titania aerogel powder that nanometer sheet coexists with nanoporous pattern.Preparation process can be with
Briefly include：(1)TiO2It is prepared by colloidal sol and gel：It is 1 by mol ratio：10-100：8-20：0.2-0.6 titanium source, water, alcohol
Solvent, amino agents are prepared into A liquid and B liquid respectively, and with vigorous stirring mix the two, stand 10 seconds to 60 minutes, obtain
To TiO2Gel；(2) aging：Gained TiO2Gel is aging 1-72 hours under the conditions of 50-99 DEG C；(3) exchange of solvent：Use respectively
Ethanol and low boiling alkyl solvents are to TiO2Gel carries out exchange of solvent；(4) constant pressure and dry：Under 60-200 DEG C, condition of normal pressure
Drying 0.5-24 hours；(5) high-temperature roasting：In 300-800 DEG C of Muffle kiln roasting 0.5-24 hours.In gained aerogel powder
Nanometer sheet can assign material good electric conductivity, nano-porous structure can assign material high specific surface area, so that at some
The application of demand high-specific surface area and the special occasions of high conductivity, the light anode of such as DSSC, lithium simultaneously
The fields such as ion battery electrode, photocatalysis, photocatalytic water.
The present invention technical solution be：
The alcoholic solution of organic titanium salt is used for presoma, passes through the displacement of sol-gel process combination solvent, constant pressure and dry, height
The techniques such as temperature roasting, prepare titania aerogel.Amino agents are introduced in organic titanium salt presoma, are discharged using its heating
OH-Characteristic prevents titanium oxide gel peptization in ageing process, and improves aeroge crystallinity；Roasted using amino agents in high temperature
Oriented attachment is discharged during burning in the-NH of titanium oxide high energy crystal face2Group, promotes TiOx nano crystal grain self assembly, obtains
Titanium oxide laminated structure.And not by-NH2Self assembly does not occur for the nanocrystal of group cladding, forms nanoporous after baking
Pattern.By controlling the addition of amino agents, the content of nanometer sheet in aerogel powder can be adjusted.By such scheme,
It can obtain while having the titania aerogel powder of nanometer sheet and nanoporous pattern.
The present invention's concretely comprises the following steps：
(1) TiO2It is prepared by colloidal sol and gel
The organic compound for selecting Titanium is titanium source (1), multiple with water, alcoholic solvent (2), hydrochloric acid (3), amino agents (4)
Close and prepare TiO2Colloidal sol (5).Specifically divide following three step：
A) alcoholic solvent (2) of organic titanium source (1) and isometric ratio, appropriate hydrochloric acid are mixed, adjustment pH value to 1-5 scopes,
Stir 5-120 minutes at room temperature, obtain A liquid (6)；
B) remaining alcoholic solvent (2), water, appropriate hydrochloric acid (3) and amino agents (4) are mixed, adjust pH value to 1-5 scopes,
Stir 5-60 minutes at room temperature, obtain B liquid (7)；
C) with vigorous stirring, A liquid (6) and B liquid (7) are mixed rapidly, after disappearance to be precipitated, arrest reaction liquid 10 seconds is extremely
60 minutes, obtain TiO2Gel (8)；
In presoma system, titanium source, water, alcoholic solvent, the mol ratio of amino agents are 1：10-100：8-20：0.2-0.6.
Titanium source is the compound containing one or more " O-Ti " keys, such as butyl titanate, tetraethyl titanate, isopropyl titanate in molecule
Deng；Alcoholic solvent is the low boiling point solvent containing " OH " functional group, such as methanol, ethanol, propyl alcohol, isopropanol in molecule；Ammonia
Base reagent be molecule in contain one or more-NH3、NH2, NH groups inorganic or organic compound, such as urea, hexa-methylene
Tetramine, ammoniacal liquor, ethylenediamine, triethanolamine etc..
(2) aging
The TiO that step (1) is obtained2Gel (8) is placed in closed container, and aging 1 to 72 is small in 50-99 DEG C of baking oven
When, preferably 4-8 hours, obtain aging TiO2Gel (9).
