CN104192896A - TiO2 nanocrystal and synthetic method thereof - Google Patents
TiO2 nanocrystal and synthetic method thereof Download PDFInfo
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- CN104192896A CN104192896A CN201410411656.2A CN201410411656A CN104192896A CN 104192896 A CN104192896 A CN 104192896A CN 201410411656 A CN201410411656 A CN 201410411656A CN 104192896 A CN104192896 A CN 104192896A
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- tio
- nanocrystalline
- synthetic
- presoma
- titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The embodiment of the invention discloses a TiO2 nanocrystal and a synthetic method thereof. The nanocrystal is an anatase TiO2 nanocrystal, and the exposed crystal surface of the nanocrystal is perpendicular to a crystal zone axis [111]. The TiO2 nanocrystal is high in purity and uniform in particle size distribution, and can be used for degrading a methyl blue solution and a dye-sensitized solar cell; compared with commercial P25TiO2, the catalytic and photovoltaic performances of the TiO2 nanocrystal are remarkably improved.
Description
Technical field
The present invention relates to crystalline material field, particularly a kind of TiO
2nanocrystalline and synthetic method.
Background technology
1972, Japanese Honda and Fujishima found under UV-irradiation, TiO
2(titanium dioxide) is nanocrystalline can generate H by water of decomposition
2and O
2.Henceforth, TiO
2nanocrystalline great attention and the further investigation that has caused domestic and international investigator.
TiO
2nanocrystalline have a high stability, nontoxic, environmentally friendly, and the distinguishing feature such as cheap, not only be widely used in photolysis water hydrogen, and be widely used in dye sensitization solar battery, photocatalytic degradation toxic pollutants, energy storage and conversion, electrochromism and sensory field etc.Due to TiO
2nanocrystalline its photocatalysis performance of exposure crystal face strong effect and photovoltaic performance, therefore, the anatase titanium dioxide TiO of synthetic tool particular exposed crystal face
2nanocrystalline is very important.
In recent years, synthetic { 101}, { 010}, { the anatase titanium dioxide TiO of 001} crystal plane have been reported
2nanocrystalline certain methods and application.Yet, in prior art, do not have about exposing crystal plane perpendicular to the anatase titanium dioxide TiO of [111] zone axis
2report.
Summary of the invention
The inventor has found to have the anatase titanium dioxide TiO of high miller index surface unexpectedly
2nanocrystalline, and find that it has very important purposes in fields such as catalyzed degradation toxic pollutant, dye sensitization solar batterys.
For addressing the above problem, the embodiment of the invention discloses a kind of TiO
2nanocrystalline and synthetic method.Technical scheme is as follows:
A kind of TiO
2nanocrystalline, described nanocrystalline be anatase titanium dioxide TiO
2nanocrystalline, it exposes crystal face perpendicular to [111] zone axis.
Wherein, described TiO
2nanocrystalline pattern is bar-shaped.
The present invention provides a kind of TiO simultaneously
2nanocrystalline synthetic method, can comprise the following steps:
The four metatitanic acid nanometer sheet colloidal suspension liquids of take are presoma, regulate the pH value of presoma, make its pH value between 1～4; Presoma by pH value between 1～4 carries out hydro-thermal reaction, obtains TiO
2nanocrystalline.
Wherein, hydro-thermal reaction finishes rear separating obtained product, then products therefrom is washed, is filtered and be dried.
In a kind of preferred implementation of the present invention, the presoma by pH value between 1～4 carries out hydro-thermal reaction, is specially:
Presoma by pH value between 1～4 was 160 ℃～200 ℃ microwave radiations 1 hour～2 hours;
Or
PH value is heated to after 140 ℃～200 ℃ at the presoma between 1～4, is incubated 18 hours～30 hours.
In a kind of preferred implementation of the present invention, with the first hydrochloric acid soln and the first tetramethyl ammonium hydroxide solution, regulate the pH value of presoma, the concentration of described the first hydrochloric acid soln is 2mol/L～4mol/L; The concentration of described the first tetramethyl ammonium hydroxide solution is 0.5mol/L～2mol/L.
