CN105217676A - There is titania aerogel of nanometer sheet and nano-porous structure and preparation method thereof - Google Patents
There is titania aerogel of nanometer sheet and nano-porous structure and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to and a kind ofly have titania aerogel of nanometer sheet and nano-porous structure and preparation method thereof, described titania aerogel has nanometer sheet and nano-porous structure, and the BET specific surface area of described titania aerogel is 50-300m
2/ g.
Description
Technical field
The invention belongs to new chemical materials field, be specifically related to a kind of to there is titania aerogel of nanometer sheet and nano-porous structure and preparation method thereof.
Background technology
Aerogel is current the lightest known solid in the world, and its porosity can up to 99.8%, and bore hole size is at 1 ~ 100nm, and specific surface area can up to 1000m
2/ g, volume density can at 3 ~ 500kg/m
3between change, be a kind of hi-tech, environmental protection, efficiently energy-saving and heat-insulating material, minimumly under its thermal conductivity normal temperature and pressure reach 0.015W/ (mK)), be the one that thermal conductivity is minimum in known solid-state material at present.Due to unique texture and the performance of aerogel, this material is expected there is huge application prospect in field widely at Aeronautics and Astronautics, industrial energy saving, building energy conservation and sound insulation, damping, explosion-proof, environmental protection, energy storage etc.On August 19th, 2007, London Sunday Times of Britain publishes an article title, " aerogel will be the material changing the world ".
Titanium dioxide (TiO
2) be a kind of broad-band gap oxide semiconductor material, usually anatase octahedrite and rutile two kinds of crystal formations are had, not only as titanium dioxide and matting agent, a large amount of application is had in fields such as paint, enamel, and as semi-conductor and photocatalyst material, be all widely used in fields such as indoor air purification, waste water treatment, PM2.5 improvement, makeup, solar cells.
Titania aerogel is the nano-porous materials of a kind of low density, high porosity, high-specific surface area, the pore structure of its uniqueness and semiconductor light is electroactive makes it have wide practical use in fields such as catalysis, support of the catalyst, electrode, absorption, heat insulatings.As, in electrode, titania aerogel can be used as the light anode of dye sensitization solar battery, due to its high-specific surface area, can the more dyestuff of load, thus improve photo-excited electron density and battery efficiency; In catalysis, titania aerogel can be widely used in photocatalytic air, water extraction is pure and other are based on the field such as photochemical catalytic oxidation and organic pollutant degradation.
The preparation of titania aerogel generally adopts collosol and gel in conjunction with supercritical drying process preparation, and complex process, danger is comparatively large, and cost is high.But it is very difficult to adopt constant pressure and dry technique to prepare pure titania aerogel, due to all factors such as Titanium alkoxides activity are high, Titanium alkoxides gelatinization process is complicated, adopt constant pressure and dry method to be difficult to acquisition and there is good microtexture and more low-density titania aerogel material.Preparation both at home and abroad about titania aerogel has some reports.Chinese patent 200610024301.3 discloses a kind of preparation method that can be used for the titania aerogel of photocatalyst material, non-Titanium alkoxides and water-containing solvent is adopted to be made into presoma, mix with epoxide again, the block alcogel of titanium oxide can be obtained being as short as in several minutes, and through aging, the means such as supercritical drying, calcination process obtain titania aerogel powder or block.Chinese patent 201310012851.3 discloses and a kind ofly in precursor solution, adds tensio-active agent, sequestrant and drying control agent to prepare the method for titania aerogel simultaneously.Chinese patent 201310459800.5 discloses a kind of aniline-acetone in-situ preparation water law control sol-gel process and prepares titanium oxide gel, again by aging, solvent replacing and supercritical drying process, obtain the method for high-specific surface area, block titania aerogel that controllability is good.Chinese patent 201310755307.8 prepares the method for hydrophobic titania aerogel under disclosing a kind of normal pressure, be characterized in, after titanium oxide gel carries out exchange of solvent, in the cyclohexane solvent of hexamethyldisilazane, carry out hydrophobically modified again, thus Hydrophobic silica aerogel can be obtained after drying box cooling.
