CN106241865A - The preparation method that a kind of high (001) face anatase titanium dioxide is nanocrystalline - Google Patents
The preparation method that a kind of high (001) face anatase titanium dioxide is nanocrystalline Download PDFInfo
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Abstract
The invention discloses the preparation method that a kind of high (001) face anatase titanium dioxide is nanocrystalline, comprise the following steps: (1) choose potassium fluotitanate soluble in water potassium fluotitanate solution, potassium fluotitanate solution is placed in hydrothermal reaction kettle, regulating hydrothermal reaction kettle interior reaction temperature after sealing is 150～230 DEG C, and use noble gas regulation hydrothermal reaction kettle in pressure be 50～150MPa, be hydrolyzed reaction 0.5～10h, is quickly cooled to room temperature after reaction；(2) opening hydrothermal reaction kettle, reclaim residual solution in still, collect sample, gained sample is scrubbed, it is nanocrystalline i.e. to obtain high (001) face nano-anatase mine-titanium oxide after drying.Simply, easily obtain, the response time is short, and reaction temperature is low for this preparation method raw material, avoid the reaction process of complexity, simplifying technique, cost is relatively low, simultaneously synthesizing go out anatase titanium dioxide nano-crystalline granule homogeneous, crystal form is intact, high (001) face accounting.
Description
Technical field
The invention belongs to nano titanium oxide technical field, be specifically related to a kind of high (001) face anatase titanium dioxide
Nanocrystalline preparation method.
Background technology
Nano titanium oxide is currently used widest catalysis material.Wherein, anatase-type nanometer titanium dioxide by
The features such as, environmental friendliness, stock number sufficient, photocatalysis performance excellence good in its chemical physical stability, are widely used in light and urge
At change, solaode, UV resistance additive, organism transplanting, antibacterial and deodouring, vessel material, photonic crystal, heavy metal pollution
The advanced field such as reason, is most to have the photoelectricity of DEVELOPMENT PROSPECT, green material.
Anatase titanium dioxide (001) crystal face, due to higher energy, has good reactivity, and therefore accounting is more
Height, then the photocatalysis performance of material is the best.But, during natural nucleating growth, (001) of anatase titanium dioxide is brilliant
Look unfamiliar long rapid, it is generally difficult to synthesizing, this constrains the industry of highlight catalytic active nano titanium dioxide to a certain extent
Produce and promote.
First the surface that report utilized fluorion to reduce (001) from 2008 and then can synthesize the micron in height (001) face
(Yang et al.2008.Anatase TiO after the research of monocrystalline anatase titanium dioxide2single crystals with
A large percentage of reactive facets.Nature, 453:638-642), utilize fluorine-containing composition synthesis height
(001) method of the anatase titanium dioxide in face is widely popularized.
The anatase titanium dioxide synthesizing height (001) face at present is all to use presoma and derivant, controlling agent to carry out
Reaction obtains, and wherein precursor solution has titanium tetrafluoride, titanium tetrachloride, titanous chloride., titanium valve+hydrogen peroxide, titanium tetrachloride+oxygen
The Titanium alkoxides such as gas, titanium sheet+ammonium fluoride, titanium sulfate, titanium nitride, titanium disulfide, titanium boride and butyl titanate, and derivant or
Controlling agent the most generally uses all kinds of organic reagent (Liu such as Fluohydric acid. and (or) dehydrated alcohol, carboxylic acid, toluene, acetone, glycerol
et al.2011.Crystal facet engineering of semiconductor photocatalysts:
motivations,advances and unique properties.Chem.Commun.,47:6763-6783.)。
Due to building-up process uses one or more predecessors as titanium source, also use one or more inorganic simultaneously and
(or) organic reagent as nanocrystalline morphology control agent, cause the reagent of synthesis high (001) face anatase titanium dioxide to prepare
More, process is more numerous, and cost is the lowest.