(3) solvent is replaced
The aging TiO that step (2) is obtained2Gel (9) is smashed to pieces, and fragment full-size is less than 5mm, with 1-10 times of volume
Ethanol mixing, be placed in closed container, aging 1 to 72 hour in 50-78 DEG C of baking oven, preferably 4-8 hour.Remove upper strata molten
Agent, obtains TiO2Alcogel (10)；
By TiO2Alcogel (10) is mixed with the alkyl solvents (11) of 1-10 times of volume, is placed in closed container, in 50-78
Aging 1 to 72 hour, preferably 4-8 hours in DEG C baking oven.Upper strata solvent is removed, TiO is obtained2Alkane gel (12).Alkyl solvents
(11) it is less than 25N/m alkane, such as hexamethylene, normal heptane, n-hexane for surface tension.
(4) constant pressure and dry
The TiO that step (3) is obtained2Alkane gel (12) is placed under 60-200 DEG C of condition of normal pressure and dried 0.5-24 hours, obtains
To TiO2Aeroge (13).
(5) high-temperature calcination
The TiO that step (4) is obtained2Aeroge (13) is placed in 300-800 DEG C of Muffle kiln roasting 0.5-24 hours, obtains
To final product --- the TiO with nanometer sheet and nanoporous pattern2Aeroge (14).
The present invention's is mainly characterized by, and TiO is prepared using Gao Shui-titanium mol ratio2Gel and aeroge, large quantity of moisture are deposited
The aquation of organic titanium source and gelling process can be greatly facilitated, gelling was realized so as to (more than ten seconds) in very short time, so that
Significantly improve production efficiency.
The features of the present invention is also resided in, and the ageing process that amino agents regulate and control titanium oxide wet gel is added in presoma,
The acid that the distinctive alkalescence of amino agents will be neutralized in presoma, it is to avoid inevitable peptization shows in conventional sol gel process
As so as to smoothly obtain the TiO with some strength2Wet gel.
The features of the present invention is also resided in, and the amino agents added in precursor solution can release NH2Group, can be directed to
It is adsorbed in TiO2Nanocrystalline high energy crystal face.When in high-temperature roasting stage, NH2Group is removed, and will promote TiO2Nanocrystal from
Assembling, so as to form flaky nanometer structure.
The features of the present invention is also resided in, the TiO prepared using above-mentioned technique2Aeroge is only by size under nanoscale
5-30nm TiO2Crystal grain is constituted, under micron, submicron-scale, while having two kinds of shapes of nanometer sheet and nanoporous aggregation
Looks, its pattern feature participates in accompanying drawing 1.Accompanying drawing 2-4 gives the X-ray according to titania aerogel powder made from embodiment 1
Diffracting spectrum and transmission electron microscope photo.As can be seen that before not thermally treated, titania aerogel powder has had good
Crystallinity, but in the single porous pattern of nanoscale presentation；After high-temperature roasting, the crystallinity of titania aerogel powder is obtained
Increase substantially, two kinds of patterns are showed on nanoscale：Fine and close nano flake and porous nanocrystal aggregates.
The features of the present invention is also resided in, and gained titania aerogel powder has higher specific surface area, according to embodiment 1
The powder BET specific surface area of preparation is up to 170m2/ g, far above conventional Ti O2Nano-powder (such as goldschmidt chemical corporation P25 types TiO2
Powder specific-surface area detection is 55m2/ g), so as to increase considerably the load capacity of electrode pair dyestuff and in various catalytic reactions
Activity and catalytic efficiency.
Fig. 1 is the titanium oxide airsetting with nanometer sheet and nano-porous structure prepared in an embodiment of the invention
Rubber powder body microstructure schematic diagram, wherein 1-TiO2Nano-particle, 2-TiO2Nanometer sheet, 3-TiO2Nano-porous structure；
Fig. 2 is the X ray diffracting spectrum of the titania aerogel powder prepared in an embodiment of the invention；
The transmission electron microscope of titania aerogel powders of the Fig. 3 to be prepared in an embodiment of the invention shines
White dashed line marks region for nanometer sheet in piece, figure；
Fig. 4 is the transmission of the titania aerogel powder without high-temperature roasting prepared in an embodiment of the invention
Electron micrograph.
Some exemplary embodiments are included further below the present invention is better described.It should be understood that the present invention is in detail
The above-mentioned embodiment stated, and following examples are only illustrative of the invention and is not intended to limit the scope of the invention, this area
Technical staff the protection of the present invention is belonged to according to some nonessential modifications and adaptations for making of the above of the present invention
Scope.In addition, specific proportioning, time, temperature in following technological parameters etc. is also only exemplary, those skilled in the art can be with
Suitable value is selected in the range of above-mentioned restriction.