Although the preparation technology about titania aerogel has large quantity research, people also cannot realize the multilevel hierarchy aerogel simultaneously obtaining different morphologies in same titania aerogel at present.No matter such multistage material aerogel is all significantly increased than conventional oxidation titanium aerogel in specific surface area and Electronic Transport of Two Benzene etc., thus can be used widely in fields such as dye sensitization solar battery, lithium ion battery electrode material, photochemical catalysis.Therefore, the new technology of such material of exploitation preparation has important scientific meaning and wide market outlook.
Summary of the invention
The present invention is intended to fill up the blank that prior art cannot realize obtaining different morphologies in same titania aerogel simultaneously, the invention provides a kind ofly to have titania aerogel of nanometer sheet and nano-porous structure and preparation method thereof.
The invention provides a kind of titania aerogel, described titania aerogel has nanometer sheet and nano-porous structure, and the BET specific surface area of described titania aerogel is 50-300m
2/ g.
Preferably, in described titania aerogel, the thickness of nanometer sheet is 3-50nm, and the aperture of nanoporous is 1-100nm, and the porosity of aerogel is 50-98%.
Preferably, the density of described titania aerogel is 0.3-1.5g/cm
3.
Present invention also offers a kind of method preparing above-mentioned titania aerogel, described method comprises:
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 obtain B liquid with acid for adjusting pH to 1 ~ 5;
3) by step 1) the A liquid prepared and step 2) the B liquid mixing prepared, be stirred to after throw out disappears and leave standstill, obtain titania gel;
4) by step 3) in preparation titania gel under aging;
5) by step 4) prepare after aging titania gel fragmentation, mix with alcohol after aging, obtain titanium dioxide alcogel;
6) by step 5) the titanium dioxide alcogel prepared, agingly after mixing with alkane solvent obtain titanium dioxide alkane gel; And
7) by step 6) after obtained titanium dioxide alkane gel drying, calcining, must have the titania aerogel of nanometer sheet and nanoporous pattern.
Preferably, step 1) in, at least one O-Ti key is contained in described organic titanium source, the preferred tetrabutyl titanate in organic titanium source, tetraethyl titanate, isopropyl titanate.
Preferably, step 1) in, the volume ratio of organic titanium source and alcohol is 1:(1-5).
Preferably, step 1) and step 2) in, acid is hydrochloric acid, acetic acid, sulfuric acid or nitric acid; Alcohol is the low-boiling point alcohol containing a hydroxy functional group, particular methanol, ethanol, propyl alcohol, Virahol.
Preferably, step 2) in, amino agents is for being selected from-NH containing at least one
3,-NH
2with the compound of the group of-NH, preferred urea, vulkacit H, ammoniacal liquor, quadrol, trolamine.
Preferably, step 3) in, in TiO 2 sol, the mol ratio of titanium source, water, alcohol, amino agents is 1:(10-100): (8-20): (0.1-5).
Preferably, step 4) in, aging 1-72 hour at 50-99 DEG C, preferred 4-8 hour.
Preferably, step 5) in, by step 4) overall dimension smashed to pieces to fragment of the aging TiO 2 sol prepared is less than 5mm, the alcohol being its 1-10 times with volume mixes, aging 1-72 hour at 50-78 DEG C, obtain titanium dioxide alcosol, wherein, alcohol preferred alcohol, methyl alcohol, Virahol.
Preferably, step 6) in, titanium dioxide alcosol, the alkyl solvents being its 1-10 times with volume mixes, and at 50-78 DEG C, aging 1-72 hour obtains titanium dioxide alkane gel, wherein, alkyl solvents preferred surface tension force is lower than the alkane of 25N/m, particularly preferably hexanaphthene, normal heptane, normal hexane.
Preferably, step 7) in, the parameter of drying process is: drying temperature is 60-200 DEG C, and time of drying is 0.5-24 hour; The processing parameter of high-temperature calcination is: calcining temperature is 300-800 DEG C, and calcination time is 0.5-24 hour.