Summary of the invention
It is an object of the invention to provide the preparation method that a kind of high (001) face anatase titanium dioxide is nanocrystalline, should
Simply, easily obtain, the response time is short, and reaction temperature is low preparation method raw material, it is to avoid complicated reaction process, simplifies work
Skill, cost is relatively low, simultaneously synthesizing go out anatase titanium dioxide nano-crystalline granule homogeneous, crystal form is intact, high (001) face accounts for
Ratio.
The above-mentioned purpose of the present invention is achieved by the following technical solution: above-mentioned height (001) face Detitanium-ore-type dioxy
Change the preparation method of the preparation method of nanocrystalline Ti, comprise the following steps:
(1) potassium fluotitanate K is chosen2TiF6Potassium fluotitanate K soluble in water2TiF6Solution, is placed in water by potassium fluotitanate solution
In thermal response still, regulating hydrothermal reaction kettle interior reaction temperature after sealing is 150～230 DEG C, and uses noble gas to regulate hydro-thermal
Reacting kettle inner pressure is 50～150MPa, and be hydrolyzed reaction 0.5～10h, is quickly cooled to room temperature after reaction；
(2) opening hydrothermal reaction kettle, reclaim residual solution in still, collect sample, gained nano titanium oxide sample is through washing
Wash, after drying i.e. to obtain high (001) face nano-anatase mine-titanium oxide nanocrystalline.
In the preparation method that above-mentioned height (001) face anatase titanium dioxide is nanocrystalline:
In step (1), water is preferably deionized water, potassium fluotitanate K2TiF6The molar concentration of solution be preferably 0.005～
0.04mol/L, the volume of potassium fluotitanate solution preferably comprises the 10%～80% of hydrothermal reaction kettle cumulative volume.
Response time in step (1) includes the time consumed of heating up.
Regulate hydrothermal reaction kettle interior reaction temperature after step (1) seals and be preferably 180～210 DEG C, and use indifferent gas
In body regulation hydrothermal reaction kettle, pressure is preferably 80～120MPa, and be preferably hydrolyzed reaction 0.5～5h.
Noble gas described in step (1) is preferably argon or helium, it is preferred to use frozen water or compressed air are to reaction
Still carries out fast cooling.
In step (2), residual solution includes potassium fluotitanate, Fluohydric acid. and potassium fluoride, adds excess titanium in residual solution
Powder, can obtain initial feed potassium fluotitanate K2TiF6Solution, and can to a certain degree eliminate Fluohydric acid. pollution.
As a kind of preferably technical scheme of the present invention, step (2) described hydrothermal reaction kettle is salable high-temperature high pressure water
Thermal response still, described salable High Temperature High Pressure hydro-thermal reaction still includes that metal shell and the resistance to strong acid being arranged in metal shell are strong
Alkali liner, the material of described strong alkali-acid resistance liner is politef, polybenzoate, polyimides, silver, gold, platinum alloy, gold
Palldium alloy or silver palladium alloy.
When described salable High Temperature High Pressure hydro-thermal reaction still includes metal shell and the resistance to strong acid being arranged in metal shell
During highly basic liner, the process collecting sample is: use deionized water to clean hydrothermal reaction kettle inner surface, collects the fluid cleaned and obtains
The turbid liquid of nano titanium oxide, is centrifuged turbid for nano titanium oxide liquid, takes lower sediment after being centrifuged, lower sediment is washed,
I.e. obtain high (001) face nano-anatase mine-titanium oxide after drying nanocrystalline.
As another preferred technical scheme of the present invention, step (2) described hydrothermal reaction kettle is salable high temperature
High-pressure hydrothermal reaction kettle, described salable High Temperature High Pressure hydro-thermal reaction still include metal shell, be arranged in metal shell resistance to
Strong acid and strong base liner and be arranged on the plated film thin plate bottom described hydrothermal reaction kettle, the material of described plated film thin plate is polytetrafluoro
The plastics such as ethylene, polybenzoate, polyimides；Or the inert metal sheet such as silver, gold, platinum alloy, rhotanium or silver palladium alloy.