Embodiment 1：
(1) using butyl titanate as titanium source, ethanol is alcoholic solvent, and hexa is amino agents, and hexamethylene is alkane
Based solvent.5ml butyl titanates are mixed with 5ml ethanol, a small amount of hydrochloric acid is added dropwise and adjusts pH value to 1.0, stirs at room temperature
20min, obtains A liquid；3ml ethanol, 5ml water, 0.2g hexas are mixed, dropwise addition hydrochloric acid adjustment pH value to 5.0, at room temperature
20min is stirred, B liquid is obtained；With vigorous stirring, A liquid, B liquid are mixed rapidly, stands 1min, obtain TiO2Gel；
(2) by TiO2Gel is placed in beaker, is sealed with preservative film, aging 4 hours in 60 DEG C of baking ovens, obtains aging TiO2
Gel；
(3) with glass bar by aging TiO2Gel is smashed to pieces, fragment maximum particle diameter is less than 5mm.Mixed with the ethanol of 4 times of volumes
Close, be placed in beaker, sealed with preservative film, exchange of solvent 6h is carried out in 60 DEG C of baking ovens, filtering obtains TiO2Alcogel；Will
TiO2Alcogel is mixed with the hexamethylene of 4 times of volumes, is placed in beaker, is sealed with preservative film, and solvent is carried out in 60 DEG C of baking ovens
6h is exchanged, filtering obtains TiO2Alkane gel；
(4) by TiO2Alkane gel is placed in opening beaker, and constant pressure and dry 8h, obtains TiO in 60 DEG C of baking ovens2Aeroge；
(5) by TiO2Aeroge is placed in 500 DEG C of Muffle kiln roastings 2 hours, obtains while having nanometer sheet and nanoporous
The TiO of pattern2Aeroge.The BET specific surface area of obtained titania aerogel is 170m2/ g, the thickness of nanometer sheet is 20nm,
The average pore size of nano-pore is 12nm, and the porosity of aeroge is 90%, and density is 0.7g/cm3。
The TiO prepared using above-mentioned technique2Aeroge is under nanoscale only by TiO of the size for 5-30nm2Crystal grain structure
Into, under micron, submicron-scale, while have two kinds of patterns of nanometer sheet and nanoporous aggregation, its pattern feature referring to
Accompanying drawing 1.Accompanying drawing 2-4 gives the X ray diffracting spectrum and transmitted electron according to titania aerogel powder made from embodiment 1
Microphotograph.As can be seen that before not thermally treated, titania aerogel powder has good crystallinity, but in nanometer chi
Single porous pattern is presented in degree；After high-temperature roasting, the crystallinity of titania aerogel powder is greatly improved, in nanometer
Two kinds of patterns are showed on yardstick：Fine and close nano flake and porous nanocrystal aggregates.
Embodiment 2：
(1) using isopropyl titanate as titanium source, ethanol is alcoholic solvent, and hexa is amino agents, and hexamethylene is alkane
Based solvent.2ml isopropyl titanates are mixed with 2ml ethanol, a small amount of hydrochloric acid is added dropwise and adjusts pH value to 2.0, stirs at room temperature
20min, obtains A liquid；2ml ethanol, 3ml water, 0.15g hexas are mixed, hydrochloric acid is added dropwise and adjusts pH value to 4.0, room temperature
Lower stirring 20min, obtains B liquid；With vigorous stirring, A liquid, B liquid are mixed rapidly, stands 5min, obtain TiO2Gel；
(2) by TiO2Gel is placed in small beaker, is sealed with preservative film, and aging 8 hours, obtain aging in 65 DEG C of baking ovens
TiO2Gel；
(3) with glass bar by aging TiO2Gel is smashed to pieces, fragment maximum particle diameter is less than 5mm.Mixed with the ethanol of 4 times of volumes
Close, be placed in small beaker, sealed with preservative film, exchange of solvent 4h is carried out in 60 DEG C of baking ovens, filtering obtains TiO2Alcogel；
By TiO2Alcogel is mixed with the hexamethylene of 4 times of volumes, is placed in small beaker, is sealed with preservative film, is carried out in 60 DEG C of baking ovens
Exchange of solvent 4h, filtering, obtains TiO2Alkane gel；
(4) by TiO2Alkane gel is placed in opening small beaker, and constant pressure and dry 24h, obtains TiO in 80 DEG C of baking ovens2Aeroge；
(5) by TiO2Aeroge is placed in 500 DEG C of Muffle kiln roastings 6 hours, obtains while having nanometer sheet and nanoporous
The TiO of pattern2Aeroge；
The BET specific surface area of obtained titania aerogel is 100m2/ g, the thickness of nanometer sheet is 5nm, nano-pore it is flat
Equal aperture is 25nm, and the porosity of aeroge is 85%, and density is 0.8g/cm3。
Embodiment 3：
(1) using butyl titanate as titanium source, isopropanol is alcoholic solvent, and urea is amino agents, and hexamethylene is alkyl solvents.