Beneficial effect of the present invention:
Principal feature of the present invention is, adopts Gao Shui-titanium mol ratio to prepare TiO
2gel and aerogel, the existence of large quantity of moisture greatly can promote aquation and the gelling process in organic titanium source, thus in very short time, (tens seconds) can realize gelling, thus significantly improves production efficiency;
Feature of the present invention is also, the weathering process of amino agents regulation and control titanium oxide wet gel is added in presoma, the distinctive alkalescence of amino agents by and acid in presoma, avoid inevitable peptization phenomenon in conventional sol gel process, thus smoothly acquisition has the TiO of some strength
2wet gel;
Feature of the present invention is also, the amino agents added in precursor solution can discharge NH
2group, is orientablely adsorbed in TiO
2nanocrystalline high energy crystal face.When in the high-temperature roasting stage, NH
2group removes, and will promote TiO
2the self-assembly of nanocrystal, thus form flaky nanometer structure;
Feature of the present invention is also, adopts TiO prepared by above-mentioned technique
2aerogel under nanoscale only by the TiO being of a size of 5-30nm
2crystal grain is formed, and under micron, submicron-scale, has nanometer sheet and nanoporous aggregate two kinds of patterns simultaneously.Before thermal treatment, titania aerogel powder has good crystallinity, but presents single porous pattern at nanoscale; After high-temperature roasting, the crystallinity of titania aerogel powder is greatly improved, and nanoscale presents two kinds of patterns: fine and close nano flake and the nanocrystal aggregates of porous;
Feature of the present invention is also, gained titania aerogel powder has higher specific surface area, and the powder BET specific surface area of preparation is up to 170m
2/ g, far above conventional Ti O
2nano-powder is (as goldschmidt chemical corporation P25 type TiO
2powder specific-surface area detection is 55m
2/ g), thus the charge capacity of electrode pair dyestuff and the activity in various catalyzed reaction and catalytic efficiency can be increased considerably.
Accompanying drawing explanation
Fig. 1 is the titania aerogel powder microtexture schematic diagram with nanometer sheet and nano-porous structure prepared in an embodiment of the invention, wherein 1-TiO
2nanoparticle, 2-TiO
2nanometer sheet, 3-TiO
2nano-porous structure;
Fig. 2 is the X ray diffracting spectrum of the titania aerogel powder prepared in an embodiment of the invention;
Fig. 3 is the transmission electron microscope photo of the titania aerogel powder prepared in an embodiment of the invention, and in figure, white dashed line marks region is nanometer sheet;
Fig. 4 is the transmission electron microscope photo of the titania aerogel powder without high-temperature roasting prepared in an embodiment of the invention.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The invention discloses a kind of titania aerogel powder and the technology of preparing thereof with nanometer sheet and nano-porous structure.The object of the invention is: by introducing " amino agents " in precursor solution, regulate and control the gelling of titanium oxide sol, weathering process and high temperature sintering behavior, and in conjunction with means such as exchange of solvent, constant pressure and dry, high-temperature roastings, there is under being prepared in micro/nano-scale the multilevel hierarchy titania aerogel powder of nanometer sheet and nanoporous pattern simultaneously.The technical characterstic that the present invention prepares titania aerogel powder is: prevent titanium oxide gel distinctive in weathering process " peptization " phenomenon by adding amino agents in presoma, improves aerogel frame strength and crystallization property; By-NH under high temperature
2the burn off of group brings out TiO
2nanocrystal self-assembly, obtains the multilevel hierarchy titania aerogel powder that nanometer sheet and nanoporous pattern coexist.Preparation process can briefly comprise: (1) TiO
2colloidal sol and gel preparation: be the titanium source of 1:10-100:8-20:0.2-0.6 by mol ratio, water, alcoholic solvent, amino agents be prepared into A liquid and B liquid respectively, and with vigorous stirring the two is mixed, leave standstill 10 seconds to 60 minutes, obtain TiO
2gel; (2) aging: gained TiO
2gel is aging 1-72 hour under 50-99 DEG C of condition; (3) exchange of solvent: use ethanol and lower boiling alkyl solvents to TiO respectively
2gel carries out exchange of solvent; (4) constant pressure and dry: 60-200 DEG C, dry 0.5-24 hour under condition of normal pressure; (5) high-temperature roasting: roasting 0.5-24 hour in 300-800 DEG C of retort furnace.Nanometer sheet in gained aerogel powder can give material good electroconductibility, nano-porous structure can give material high specific surface area, thus in the application of some simultaneously special occasions of demand high-specific surface area and high conductivity, as the field such as light anode, lithium ion cell electrode, photochemical catalysis, photocatalytic water of dye sensitization solar battery.