When described salable High Temperature High Pressure hydro-thermal reaction still include metal shell, the resistance to strong acid that is arranged in metal shell strong
Alkali liner and when being arranged on the plated film thin plate bottom described hydrothermal reaction kettle, the process collecting sample is: take out plated film thin plate,
By scrubbed for plated film thin plate, nanocrystalline at plated film thin sheet surface prepared high (001) face nano-anatase mine-titanium oxide after drying.
Wherein strong alkali-acid resistance liner can be directly to be welded in inert metal or compo pipe；Or directly first make resistance to by force
Acid highly basic liner, then be arranged in metal shell.
Surpass it addition, the Pressure gauge, breather line and the stop valve that are connected with High Temperature High Pressure hydro-thermal reaction still are preferably high accuracy
High-pressure manometer, breather line and stop valve.
Washing preferably employs deionized water and dehydrated alcohol respectively washs 2～3 times in step (2), be dried preferably employ air-dried
Or drying basin preserves.
The principle of the present invention is: the core of height (001) the face nanocrystalline preparation method of anatase titanium dioxide of the present invention
It is that the hydrolysis utilizing potassium fluotitanate single agents self generates titanium dioxide nanocrystalline, with fluotitanic acid common on market
Potassium powder and deionized water are mixed with potassium fluotitanate weak solution as titanium source, and potassium fluotitanate solution is put into hydrothermal reaction kettle,
Hydrothermal reaction kettle heated and pressurizes, after reaction terminates, hydrothermal reaction kettle being quickly cooled to room temperature, heavy by obtained
Height (001) the face nanocrystalline sample of anatase titanium dioxide can be obtained after the material cleaning, drying of shallow lake.
In height (001) the face nanocrystalline preparation method of anatase titanium dioxide of the present invention, unique core reagent used
For potassium fluotitanate solution, under hydrothermal conditions, there is following hydrolysis in potassium fluotitanate and water:
K2TiF6+2H2O→TiO2↓+4HF+2KF
Potassium fluotitanate generation hydrolysis can generate that anatase titanium dioxide is nanocrystalline and potassium, hydrogen, fluorion, in product
Fluorion can reduce the surface energy in anatase titanium dioxide nanocrystalline (001) face, promotes the growth in (001) face, finally makes
The nano titanium oxide of synthesis has high photocatalytic activity, thus avoids the extra Fluohydric acid. etc. that adds in traditional handicraft and try
Agent.
Owing to step of the present invention (1) controlling nanocrystalline type and crystal form by temperature and pressure, pass through the response time
Control said hydrolyzed reaction carries out degree and the accounting of (001) crystal face, in order to obtain high (001) face accounting, needs control
Said hydrolyzed processed reaction is incomplete reaction, and the recovery solution in step the most of the present invention (2) mainly comprises potassium fluotitanate, hydrogen fluorine
Acid and potassium fluoride, mix excess titanium valve in solution toward reclaiming, it is thus achieved that recovery solution can continue on for the most former of the present invention
Material, on the one hand can efficient recovery and reduce cost, on the other hand can eliminate Fluohydric acid. and pollute, maintain process safety.