In a kind of preferred implementation of the present invention, the preparation method of presoma four metatitanic acid nanometer sheet colloidal suspension liquids comprises the following steps:
A) synthetic stratiform potassium tetratitanate: with K
2cO
3with anatase titanium dioxide TiO
2for raw material, by K
2cO
3with anatase titanium dioxide TiO
2after mixing, be warming up to 800 ℃～1000 ℃, react 20 hours～30 hours, the speed of intensification is 2 ℃/min～8 ℃/min, makes stratiform potassium tetratitanate, wherein, and described K
2cO
3with anatase titanium dioxide TiO
2mol ratio be (1～1.1): 4;
B) synthetic four metatitanic acids: by step a) in synthetic potassium tetratitanate be dissolved in the second hydrochloric acid soln, carry out proton-exchange reaction, after reaction finishes, separating obtained product, then washs, filters products therefrom and dry, obtains four metatitanic acids;
C) synthetic four metatitanic acid nanometer sheet colloidal suspension liquids: by step b), four synthetic metatitanic acids join in the second tetramethyl ammonium hydroxide solution, obtain mixed solution, and wherein, the mass ratio of four metatitanic acids and Tetramethylammonium hydroxide is 1:(1.2～3); Described mixed solution is reacted 20 hours～30 hours at 90 ℃～110 ℃, after reaction finishes, gained reactant is mixed with water and stir, static rear filtration, obtains presoma four metatitanic acid nanometer sheet colloidal suspension liquids.
In a kind of preferred implementation of the present invention, step a) in, by K
2cO
3with anatase titanium dioxide TiO
2after mixing, be warming up to before 800 ℃～1000 ℃, also comprising: fully grinding.
The concentration of the second hydrochloric acid soln in a kind of preferred implementation of the present invention, step b) is 0.7mol/L～2mol/L.
In a kind of preferred implementation of the present invention, step b) described in by step a) in synthetic potassium tetratitanate be dissolved in the second hydrochloric acid soln, carry out proton-exchange reaction, be specially:
By step a) in synthetic potassium tetratitanate be dissolved in the second hydrochloric acid soln, stir 3～5 days, and change the second hydrochloric acid soln every day one time.
The present invention has synthesized the anatase titanium dioxide TiO of exposure crystal face perpendicular to [111] zone axis
2nanocrystalline, this TiO
2nanocrystalline purity is high, size distribution is even, can be used for degrading in Methylene blue solution and dye sensitization solar battery, and the P25TiO using with business
2compare, catalytic performance and photovoltaic performance are all significantly improved.Meanwhile, the present invention is that the preferential crystal face that exposes is perpendicular to the anatase titanium dioxide TiO of [111] zone axis first
2nanocrystalline synthetic a kind of method that provides, this method cost is low, pollution-free, preparation technology is simple, controllability is strong, with short production cycle, favorable repeatability, is applicable to suitability for industrialized production.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 be embodiment 1 step a) in synthetic potassium tetratitanate (K
2ti
4o
9), step b) in four synthetic metatitanic acid (H
2ti
4o
90.25H
2o), synthetic tetramethyl-ammonium ion (TMA step c)
+) the four metatitanic acid (TMA that insert
+-intercalated H
2ti
4o
9) and four metatitanic acid nanometer sheet colloidal suspension liquids in the XRD spectra of four metatitanic acids (Nanoribbon) of the nano strip of peeling off;
Fig. 2 is the anatase titanium dioxide TiO of embodiment 2, embodiment 4, embodiment 5, embodiment 6, embodiment 7 synthesizeds
2nanocrystalline XRD spectra, wherein, (a) is the anatase titanium dioxide TiO of embodiment 4 synthesizeds
2nanocrystalline XRD spectra; (b) be the anatase titanium dioxide TiO of embodiment 5 synthesizeds
2nanocrystalline XRD spectra; (c) be the anatase titanium dioxide TiO of embodiment 6 synthesizeds
2nanocrystalline XRD spectra; (d) be the anatase titanium dioxide TiO of embodiment 7 synthesizeds
2nanocrystalline XRD spectra; (e) be the anatase titanium dioxide TiO of embodiment 2 synthesizeds
2nanocrystalline XRD spectra;
Fig. 3 is embodiment 2, embodiment 4, the synthetic anatase titanium dioxide TiO of embodiment 5, embodiment 6