Technical solution of the present invention is:
The alcoholic solution adopting organic titanium salt is presoma, by sol-gel process in conjunction with techniques such as solvent exchange, constant pressure and dry, high-temperature roastings, prepares titania aerogel.In organic titanium salt presoma, introduce amino agents, utilize it to add Thermal release OH
-characteristic prevents titanium oxide gel peptization in weathering process, and improves aerogel crystallinity; Amino agents is utilized in high-temperature calcination process, to discharge oriented adsorption in the-NH of titanium oxide high energy crystal face
2group, the self-assembly of accelerating oxidation nanocrystalline Ti grain, obtains titanium oxide sheet structure.And not by-NH
2there is not self-assembly in the coated nanocrystal of group, forms nanoporous pattern after baking.By controlling the add-on of amino agents, the content of nanometer sheet in aerogel powder can be adjusted.By such scheme, the titania aerogel powder simultaneously with nanometer sheet and nanoporous pattern can be obtained.
Concrete steps of the present invention are:
(1) TiO
2colloidal sol and gel preparation
The organic compound selecting metal titanium is titanium source (1), prepares TiO with water, alcoholic solvent (2), hydrochloric acid (3), amino agents (4) compound
2colloidal sol (5).Concrete point following three steps:
A) alcoholic solvent (2) of organic titanium source (1) and equal-volume ratio, appropriate hydrochloric acid are mixed, adjusted to ph is to 1-5 scope, and stirred at ambient temperature 5-120 minute, obtains A liquid (6);
B) will remain the mixing of alcoholic solvent (2), water, appropriate hydrochloric acid (3) and amino agents (4), adjusted to ph is to 1-5 scope, and stirred at ambient temperature 5-60 minute, obtains 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 obtained TiO to 60 minutes in 10 seconds
2gel (8);
In presoma system, the mol ratio of titanium source, water, alcoholic solvent, amino agents is 1:10-100:8-20:0.2-0.6.Titanium source is the compound containing one or more " O-Ti " key in molecule, as tetrabutyl titanate, tetraethyl titanate, isopropyl titanate etc.; Alcoholic solvent is the low boiling point solvent containing " OH " functional group in molecule, as methyl alcohol, ethanol, propyl alcohol, Virahol etc.; Amino agents is containing one or more-NH in molecule
3, NH
2, NH group inorganic or organic compound, as urea, vulkacit H, ammoniacal liquor, quadrol, trolamine etc.
(2) aging
By the TiO that step () obtains
2gel (8) is placed in encloses container, in 50-99 DEG C of baking oven aging 1 to 72 hour, and preferred 4-8 hour, obtains aging TiO
2gel (9).
(3) solvent exchange
By the aging TiO that step (two) obtains
2gel (9) is smashed to pieces, and fragment overall dimension is less than 5mm, mixes, be placed in encloses container with the ethanol of 1-10 times of volume, in 50-78 DEG C of baking oven aging 1 to 72 hour, preferred 4-8 hour.Remove upper strata solvent, obtain TiO
2alcogel (10);
By TiO
2alcogel (10) mixes with the alkyl solvents (11) of 1-10 times of volume, is placed in encloses container, in 50-78 DEG C of baking oven aging 1 to 72 hour, preferred 4-8 hour.Remove upper strata solvent, obtain TiO
2alkane gel (12).Alkyl solvents (11) for surface tension is lower than the alkane of 25N/m, as hexanaphthene, normal heptane, normal hexane etc.