Present invention have the advantage that
(1) the preparation method employing potassium fluotitanate solution of the present invention is as single agents, by potassium fluotitanate at hydro-thermal bar
Under part, to generate high (001) face anatase titanium dioxide nanocrystalline for the hydrolysis of self, the hydrion that simultaneously generates and fluorine from
Son instead of the Fluohydric acid. added in traditional handicraft, thus realize single agents autoreaction generation high catalytic performance titanium dioxide and receive
Meter Jing；
(2) preparation method of the present invention synthesizes high catalytic performance titanium dioxide nanocrystalline by single agents autoreaction, keeps away
The proportioning of multiple predecessor and morphology control agent during having exempted from traditional handicraft weighs and priority processing step, therefore the method
Technique control simple, easily operated, advantage of lower cost；
(3) preparation method of the present invention incomplete hydrolysis synthesis high catalytic performance dioxy by potassium fluotitanate self
Change nanocrystalline Ti, reclaim solution and mainly comprise potassium fluotitanate, Fluohydric acid. and potassium fluoride, thus reclaim solution and can continue directly to conduct
The low concentration initial feed of the present invention, thus reduce cost；
(4) the recovery solution that the preparation method of the present invention obtains mainly comprises potassium fluotitanate, Fluohydric acid. and potassium fluoride, back
Receive incorporation excess titanium valve in solution to reprocess, Fluohydric acid. and potassium fluoride can continue to synthesize potassium fluotitanate, thus obtain
Reclaim solution and can continue on for the initial feed of the present invention, on the one hand can efficient recovery and reduce cost, on the other hand can disappear
Dehydrogenation fluoric acid pollutes, and maintains process safety.
Accompanying drawing explanation
Fig. 1 is LR laser raman collection of illustrative plates (a) that the anatase titanium dioxide prepared in the embodiment of the present invention 1 is nanocrystalline
And stereoscan photograph；
Fig. 2 is the stereoscan photograph that the anatase titanium dioxide prepared in the embodiment of the present invention 2 is nanocrystalline,
A () is low range photo, (b) is high magnification photo；
Fig. 3 is the nanocrystalline photo of the anatase titanium dioxide prepared in the embodiment of the present invention 3 and identifies collection of illustrative plates,
A () is 200 magnification micrographs of the nano titanium oxide plated film of metal surface, (b) is that the laser of nano titanium oxide plated film draws
Graceful collection of illustrative plates, (c) is high power stereoscan photograph, and (d) is low power stereoscan photograph.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is further illustrated, but the scope of protection of present invention is as anti-
The volume answering device and reaction temperature, response time and reaction liquid is not limited to embodiment and is lifted.
Embodiment 1
The nanocrystalline preparation method of height (001) face anatase titanium dioxide that the present embodiment provides, comprises the following steps:
(1) by 0.48g potassium fluotitanate (K2TiF6, commercially available, lower with) be dissolved in 100mL deionized water fully dissolving and prepare
0.02mol/L reaction solution, puts into 200mL hydrothermal reaction kettle by prepared reaction solution, and it is about 70% that compactedness controls, water
Thermal response still is sealed high-temp high-pressure hydrothermal reaction kettle, High Temperature High Pressure hydro-thermal reaction still connect have high accuracy ultra high pressure table,
Breather line and stop valve, high-temperature high-pressure reaction kettle has metal shell, is provided with polytetrafluoroethyllining lining in metal shell, will
After reactor is tightened, in still, inject argon by breather line and stop gas injection, by adding to pressure 20MPa, closedown stop valve
Reactor is heated by hot stove, and arranging reaction temperature is 150 DEG C；After temperature rises to 150 DEG C, cut-off in opening steps (1)
Valve, the supplementary argon that injects of continuation, to pressure 50MPa, keeps 0.5 hour response time, uses frozen water to water pouring step after having reacted
(1) in, reactor carries out fast cooling to room temperature；
(2) reactor in step (1) is opened, reclaim residual solution in still, make to be washed with deionized still Nell wall, receive
The fluid of collection washing can get the turbid liquid of nano titanium oxide, is centrifuged in turbid for gained liquid is placed on centrifuge, after centrifugal end
Take out lower sediment and rinse 2～3 times, finally by height i.e. available after precipitate natural air drying with deionized water and dehydrated alcohol
(001) active nano anatase titanium dioxide in face is nanocrystalline, and Fig. 1 (a) LR laser raman analysis shows that obtained nanocrystalline is
Anatase, the anatase titanium dioxide nano-crystalline granule of Fig. 1 (b) stereoscan photograph display synthesis is homogeneous, and particle diameter is many several
Ten ran, crystal form is preferable, and how in flat, (001) face exposes more.