2nanocrystalline scanning electron microscope (SEM) photograph, wherein, (a) is the synthetic TiO of embodiment 4
2nanocrystalline scanning electron microscope (SEM) photograph; (b) be the synthetic TiO of embodiment 5
2nanocrystalline scanning electron microscope (SEM) photograph; (c) be the synthetic TiO of embodiment 6
2nanocrystalline scanning electron microscope (SEM) photograph; (d) be the synthetic TiO of embodiment 2
2nanocrystalline scanning electron microscope (SEM) photograph;
Fig. 4 is embodiment 4, embodiment 6, the synthetic anatase titanium dioxide TiO of embodiment 7
2nanocrystalline scanning electron microscope (SEM) photograph wherein, is (a) and (b) the synthetic TiO of embodiment 4
2nanocrystalline scanning electron microscope (SEM) photograph is (c) and (d) the synthetic TiO of embodiment 6
2nanocrystalline scanning electron microscope (SEM) photograph is (e) and (f) the synthetic TiO of embodiment 7
2nanocrystalline scanning electron microscope (SEM) photograph;
Fig. 5 is the synthetic anatase titanium dioxide TiO of embodiment 5, embodiment 2
2nanocrystalline scanning electron microscope (SEM) photograph, wherein, (a) is the synthetic TiO of embodiment 5
2nanocrystalline scanning electron microscope (SEM) photograph; (b) be and (c) the synthetic TiO of embodiment 2
2nanocrystalline scanning electron microscope (SEM) photograph;
Fig. 6 is the synthetic TiO of embodiment 2
2nanocrystalline degradation efficiency and light application time rational curve;
Fig. 7 is the synthetic TiO of embodiment 5
2nanocrystalline degradation efficiency and light application time rational curve;
Fig. 8 is the synthetic TiO of embodiment 2
2nanocrystalline photoelectric current-voltage characteristic graphic representation;
Fig. 9 is the synthetic TiO of embodiment 5
2nanocrystalline photoelectric current-voltage characteristic graphic representation.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
First, it should be noted that, the embodiment of the present invention is at synthetic TiO
2in nanocrystalline process, the water using is preferably deionized water or distilled water.
Further it should be noted that, all reagent that the embodiment of the present invention adopts, do not have special restriction to its source, buy or make by oneself and all can on market; For example:
K
2cO
3: specification AR, Tianjin Ke Miou chemical reagent development company buys;
Anatase titanium dioxide TiO
2: specification AR, Tianjin Ke Miou chemical reagent development company buys;
Hydrochloric acid: specification 36.5% (massfraction), Tianjin Ke Miou chemical reagent development company buys;
Tetramethylammonium hydroxide (TMAOH): specification AR, Tianjin Ke Miou chemical reagent development company buys.
Also it should be noted that, the embodiment of the present invention is at synthetic TiO
2the experimental installation adopting in nanocrystalline process, is the general equipment in this area, there is no special requirement, all can on market, buy.Contriver believes, those skilled in the art completely can be by the description of technical solution of the present invention is selected to suitable experimental installation, and the present invention does not carry out concrete restriction and explanation to experimental installation at this.
One, TiO
2nanocrystalline is synthetic
Embodiment 1
A) synthetic stratiform potassium tetratitanate: be 1:4 according to the ratio of amount of substance, weigh 13.821g (0.1mol) K
2cO
3and 31.960g (0.4mol) anatase titanium dioxide TiO
2be placed in agate mortar, after mixing, fully grind.Then transferred in corundum crucible, put into retort furnace in 900 ℃ of heating 24 hours, temperature rise rate is 5 ℃/min; Make Fiber Laminated shape potassium tetratitanate (K
2ti
4o
9).
B) synthetic four metatitanic acids: take 10.0g step a) in synthetic K
2ti
4o
9, adding in the large beaker that fills 1000mL 1mol/L the second hydrochloric acid soln, room temperature lower magnetic force stirs three days, changes the second hydrochloric acid soln every day one time, makes K
2ti
4o
9be converted into H completely
2ti
4o
9.After three proton-exchange reactions, product, by centrifugation, is used deionized water wash 4 times, and repeated centrifugation three times, finally, by resulting sample lyophilize, obtains H
2ti
4o
90.25H
2o.