5ml butyl titanates are mixed with 5ml isopropanols, a small amount of hydrochloric acid is added dropwise and adjusts pH value to 3.0,20min is stirred at room temperature, A is obtained
Liquid；5ml isopropanols, 10ml water, 1g urea are mixed, hydrochloric acid is added dropwise and adjusts pH value to 4.0,20min is stirred at room temperature, B is obtained
Liquid；With vigorous stirring, A liquid, B liquid are mixed rapidly, stands 20min, obtain TiO2Gel；
(2) by TiO2Gel is placed in small beaker, is sealed with preservative film, and aging 4 hours, obtain aging in 65 DEG C of baking ovens
TiO2Gel；
(3) with glass bar by aging TiO2Gel is smashed to pieces, fragment maximum particle diameter is less than 5mm.Mixed with the ethanol of 4 times of volumes
Close, be placed in small beaker, sealed with preservative film, exchange of solvent 12h is carried out in 70 DEG C of baking ovens, filtering obtains TiO2Alcogel；
By TiO2Alcogel is mixed with the hexamethylene of 4 times of volumes, is placed in small beaker, is sealed with preservative film, is carried out in 60 DEG C of baking ovens
Exchange of solvent 12h, filtering, obtains TiO2Alkane gel；
(4) by TiO2Alkane gel is placed in opening small beaker, and constant pressure and dry 24h, obtains TiO in 90 DEG C of baking ovens2Aeroge；
(5) by TiO2Aeroge is placed in 500 DEG C of Muffle kiln roastings 6 hours, obtains while having nanometer sheet and nanoporous
The TiO of pattern2Aeroge；
The BET specific surface area of obtained titania aerogel is 80m2/ g, the thickness of nanometer sheet is 30nm, nano-pore it is flat
Equal aperture is 38nm, and the porosity of aeroge is 83%, and density is 0.9g/cm3。
Embodiment 4：
(1) using butyl titanate as titanium source, isopropanol is alcoholic solvent, and ethylenediamine is amino agents, and normal heptane is that alkyl is molten
Agent.4ml butyl titanates are mixed with 4ml isopropanols, a small amount of hydrochloric acid is added dropwise and adjusts pH value to 2.5,20min is stirred at room temperature,
Obtain A liquid；3ml isopropanols, 5ml water, 2g ethylenediamines are mixed, hydrochloric acid is added dropwise and adjusts pH value to 5.0,20min is stirred at room temperature, is obtained
To B liquid；With vigorous stirring, A liquid, B liquid are mixed rapidly, stands 30min, obtain TiO2Gel；
(2) by TiO2Gel is placed in small beaker, is sealed with preservative film, and aging 48 hours, obtain aging in 65 DEG C of baking ovens
TiO2Gel；
(3) with glass bar by aging TiO2Gel is smashed to pieces, fragment maximum particle diameter is less than 5mm.Mixed with the ethanol of 4 times of volumes
Close, be placed in small beaker, sealed with preservative film, exchange of solvent 24h is carried out in 60 DEG C of baking ovens, filtering obtains TiO2Alcogel；
By TiO2Alcogel is mixed with the hexamethylene of 4 times of volumes, is placed in small beaker, is sealed with preservative film, is carried out in 60 DEG C of baking ovens
Exchange of solvent 24h, filtering, obtains TiO2Alkane gel；
(4) by TiO2Alkane gel is placed in opening small beaker, and constant pressure and dry 4h, obtains TiO in 110 DEG C of baking ovens2Aeroge；
(5) by TiO2Aeroge is placed in 650 DEG C of Muffle kiln roastings 2 hours, obtains while having nanometer sheet and nanoporous
The TiO of pattern2Aeroge；
The BET specific surface area of obtained titania aerogel is 150m2/ g, the thickness of nanometer sheet is 20nm, nano-pore
Aperture is 18nm, and the porosity of aeroge is 92%, and density is 0.6g/cm3。
Claims (15)
1. a kind of titania aerogel, it is characterised in that the titania aerogel has nanometer sheet and nano-porous structure, institute
The BET specific surface area for stating titania aerogel is 50-300 m2/ g, the titania aerogel is prepared by following methods：
1）Organic titanium source, alcohol are mixed and A liquid is obtained with acid for adjusting pH to 1~5；
2）Alcohol, water, amino agents are mixed and B liquid are obtained with acid for adjusting pH to 1~5；
3）By step 1）The A liquid and step 2 of preparation）The B liquid mixing of preparation, stirring to sediment is stood after disappearing, and obtains dioxy
Change titanium gel；
4）By step 3）The titania gel aging of middle preparation；
5）By step 4）After the titania gel through aging prepared is crushed, aging after being mixed with alcohol obtains titanium dioxide alcohol
Gel；
6）By step 5）The titanium dioxide alcogel of preparation, aging obtains titanium dioxide alkane gel after being mixed with alkane solvent；With
And
7）By step 6）After obtained titanium dioxide alkane gel drying, calcining is produced with nanometer sheet and nanoporous pattern
Titania aerogel.