Nano-anatase synthesis technique (the Liu et al.2011.Crystal facet that comparison forefathers sum up
engineering of semiconductor photocatalysts:motivations,advances and unique
Properties.Chem.Commun., 47:6763-6783.), nano-anatase size and crystal formation that this example is prepared are similar to
In Amano (Amano et al.2009.Chem.Mater., 21,2601) and Alivov (Alivov and
Fan.2009.J.Phys.Chem.C., 113,12954) anatase nanometer crystal et al. prepared, thus (001) face is sudden and violent
Dew rate similarly, up to more than 55%, belongs to the anatase nanometer crystal in high (001) face.The anatase nanometer crystal of this kind of crystal form
The ability of photodissociation glacial acetic acid is the highest with the photocatalyst P25 sold on market, and the ability of photodissociation methanol is then high than P25 to be obtained
Many (Amano et al.2009.Chem.Mater., 21,2601).
Wherein residual solution mainly comprises potassium fluotitanate, Fluohydric acid. and potassium fluoride, mixes excess titanium valve in residual solution
Reprocess, Fluohydric acid. and potassium fluoride can continue to synthesize potassium fluotitanate, thus the recovery solution obtained can continue on for
The initial feed of the present invention, on the one hand can efficient recovery and reduce cost, on the other hand can eliminate Fluohydric acid. and pollute, maintain technique
Safety.
Embodiment 2
The nanocrystalline preparation method of height (001) face anatase titanium dioxide that the present embodiment provides, comprises the following steps:
(1) by 0.96g potassium fluotitanate (K2TiF6) be dissolved in 100mL deionized water and fully dissolve that to prepare 0.04mol/L anti-
Answering solution, carry out sealing after in the reaction solution 5mL threading diameter 4.5mm gold pipe of preparation, compactedness controls to be 50% left side
The right side, then puts gold pipe into high-temperature high-pressure reaction kettle, after tightening reactor, injects argon to pressure by breather line in still
Power 50MPa, is closed stop valve and stops gas injection, heated reactor by heating furnace, and arranging reaction temperature is 200 DEG C；Temperature
After degree rises to 200 DEG C, stop valve in opening steps (1), continues to supplement and injects argon to pressure 100MPa, holding response time
3 hours, use frozen water to water reactor in pouring step (1) after having reacted and carry out fast cooling to room temperature；
(2) reactor in step (1) is opened, the gold pipe in step (2) is taken out and breaks, make to be washed with deionized
Gold inside pipe wall, the fluid collecting washing can get the turbid liquid of nano titanium oxide, is centrifuged in turbid for gained liquid is placed on centrifuge,
Centrifugal terminate after take out lower sediment and with deionized water rinsing 2～3 times, finally i.e. will can get high after precipitate natural air drying
(001) face active nano anatase, Fig. 2 (a) scanning electron microscope display precipitate particles is homogeneous, and Fig. 2 (b) shows Detitanium-ore-type dioxy
Change nanocrystalline Ti particle diameter more to grow in about 100nm, crystal form perfection idiomorphism, (001) face.The sharp titanium of nanometer that this example is prepared
Ore deposit size and crystal formation are similar to the sharp titanium that Liu et al. (Liu et al.2010.Chem.Commum., 46,1664) prepares
Ore deposit is nanocrystalline.The anatase nanometer crystal of this kind of crystal form compares for normal light catalyst, can be by the ability of photodissociation methylene blue
Improve 82.5% (Liu et al.2010.Chem.Commum., 46,1664).
The recycling of residual solution is with embodiment 1.