C) synthetic H synthetic four metatitanic acid nanometer sheet colloidal suspension liquids: take 3.5g (about 0.01mol) step b)
2ti
4o
90.25H
2o, joining volume is in four polyethylene reaction kettles of 70mL, then adds wherein 40g (massfraction is 12.5%) the second tetramethyl ammonium hydroxide solution, after sealing, puts into High Temperature Rotating Reaktionsofen in 100 ℃ of heating 24 hours.To be cooled to room temperature, the product in reactor is transferred in beaker, then added 360mL deionized water, stirring at room after 24 hours on magnetic stirring apparatus, more static 24 hours, then suction filtration, obtains four metatitanic acid nanometer sheet colloidal suspension liquid, i.e. presomas.
D) synthetic TiO
2nanocrystalline: with the first hydrochloric acid soln of 3mol/L and the first tetramethyl ammonium hydroxide solution regulating step c of 1mol/L) in the pH value of synthetic four metatitanic acid nanometer sheet colloidal suspension liquids be 1.5.Get the nanometer sheet suspension that 40mL regulates pH value and join in four polyethylene reaction kettles that internal capacity is 80mL, put into microwave oven microwave radiation 1.5 hours at 180 ℃.Be cooled to after room temperature centrifugation, use deionized water wash 4 times, then lyophilize.Obtain exposing crystal face perpendicular to the TiO of [111] zone axis
2nanocrystalline, its pattern is bar-shaped.
Embodiment 2
A) synthetic stratiform potassium tetratitanate: be 1.05:4 according to the ratio of amount of substance, weigh 14.512g (0.105mol) K
2cO
3and 31.960g (0.4mol) anatase titanium dioxide TiO
2be placed in agate mortar, after mixing, fully grind.Then transferred in corundum crucible, put into retort furnace in 800 ℃ of heating 30 hours, temperature rise rate is 2 ℃/min; Make Fiber Laminated shape potassium tetratitanate (K
2ti
4o
9).
B) synthetic four metatitanic acids: take 10.0g step a) in synthetic K
2ti
4o
9, adding in the large beaker that fills 1000mL0.7mol/L the second hydrochloric acid soln, room temperature lower magnetic force stirs three days, changes the second hydrochloric acid soln every day one time, makes K
2ti
4o
9be converted into H completely
2ti
4o
9.After three proton-exchange reactions, product, by centrifugation, is used deionized water wash 4 times, and repeated centrifugation three times, finally, by resulting sample lyophilize, obtains H
2ti
4o
91.4H
2o.
C) synthetic H synthetic four metatitanic acid nanometer sheet colloidal suspension liquids: take 3.5g (about 0.01mol) step b)
2ti
4o
9h
2o, joining volume is in four polyethylene reaction kettles of 70mL, then adds wherein 40g (massfraction is 25%) the second tetramethyl ammonium hydroxide solution, after sealing, puts into High Temperature Rotating Reaktionsofen in 90 ℃ of heating 30 hours.To be cooled to room temperature, the product in reactor is transferred in beaker, then added 360mL deionized water, stirring at room after 24 hours on magnetic stirring apparatus, more static 24 hours, then suction filtration, obtains four metatitanic acid nanometer sheet colloidal suspension liquid, i.e. presomas.
D) synthetic TiO
2nanocrystalline: with the first hydrochloric acid soln of 2mol/L and the first tetramethyl ammonium hydroxide solution regulating step c of 0.5mol/L) in the pH value of synthetic four metatitanic acid nanometer sheet colloidal suspension liquids be 3.0.Get the nanometer sheet suspension that 40mL regulates pH value and join in four polyethylene reaction kettles that internal capacity is 80mL, put into microwave oven microwave radiation 2 hours at 160 ℃.Be cooled to after room temperature centrifugation, use deionized water wash 4 times, then lyophilize.Obtain exposing crystal face perpendicular to the TiO of [111] zone axis
2nanocrystalline, its pattern is bar-shaped.
Embodiment 3
A) synthetic stratiform potassium tetratitanate: be 1.1:4 according to the ratio of amount of substance, weigh 15.203g (0.11mol) K
2cO
3and 31.960g (0.4mol) anatase titanium dioxide TiO
2be placed in agate mortar, after mixing, fully grind.Then transferred in corundum crucible, put into retort furnace in 1000 ℃ of heating 20 hours, temperature rise rate is 8 ℃/min; Make Fiber Laminated shape potassium tetratitanate (K
2ti
4o
9).