(4) constant pressure and dry
By the TiO that step (three) obtains
2alkane gel (12) dries 0.5-24 hour under being placed in 60-200 DEG C of condition of normal pressure, obtains TiO
2aerogel (13).
(5) high-temperature calcination
By the TiO that step (four) obtains
2aerogel (13) is placed in 300-800 DEG C of retort furnace roasting 0.5-24 hour, obtains final product---there is the TiO of nanometer sheet and nanoporous pattern
2aerogel (14).
Principal feature of the present invention is, adopts Gao Shui-titanium mol ratio to prepare TiO
2gel and aerogel, the existence of large quantity of moisture greatly can promote aquation and the gelling process in organic titanium source, thus in very short time, (tens seconds) can realize gelling, thus significantly improves production efficiency.
Feature of the present invention is also, the weathering process of amino agents regulation and control titanium oxide wet gel is added in presoma, the distinctive alkalescence of amino agents by and acid in presoma, avoid inevitable peptization phenomenon in conventional sol gel process, thus smoothly acquisition has the TiO of some strength
2wet gel.
Feature of the present invention is also, the amino agents added in precursor solution can discharge NH
2group, is orientablely adsorbed in TiO
2nanocrystalline high energy crystal face.When in the high-temperature roasting stage, NH
2group removes, and will promote TiO
2the self-assembly of nanocrystal, thus form flaky nanometer structure.
Feature of the present invention is also, adopts TiO prepared by above-mentioned technique
2aerogel under nanoscale only by the TiO being of a size of 5-30nm
2crystal grain is formed, and under micron, submicron-scale, has nanometer sheet and nanoporous aggregate two kinds of patterns simultaneously, and its pattern feature participates in accompanying drawing 1.Accompanying drawing 2-4 gives X ray diffracting spectrum and the transmission electron microscope photo of the titania aerogel powder obtained according to embodiment 1.Can find out, before thermal treatment, titania aerogel powder has good crystallinity, but presents single porous pattern at nanoscale; After high-temperature roasting, the crystallinity of titania aerogel powder is greatly improved, and nanoscale presents two kinds of patterns: fine and close nano flake and the nanocrystal aggregates of porous.
Feature of the present invention is also, gained titania aerogel powder has higher specific surface area, and the powder BET specific surface area prepared according to embodiment 1 is up to 170m
2/ g, far above conventional Ti O
2nano-powder is (as goldschmidt chemical corporation P25 type TiO
2powder specific-surface area detection is 55m
2/ g), thus the charge capacity of electrode pair dyestuff and the activity in various catalyzed reaction and catalytic efficiency can be increased considerably.
Fig. 1 is the titania aerogel powder microtexture schematic diagram with nanometer sheet and nano-porous structure prepared in an embodiment of the invention, wherein 1-TiO
2nanoparticle, 2-TiO
2nanometer sheet, 3-TiO
2nano-porous structure;
Fig. 2 is the X ray diffracting spectrum of the titania aerogel powder prepared in an embodiment of the invention;
Fig. 3 is the transmission electron microscope photo of the titania aerogel powder prepared in an embodiment of the invention, and in figure, white dashed line marks region is nanometer sheet;
Fig. 4 is the transmission electron microscope photo of the titania aerogel powder without high-temperature roasting prepared in an embodiment of the invention.