Embodiment 3
The nanocrystalline preparation method of height (001) face anatase titanium dioxide that the present embodiment provides, comprises the following steps:
(1) 0.96g potassium fluotitanate (K2TiF6) is dissolved in 100mL deionized water the prepared 0.04mol/L of fully dissolving anti-
Answering solution, prepared reaction solution is put into hydrothermal reaction kettle, it is about 60% that compactedness controls, and is having polytetrafluoroethyllining lining
Reactor bottom place a smooth gold slice, after being tightened by reactor, in still, inject argon extremely by breather line
Pressure 20MPa, is closed stop valve and stops gas injection, heated reactor by heating furnace, and arranging reaction temperature is 200 DEG C,
After temperature rises to 200 DEG C, stop valve in opening steps (1), the supplementary argon that injects of continuation is to pressure 50MPa, when keeping reaction
Between 10 hours, use frozen water to water reactor in pouring step (1) after having reacted and carry out fast cooling to room temperature；
(2) being opened by reactor in step (1), reclaim residual solution in still, the gold taken out in step (1) in still is thin
Sheet, makes to be washed with deionized 2～3 times, and after natural air drying, visible gold slice surface exists one layer of nano titanium oxide plated film,
Fig. 3 (a) is the microphotograph (amplifying 200 times) of gold slice surface nano-titanium dioxide film plating layer, and Fig. 3 (b) LR laser raman divides
Analysis shows that these film plating layer mineral are that anatase titanium dioxide is nanocrystalline, and stereoscan photograph (Fig. 3 (c) and (d)) shows that this is received
Rice film plating layer is comparatively dense, and nano-crystalline granule is homogeneous, is likely to be due to the response time longer, causes anatase crystal form by Fluohydric acid.
Corrosion, thus cause crystal form to be not so good as embodiment 1 and the idiomorphism of embodiment 2, but (001) face specific surface area is higher.Prepared by this example
The nano-anatase size gone out and crystal formation are similar to Liu et al. (Liu et al.2009.J.Am.Chem.Soc, 131,12868)
The anatase nanometer crystal prepared.Anatase nanometer crystal (001) the face exposure of this kind of crystal form is up to 64%, it may have notable
Photocatalysis performance (Liu et al.2009.J.Am.Chem.Soc, 131,12868).
The recycling of residual solution is with embodiment 1.
Embodiment 4
The nanocrystalline preparation method of height (001) face anatase titanium dioxide that the present embodiment provides, comprises the following steps:
(1) by 0.48g potassium fluotitanate (K2TiF6) be dissolved in 100mL deionized water and fully dissolve prepared 0.02mol/L reaction
Solution, carries out sealing after in the reaction solution 5mL threading diameter 4.5mm gold pipe of preparation, and it is about 40% that compactedness controls,
Then put gold pipe into high-temperature high-pressure reaction kettle, after tightening reactor, in still, inject argon to pressure by breather line
100MPa, is closed stop valve and stops gas injection, heated reactor by heating furnace, and arranging reaction temperature is 200 DEG C, temperature
After rising to 200 DEG C, stop valve in opening steps (1), continues to supplement and injects argon to pressure 150MPa, holding response time
0.5 hour, use frozen water to water reactor in pouring step (1) after having reacted and carry out fast cooling to room temperature；
(2) reactor in step (1) is opened, the gold pipe in step (2) is taken out and breaks, make to be washed with deionized
Gold inside pipe wall, the fluid collecting washing can get the turbid liquid of nano titanium oxide, is centrifuged in turbid for gained liquid is placed on centrifuge,
Centrifugal terminate after take out lower sediment and with deionized water rinsing 2～3 times, finally i.e. will can get high after precipitate natural air drying
(001) face active nano anatase (TiO2)。
The recycling of residual solution is with embodiment 1.