B) synthetic four metatitanic acids: take 10.0g step a) in synthetic K
2ti
4o
9, adding in the large beaker that fills 1000mL 2mol/L the second hydrochloric acid soln, room temperature lower magnetic force stirs three days, changes the second hydrochloric acid soln every day one time, makes K
2ti
4o
9be converted into H completely
2ti
4o
9.After three proton-exchange reactions, product, by centrifugation (parameter of noncentricity comprises rotating speed and time), is used deionized water wash 4 times, and repeated centrifugation three times, finally, by resulting sample lyophilize, obtains H
2ti
4o
93H
2o.
C) synthetic H synthetic four metatitanic acid nanometer sheet colloidal suspension liquids: take 3.5g (0.01mol) step b)
2ti
4o
93H
2o, joining volume is in four polyethylene reaction kettles of 70mL, then adds wherein 50g (massfraction is 15%) the second tetramethyl ammonium hydroxide solution, after sealing, puts into High Temperature Rotating Reaktionsofen in 110 ℃ of heating 20 hours.To be cooled to room temperature, the product in reactor is transferred in beaker, then added 360mL deionized water, stirring at room after 24 hours on magnetic stirring apparatus, more static 24 hours, then suction filtration, obtains four metatitanic acid nanometer sheet colloidal suspension liquid, i.e. presomas.
D) synthetic TiO
2nanocrystalline: with the first hydrochloric acid soln of 4mol/L and the first tetramethyl ammonium hydroxide solution regulating step c of 2mol/L) in the pH value of synthetic four metatitanic acid nanometer sheet colloidal suspension liquids be 4.0.Get the nanometer sheet suspension that 40mL regulates pH value and join in four polyethylene reaction kettles that internal capacity is 80mL, put into microwave oven microwave radiation 1 hour at 200 ℃.Be cooled to after room temperature centrifugation, use deionized water wash 4 times, then lyophilize.Obtain exposing crystal face perpendicular to the TiO of [111] zone axis
2nanocrystalline, its pattern is bar-shaped.
Embodiment 4
Step a)～step c) all identical with embodiment 1,
D) synthetic TiO
2nanocrystalline: with the first hydrochloric acid soln of 3mol/L and the first tetramethyl ammonium hydroxide solution regulating step c of 1mol/L) in the pH value of synthetic four metatitanic acid nanometer sheet colloidal suspension liquids be 1.5.Get the nanometer sheet suspension that 40mL regulates pH value and join in four polyethylene reaction kettles that internal capacity is 80mL,, after sealing, put into High Temperature Rotating Reaktionsofen, at 180 ℃, heat 24 hours.Be cooled to after room temperature centrifugation, use deionized water wash 4 times, then lyophilize.Obtain exposing crystal face perpendicular to the TiO of [111] zone axis
2nanocrystalline, its pattern is bar-shaped.
Embodiment 5
Step a)～step c) all identical with embodiment 2,
D) synthetic TiO
2nanocrystalline: with the first hydrochloric acid soln of 2mol/L and the first tetramethyl ammonium hydroxide solution regulating step c of 0.5mol/L) in the pH value of synthetic four metatitanic acid nanometer sheet colloidal suspension liquids be 3.0.Get the nanometer sheet suspension that 40mL regulates pH value and join in four polyethylene reaction kettles that internal capacity is 80mL,, after sealing, put into High Temperature Rotating Reaktionsofen, at 200 ℃, heat 18 hours.Be cooled to after room temperature centrifugation, use deionized water wash 4 times, then lyophilize.Obtain exposing crystal face perpendicular to the TiO of [111] zone axis
2nanocrystalline, its pattern is bar-shaped.
Embodiment 6
Step a)～step c) all identical with embodiment 3,
D) synthetic TiO
2nanocrystalline: with the first hydrochloric acid soln of 4mol/L and the first tetramethyl ammonium hydroxide solution regulating step c of 2mol/L) in the pH value of synthetic four metatitanic acid nanometer sheet colloidal suspension liquids be 3.4.Get the nanometer sheet suspension that 40mL regulates pH value and join in four polyethylene reaction kettles that internal capacity is 80mL,, after sealing, put into High Temperature Rotating Reaktionsofen, at 140 ℃, heat 30 hours.Be cooled to after room temperature centrifugation, use deionized water wash 4 times, then lyophilize.Obtain exposing crystal face perpendicular to the TiO of [111] zone axis
2nanocrystalline, its pattern is bar-shaped.