2. titania aerogel according to claim 1, it is characterised in that in the titania aerogel, nanometer sheet
Thickness be 3-50nm, the aperture of nano-pore is 1-100nm, and the porosity of aeroge is 50-98%.
3. titania aerogel according to claim 1 or 2, it is characterised in that the density of the titania aerogel is
0.3—1.5 g/cm3。
4. a kind of method for preparing any titania aerogel in claim 1-3, it is characterised in that methods described bag
Include：
1）Organic titanium source, alcohol are mixed and A liquid is obtained with acid for adjusting pH to 1~5；
2）Alcohol, water, amino agents are mixed and B liquid are obtained with acid for adjusting pH to 1~5；
3）By step 1）The A liquid and step 2 of preparation）The B liquid mixing of preparation, stirring to sediment is stood after disappearing, and obtains dioxy
Change titanium gel；
4）By step 3）The titania gel aging of middle preparation；
5）By step 4）After the titania gel through aging prepared is crushed, aging after being mixed with alcohol obtains titanium dioxide alcohol
Gel；
6）By step 5）The titanium dioxide alcogel of preparation, aging obtains titanium dioxide alkane gel after being mixed with alkane solvent；With
And
7）By step 6）After obtained titanium dioxide alkane gel drying, calcining is produced with nanometer sheet and nanoporous pattern
Titania aerogel.
5. method according to claim 4, it is characterised in that step 1）In, the organic titanium source contains at least one O-
Ti keys.
6. method according to claim 5, it is characterised in that step 1）In, organic titanium source is butyl titanate, metatitanic acid four
Ethyl ester or isopropyl titanate.
7. method according to claim 4, it is characterised in that step 1）In, the volume ratio of organic titanium source and alcohol is 1:（1-
5）.
8. method according to claim 4, it is characterised in that step 2）In, amino agents are ammoniacal liquor or contain at least one
It is individual to be selected from-NH2With the compound of-NH group.
9. method according to claim 8, it is characterised in that step 2）In, amino agents are urea, hexa-methylene four
Amine, ethylenediamine or triethanolamine.
10. method according to claim 4, it is characterised in that step 3）In, titanium source in titania gel, water, alcohol,
The mol ratio of amino agents is 1：（10-100）：（8-20）：（0.1-5）.
11. method according to claim 4, it is characterised in that step 4）In, aging 1-72 hours at 50-99 DEG C.
12. method according to claim 4, it is characterised in that step 6）In, titanium dioxide alcogel is it with volume
1-10 times of alkane solvent mixing, obtains titanium dioxide alkane gel in aging 1-72 hours at 50-78 DEG C, wherein, alkane solvent
It is less than 25N/m alkane for surface tension.
13. method according to claim 12, it is characterised in that the alkane solvent be hexamethylene, normal heptane or just oneself
Alkane.
14. method according to claim 4, it is characterised in that step 7）In, the parameter of drying process is：Drying temperature
For 60-200 DEG C, drying time is 0.5-24 hours.
15. according to any described method in claim 4-14, it is characterised in that step 7）In, the technological parameter of calcining is：
Calcining heat is 300-800 DEG C, and calcination time is 0.5-24 hours.
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