Embodiment 5
The nanocrystalline preparation method of height (001) face anatase titanium dioxide that the present embodiment provides, comprises the following steps:
(1) by 0.12g potassium fluotitanate (K2TiF6, commercially available, lower with) be dissolved in 100mL deionized water fully dissolving and prepare
0.005mol/L reaction solution, puts into 200mL hydrothermal reaction kettle by prepared reaction solution, and it is about 20% that compactedness controls,
Hydrothermal reaction kettle is sealed high-temp high-pressure hydrothermal reaction kettle, and High Temperature High Pressure hydro-thermal reaction still connects high accuracy ultra high pressure
Table, breather line and stop valve, high-temperature high-pressure reaction kettle has metal shell, is provided with polyimides liner in metal shell,
After reactor is tightened, in still, inject argon by breather line and stop gas injection to pressure 20MPa, closedown stop valve, pass through
Reactor is heated by heating furnace, and arranging reaction temperature is 230 DEG C；After temperature rises to 230 DEG C, opening steps (1) is cut
Stopping valve, the supplementary argon that injects of continuation, to pressure 120MPa, keeps 5 hours response time, and after having reacted, use frozen water waters to drench and walks
Suddenly in (1), reactor carries out fast cooling to room temperature；
(2) reactor in step (1) is opened, reclaims residual solution in still, make to be washed with deionized still Nell wall,
The fluid collecting washing can get the turbid liquid of nano titanium oxide, is centrifuged in turbid for gained liquid is placed on centrifuge, centrifugal end
Rear taking-up lower sediment is also rinsed 2～3 times, finally by the most available after precipitate natural air drying with deionized water and dehydrated alcohol
High (001) face nanocrystalline (TiO of active nano anatase titanium dioxide2)。
The recycling of residual solution is with embodiment 1.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, be included in protection scope of the present invention.
Claims (10)
1. the preparation method that high (001) face anatase titanium dioxide is nanocrystalline, is characterized in that comprising the following steps:
(1) potassium fluotitanate K is chosen2TiF6Potassium fluotitanate K soluble in water2TiF6Solution, is placed in hydro-thermal by potassium fluotitanate solution anti-
Answering in still, regulating hydrothermal reaction kettle interior reaction temperature after sealing is 150～230 DEG C, and uses noble gas to regulate hydro-thermal reaction
In still, pressure is 50～150MPa, and be hydrolyzed reaction 0.5～10h, is quickly cooled to room temperature after reaction；
(2) opening hydrothermal reaction kettle, reclaim residual solution in still, collect sample, gained sample is scrubbed, it is high i.e. to obtain after drying
(001) face nano-anatase mine-titanium oxide is nanocrystalline.
The preparation method that height the most according to claim 1 (001) face anatase titanium dioxide is nanocrystalline, is characterized in that:
In step (1), water is deionized water, potassium fluotitanate K2TiF6The molar concentration of solution is 0.005～0.04mol/L, potassium fluotitanate
The volume of solution accounts for the 10%～80% of hydrothermal reaction kettle cumulative volume.
The preparation method that height the most according to claim 1 (001) face anatase titanium dioxide is nanocrystalline, is characterized in that:
Regulating hydrothermal reaction kettle interior reaction temperature after sealing in step (1) is 180～210 DEG C, and uses noble gas regulation hydro-thermal anti-
Answering pressure in still is 80～120MPa, and be hydrolyzed reaction 0.5～5h.
The preparation method that height the most according to claim 1 (001) face anatase titanium dioxide is nanocrystalline, is characterized in that:
Noble gas described in step (1) is argon or helium, uses frozen water or compressed air that reactor is carried out fast cooling.
The preparation method that height the most according to claim 1 (001) face anatase titanium dioxide is nanocrystalline, is characterized in that:
In step (2), residual solution includes potassium fluotitanate, Fluohydric acid. and potassium fluoride, adds excess titanium valve, can obtain in residual solution
Initial feed potassium fluotitanate K2TiF6Solution, and Fluohydric acid. pollution can be eliminated.
The preparation method that height the most according to claim 1 (001) face anatase titanium dioxide is nanocrystalline, is characterized in that:
Step (2) described hydrothermal reaction kettle is salable High Temperature High Pressure hydro-thermal reaction still, described salable High Temperature High Pressure hydro-thermal reaction still
Including metal shell and the strong alkali-acid resistance liner being arranged in metal shell, the material of described strong alkali-acid resistance liner is poly-four
Fluorothene, polybenzoate, polyimides, silver, gold, platinum alloy, rhotanium or silver palladium alloy.