Embodiment 7
Except steps d) in the pH value of four metatitanic acid nanometer sheet colloidal suspension liquids be 4.0, other is all identical with embodiment 6, obtains exposing crystal face perpendicular to the TiO of [111] zone axis
2nanocrystalline, its pattern is bar-shaped.
Above-mentioned enforcement 1～enforcement 7 is at synthetic TiO
2in nanocrystalline process, adopting the correlation parameter of centrifugation can be 8000 revs/min for centrifugal rotating speed, and centrifugation time is 10 minutes.
It should be noted that, the centrifugal correlation parameter adopting in the embodiment of the present invention is just in order to allow those skilled in the art can better understand TiO
2nanocrystalline synthetic method, do not represent can only be cited correlation parameter could realize technical scheme of the present invention, those skilled in the art can adjust this parameter according to practical situation, this is all feasible.The present invention does not do concrete restriction at this.
Above-mentioned enforcement 1～enforcement 7 is at synthetic TiO
2in nanocrystalline process, the lyophilize adopting is specially: sample is placed in the vial of freezing special use, then be arranged in refrigerator, open rotary knob, make to rotate and be frozen into ice in refrigerator containing the aqueous solution of sample, in refrigerator, the temperature of liquid is-15 ℃～30 ℃, sample freezing time is generally 30 minutes, can build-up ice, when in sample, the amount of the aqueous solution is many certainly, the time will be grown.Be frozen into after ice, close rotary knob and refrigerator, freezing bottle is taken out, be installed on drying machine, open vacuum pump, be evacuated to be approximately-0.09Mpa of tensimeter gauge pressure, make it under vacuum condition, be dried 24 hours.
In like manner, the cryodesiccated correlation parameter adopting in the present embodiment is just in order to allow those skilled in the art can better understand TiO
2nanocrystalline building-up process, do not represent can only be cited correlation parameter could realize technical scheme of the present invention, those skilled in the art can adjust this parameter according to practical situation, this is all feasible.The present invention does not do concrete restriction at this.
Two, TiO
2nanocrystalline sign
1, XRD (X-ray diffraction, X-ray diffraction) analyzes
(a) adopt SHIMADZU XRD-6100 diffractometer respectively to the embodiment of the present invention 1 step a) in synthetic potassium tetratitanate (K
2ti
4o
9), step b) in four synthetic metatitanic acid (H
2ti
4o
90.25H
2o), synthetic tetramethyl-ammonia radical ion (TMA step c)
+) four metatitanic acids (the TMA+-intercalated H that inserts
2ti
4o
9) and four metatitanic acid nanometer sheet colloidal suspension liquids in four metatitanic acids (Nanoribbon) of the nano strip of peeling off carry out XRD sign, wherein, the scope of collecting data diffraction angle (2 θ) is 3～70 °, sweep velocity is 5 °/min, and the electric current of acceleration voltage and application is respectively 40kV and 30mA.Result as shown in Figure 1.
As can be seen from Figure 1, K
2ti
4o
9the interlamellar spacing of (200) crystal face by 0.87nm, be reduced to H
2ti
4o
90.25H
2the 0.77nm of O, shows K
2ti
4o
9successfully occurred protonated, along with TMA
+the insertion of ion, the interlamellar spacing of its (200) crystal face is increased to 1.82nm, shows TMA
+with H
+there is permutoid reaction, be successfully inserted into the interlayer of four metatitanic acids.TMA
+four metatitanic acids that insert are soluble in water, stir after 2～3 days, obtain its corresponding nano belt colloidal suspension liquid.By TMA
+after the four metatitanic acid nano belt colloidal suspension liquid centrifugations of inserting, carry out XRD sign, find to be within the scope of 20 °～40 °, to have occurred showing stratiform H by a halo at 2 θ
2ti
4o
9the stripping reaction successfully having occurred, has peeled off into nano belt; In this simultaneously, in XRD diffraction spectrogram, in interlamellar spacing, be that the weak diffraction peak of peak intensity has appearred in 0.78nm, 0.58nm, 0.29nm place, show that the part nano belt of peeling off formation, after centrifugal, assortment has again occurred again, is stacked into four metatitanic acids again.