Below some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following processing parameter are also only exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1:
(1) take tetrabutyl titanate as titanium source, ethanol is alcoholic solvent, and vulkacit H is amino agents, and hexanaphthene is alkyl solvents.5ml tetrabutyl titanate is mixed with 5ml ethanol, drips a small amount of hydrochloric acid adjusted to ph to 1.0, stirred at ambient temperature 20min, obtain A liquid; By 3ml ethanol, 5ml water, the mixing of 0.2g vulkacit H, drip hydrochloric acid adjusted to ph to 5.0, stirred at ambient temperature 20min, obtains B liquid; With vigorous stirring, A liquid, B liquid are mixed rapidly, leave standstill 1min, obtain TiO
2gel;
(2) by TiO
2gel is placed in beaker, with preservative film sealing, in 60 DEG C of baking ovens aging 4 hours, obtains aging TiO
2gel;
(3) with glass stick by aging TiO
2gel is smashed to pieces, makes fragment maximum particle diameter be less than 5mm.Mix with the ethanol of 4 times of volumes, be placed in beaker, with preservative film sealing, in 60 DEG C of baking ovens, carry out exchange of solvent 6h, filter, obtain TiO
2alcogel; By TiO
2alcogel mixes with the hexanaphthene of 4 times of volumes, is placed in beaker, with preservative film sealing, in 60 DEG C of baking ovens, carries out exchange of solvent 6h, filters, obtain TiO
2alkane gel;
(4) by TiO
2alkane gel is placed in opening beaker, and in 60 DEG C of baking ovens, constant pressure and dry 8h, obtains TiO
2aerogel;
(5) by TiO
2aerogel is placed in 500 DEG C of retort furnace roastings 2 hours, obtains the TiO simultaneously with nanometer sheet and nanoporous pattern
2aerogel.The BET specific surface area of obtained titania aerogel is 170m
2/ g, the thickness of nanometer sheet is 20nm, and the mean pore size of nanoporous is 12nm, and the porosity of aerogel is 90%, and density is 0.7g/cm
3.
Adopt TiO prepared by above-mentioned technique
2aerogel under nanoscale only by the TiO being of a size of 5-30nm
2crystal grain is formed, and under micron, submicron-scale, have nanometer sheet and nanoporous aggregate two kinds of patterns, its pattern feature is see accompanying drawing 1 simultaneously.Accompanying drawing 2-4 gives X ray diffracting spectrum and the transmission electron microscope photo of the titania aerogel powder obtained according to embodiment 1.Can find out, before thermal treatment, titania aerogel powder has good crystallinity, but presents single porous pattern at nanoscale; After high-temperature roasting, the crystallinity of titania aerogel powder is greatly improved, and nanoscale presents two kinds of patterns: fine and close nano flake and the nanocrystal aggregates of porous.
Embodiment 2:
(1) take isopropyl titanate as titanium source, ethanol is alcoholic solvent, and vulkacit H is amino agents, and hexanaphthene is alkyl solvents.2ml isopropyl titanate is mixed with 2ml ethanol, drips a small amount of hydrochloric acid adjusted to ph to 2.0, stirred at ambient temperature 20min, obtain A liquid; By 2ml ethanol, 3ml water, the mixing of 0.15g vulkacit H, drip hydrochloric acid adjusted to ph to 4.0, stirred at ambient temperature 20min, obtains B liquid; With vigorous stirring, A liquid, B liquid are mixed rapidly, leave standstill 5min, obtain TiO
2gel;
(2) by TiO
2gel is placed in small beaker, with preservative film sealing, in 65 DEG C of baking ovens aging 8 hours, obtains aging TiO
2gel;
(3) with glass stick by aging TiO
2gel is smashed to pieces, makes fragment maximum particle diameter be less than 5mm.Mix with the ethanol of 4 times of volumes, be placed in small beaker, with preservative film sealing, in 60 DEG C of baking ovens, carry out exchange of solvent 4h, filter, obtain TiO
2alcogel; By TiO
2alcogel mixes with the hexanaphthene of 4 times of volumes, is placed in small beaker, with preservative film sealing, in 60 DEG C of baking ovens, carries out exchange of solvent 4h, filters, obtain TiO
2alkane gel;
(4) by TiO
2alkane gel is placed in opening small beaker, and in 80 DEG C of baking ovens, constant pressure and dry 24h, obtains TiO
2aerogel;
(5) by TiO
2aerogel is placed in 500 DEG C of retort furnace roastings 6 hours, obtains the TiO simultaneously with nanometer sheet and nanoporous pattern
2aerogel;
The BET specific surface area of obtained titania aerogel is 100m
2/ g, the thickness of nanometer sheet is 5nm, and the mean pore size of nanoporous is 25nm, and the porosity of aerogel is 85%, and density is 0.8g/cm
3.