The preparation method that height the most according to claim 6 (001) face anatase titanium dioxide is nanocrystalline, is characterized in that receiving
The process of collection sample is: use deionized water to clean hydrothermal reaction kettle inner surface, collects the fluid cleaned and obtains nano titanium oxide
Turbid liquid, is centrifuged turbid for nano titanium oxide liquid, centrifugal after take lower sediment, lower sediment is washed, i.e. obtain after drying high
(001) face nano-anatase mine-titanium oxide is nanocrystalline.
The preparation method that height the most according to claim 1 (001) face anatase titanium dioxide is nanocrystalline, is characterized in that:
Step (2) described hydrothermal reaction kettle is salable High Temperature High Pressure hydro-thermal reaction still, described salable High Temperature High Pressure hydro-thermal reaction still
The strong alkali-acid resistance liner that including metal shell, is arranged in metal shell and be arranged on the plating bottom described hydrothermal reaction kettle
Film thin plate, the material of described plated film thin plate is politef, polybenzoate, polyimides, silver, gold, platinum alloy, rhotanium
Or silver palladium alloy.
The preparation method that height the most according to claim 8 (001) face anatase titanium dioxide is nanocrystalline, is characterized in that receiving
The process of collection sample is: take out plated film thin plate, by scrubbed for plated film thin plate, after drying in plated film thin sheet surface prepared high (001)
Face nano-anatase mine-titanium oxide is nanocrystalline.
10. according to the preparation method that height (001) the face anatase titanium dioxide described in claim 1,6,7,8 or 9 is nanocrystalline,
It is characterized in that: in step (2), washing uses deionized water and dehydrated alcohol respectively to wash 2～3 times, is dried employing and air-dries or drying basin
Preserve.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185557A (en) * | 2017-06-02 | 2017-09-22 | 西北师范大学 | A kind of preparation method of titanium dioxide supported palladium zinc cadmium sulphur photochemical catalyst |
| CN108163892A (en) * | 2018-03-16 | 2018-06-15 | 中国科学院广州地球化学研究所 | A kind of single agents autoreaction prepares octahedra crystal form Ta2O5The method of nano particle |
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| CN110697770A (en) * | 2019-11-18 | 2020-01-17 | 江苏师范大学 | Anatase TiO2Method for preparing decahedron |
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| CN111392770A (en) * | 2020-03-04 | 2020-07-10 | 浙江大学 | Shuttle-like titanium dioxide nanocrystal and preparation method thereof |
| CN113151890A (en) * | 2021-02-26 | 2021-07-23 | 太原理工大学 | Single crystal titanium dioxide nano-particle with (001) surface exposed, and preparation method and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1786264A (en) * | 2005-11-01 | 2006-06-14 | 武汉理工大学 | Method of low temperature preparing C axle preferrel orientation titanium dioxide film |
| CN105209390A (en) * | 2013-03-15 | 2015-12-30 | 水晶无机化学瑞士有限公司 | Rutile titanium dioxide nanoparticles and ordered acicular aggregates of same |
-
2016
- 2016-08-23 CN CN201610708917.6A patent/CN106241865B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1786264A (en) * | 2005-11-01 | 2006-06-14 | 武汉理工大学 | Method of low temperature preparing C axle preferrel orientation titanium dioxide film |
| CN105209390A (en) * | 2013-03-15 | 2015-12-30 | 水晶无机化学瑞士有限公司 | Rutile titanium dioxide nanoparticles and ordered acicular aggregates of same |
Non-Patent Citations (2)
| Title |
|---|
| YUYU ET AL.: ""Low-cost synthesis of robust anatase polyhedral structures with a preponderance of exposed {001} facets for enhanced photoactivities"", 《NANO REC.》 * |
| 何俊杰等: ""温度、浓度对流体中氟钛络合物水解的影响：对深部地质过程中钛元素活动的制约"", 《岩石学报》 * |
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