Embodiment 3:
(1) take tetrabutyl titanate as titanium source, Virahol is alcoholic solvent, and urea is amino agents, and hexanaphthene is alkyl solvents.5ml tetrabutyl titanate is mixed with 5ml Virahol, drips a small amount of hydrochloric acid adjusted to ph to 3.0, stirred at ambient temperature 20min, obtain A liquid; By 5ml Virahol, 10ml water, the mixing of 1g urea, drip hydrochloric acid adjusted to ph to 4.0, stirred at ambient temperature 20min, obtains B liquid; With vigorous stirring, A liquid, B liquid are mixed rapidly, leave standstill 20min, obtain TiO
2gel;
(2) by TiO
2gel is placed in small beaker, with preservative film sealing, in 65 DEG C of baking ovens aging 4 hours, obtains aging TiO
2gel;
(3) with glass stick by aging TiO
2gel is smashed to pieces, makes fragment maximum particle diameter be less than 5mm.Mix with the ethanol of 4 times of volumes, be placed in small beaker, with preservative film sealing, in 70 DEG C of baking ovens, carry out exchange of solvent 12h, filter, obtain TiO
2alcogel; By TiO
2alcogel mixes with the hexanaphthene of 4 times of volumes, is placed in small beaker, with preservative film sealing, in 60 DEG C of baking ovens, carries out exchange of solvent 12h, filters, obtain TiO
2alkane gel;
(4) by TiO
2alkane gel is placed in opening small beaker, and in 90 DEG C of baking ovens, constant pressure and dry 24h, obtains TiO
2aerogel;
(5) by TiO
2aerogel is placed in 500 DEG C of retort furnace roastings 6 hours, obtains the TiO simultaneously with nanometer sheet and nanoporous pattern
2aerogel;
The BET specific surface area of obtained titania aerogel is 80m
2/ g, the thickness of nanometer sheet is 30nm, and the mean pore size of nanoporous is 38nm, and the porosity of aerogel is 83%, and density is 0.9g/cm
3.
Embodiment 4:
(1) take tetrabutyl titanate as titanium source, Virahol is alcoholic solvent, and quadrol is amino agents, and normal heptane is alkyl solvents.4ml tetrabutyl titanate is mixed with 4ml Virahol, drips a small amount of hydrochloric acid adjusted to ph to 2.5, stirred at ambient temperature 20min, obtain A liquid; By 3ml Virahol, 5ml water, the mixing of 2g quadrol, drip hydrochloric acid adjusted to ph to 5.0, stirred at ambient temperature 20min, obtains B liquid; With vigorous stirring, A liquid, B liquid are mixed rapidly, leave standstill 30min, obtain TiO
2gel;
(2) by TiO
2gel is placed in small beaker, with preservative film sealing, in 65 DEG C of baking ovens aging 48 hours, obtains aging TiO
2gel;
(3) with glass stick by aging TiO
2gel is smashed to pieces, makes fragment maximum particle diameter be less than 5mm.Mix with the ethanol of 4 times of volumes, be placed in small beaker, with preservative film sealing, in 60 DEG C of baking ovens, carry out exchange of solvent 24h, filter, obtain TiO
2alcogel; By TiO
2alcogel mixes with the hexanaphthene of 4 times of volumes, is placed in small beaker, with preservative film sealing, in 60 DEG C of baking ovens, carries out exchange of solvent 24h, filters, obtain TiO
2alkane gel;
(4) by TiO
2alkane gel is placed in opening small beaker, and in 110 DEG C of baking ovens, constant pressure and dry 4h, obtains TiO
2aerogel;
(5) by TiO
2aerogel is placed in 650 DEG C of retort furnace roastings 2 hours, obtains the TiO simultaneously with nanometer sheet and nanoporous pattern
2aerogel;
The BET specific surface area of obtained titania aerogel is 150m
2/ g, the thickness of nanometer sheet is 20nm, and the aperture of nanoporous is 18nm, and the porosity of aerogel is 92%, and density is 0.6g/cm
3.
Claims (13)
1. a titania aerogel, is characterized in that, described titania aerogel has nanometer sheet and nano-porous structure, and the BET specific surface area of described titania aerogel is 50-300m
2/ g.
2. titania aerogel according to claim 1, is characterized in that, in described titania aerogel, the thickness of nanometer sheet is 3-50nm, and the aperture of nanoporous is 1-100nm, and the porosity of aerogel is 50-98%.
3. titania aerogel according to claim 1 and 2, is characterized in that, the density of described titania aerogel is 0.3-1.5g/cm
3.
4. prepare a method for arbitrary described titania aerogel in claim 1-3, it is characterized in that, described method comprises:
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 obtain B liquid with acid for adjusting pH to 1 ~ 5;
3) the A liquid prepared by step 1) and step 2) prepare B liquid mixing, be stirred to throw out disappear after leave standstill, obtain titania gel;
4) by aging under the titania gel prepared in step 3);
5) prepared by step 4) after aging titania gel fragmentation, mix with alcohol after aging, obtain titanium dioxide alcogel;
6) titanium dioxide alcogel step 5) prepared, aging obtains titanium dioxide alkane gel after mixing with alkane solvent; And
7) by after titanium dioxide alkane gel drying obtained for step 6), calcining, must have the titania aerogel of nanometer sheet and nanoporous pattern.
5. method according to claim 4, is characterized in that, in step 1), at least one O-Ti key is contained in described organic titanium source, the preferred tetrabutyl titanate in organic titanium source, tetraethyl titanate, isopropyl titanate.
6. the method according to claim 4 or 5, is characterized in that, in step 1), the volume ratio of organic titanium source and alcohol is 1:(1-5).
7., according to described method arbitrary in claim 4-6, it is characterized in that, step 2) in, amino agents is for being selected from-NH containing at least one
3,-NH
2with the compound of the group of-NH, preferred urea, vulkacit H, ammoniacal liquor, quadrol, trolamine.
8., according to described method arbitrary in claim 4-7, it is characterized in that, in step 3), in TiO 2 sol, the mol ratio of titanium source, water, alcohol, amino agents is 1:(10-100): (8-20): (0.1-5).
9., according to described method arbitrary in claim 4-8, it is characterized in that, in step 4), aging 1-72 hour at 50-99 DEG C, preferred 4-8 hour.
10. according to described method arbitrary in claim 4-9, it is characterized in that, in step 5), the overall dimension that aging TiO 2 sol step 4) prepared is smashed to pieces to fragment is less than 5mm, the alcohol being its 1-10 times with volume mixes, and aging 1-72 hour at 50-78 DEG C, obtains titanium dioxide alcosol, wherein, alcohol preferred alcohol, methyl alcohol, Virahol.
11. according to described method arbitrary in claim 4-10, it is characterized in that, in step 6), titanium dioxide alcosol, the alkane solvent being its 1-10 times with volume mixes, and at 50-78 DEG C, aging 1-72 hour obtains titanium dioxide alkane gel, wherein, alkane solvent preferred surface tension force is lower than the alkane of 25N/m, particularly preferably hexanaphthene, normal heptane, normal hexane.
12. according to described method arbitrary in claim 4-11, and it is characterized in that, in step 7), the parameter of drying process is: drying temperature is 60-200 DEG C, and time of drying is 0.5-24 hour.
13. according to described method arbitrary in claim 4-12, and it is characterized in that, in step 7), the processing parameter of calcining is: calcining temperature is 300-800 DEG C, and calcination time is 0.5-24 hour.
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| CN106939135A (en) * | 2017-04-18 | 2017-07-11 | 汪礼军 | A kind of preparation method based on nano-titanium dioxide modified self-cleaning antibacterial coating |
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| CN108390002A (en) * | 2018-03-05 | 2018-08-10 | 奚正华 | A kind of preparation method of the lithium battery diaphragm reinforcing material based on pyrophyllite-titania aerogel |
| CN110180472A (en) * | 2019-05-31 | 2019-08-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Anti-bacterial fibre/titanium dioxide aerogel composite and its preparation and application |
| CN116130608A (en) * | 2023-04-04 | 2023-05-16 | 山东科技大学 | Method for preparing titanium oxide film flexible electrode by self-assembly technology |
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