From the above, embodiment 1 step a)～step c) synthesized corresponding target product.Due to step in embodiment 2～6 a)～step c) resulting product is identical with embodiment 1, its XRD diffraction spectrogram is with reference to Fig. 1, therefore not to repeat here in the present invention.
(b) adopt the SHIMADZU XRD-6100 diffractometer TiO to the embodiment of the present invention 2, embodiment 4, embodiment 5, embodiment 6, embodiment 7 synthesizeds respectively
2the nanocrystalline XRD sign of carrying out, wherein, the scope of collecting data diffraction angle (2 θ) is 3～70 °, and sweep velocity is 5 °/min, and the electric current of acceleration voltage and application is respectively 40kV and 30mA.Result as shown in Figure 2.
As can be seen from Figure 2, no matter microwave-assisted hydro-thermal method or the TiO of conventional hydrothermal method synthesized
2, the standard card that is all 21-1272 with JCPDS is corresponding, is anatase titanium dioxide (anatase) TiO
2, in figure, also can find out, along with the rising of pH, the diffraction peak intensity recording raises gradually, synthetic TiO
2nano-crystalline granule is larger gradually, and degree of crystallinity raises gradually.
2, field emission scanning electron microscope (field emission scanning electron microscope is called for short FE-SEM) is analyzed
Adopt the field emission scanning electron microscope of HITACHI S-90X model to the embodiment of the present invention 2, embodiment 4, embodiment 5, the synthetic TiO of embodiment 6
2nanocrystalline pattern and microstructure analysis, the preparation of sample be by sample dispersion in deionized water, ultrasonic after, with liquid-transfering gun, pipette after liquid, point one drops on silicon plate, during mensuration, acceleration voltage is 15kV, applied current is 10 μ A.Its result as shown in Figure 3.
As can be seen from Figure 3,, no matter microwave-assisted hydro-thermal method or the TiO of conventional hydrothermal method synthesized
2, resulting anatase titanium dioxide TiO
2nanocrystalline pattern is bar-shaped type.
3, transmission electron microscope (TEM) is analyzed
The TiO synthetic to embodiment 4
2nanocrystallinely carry out the test of transmission electron microscope (TEM) and high resolution transmission electron microscopy (HR-TEM), test condition is: acceleration voltage is 300kV, and preparation of samples is being loaded with on the standard copper grid of carbon film.Its result is as shown in Fig. 4 (a) and Fig. 4 (b);
The TiO synthetic to embodiment 6
2nanocrystallinely carry out the test of transmission electron microscope (TEM) and high resolution transmission electron microscopy (HR-TEM), test condition is: acceleration voltage is 300kV, and preparation of samples is being loaded with on the standard copper grid of carbon film.Its result is as shown in Fig. 4 (c) and Fig. 4 (d);
The TiO synthetic to embodiment 7
2nanocrystallinely carry out the test of transmission electron microscope (TEM) and high resolution transmission electron microscopy (HR-TEM), test condition is: acceleration voltage is 300kV, and preparation of samples is being loaded with on the standard copper grid of carbon film.Its result is as shown in Fig. 4 (e) and Fig. 4 (f);
The TiO synthetic to embodiment 5
2nanocrystallinely carry out the test of transmission electron microscope (TEM) and high resolution transmission electron microscopy (HR-TEM), test condition is: acceleration voltage is 300kV, and preparation of samples is being loaded with on the standard copper grid of carbon film.Its result is as shown in Fig. 5 (a);
The TiO synthetic to embodiment 2
2nanocrystallinely carry out the test of transmission electron microscope (TEM) and high resolution transmission electron microscopy (HR-TEM), test condition is: acceleration voltage is 300kV, and preparation of samples is being loaded with on the standard copper grid of carbon film.Its result is as shown in Fig. 5 (b) and Fig. 5 (c);
As can be seen from Figure 4, the TiO of embodiment 4, embodiment 6, embodiment 7 synthesizeds
2nanocrystalline pattern is bar-shaped.In Fig. 4, spacing
with
correspond respectively to anatase titanium dioxide TiO
2(101) and (011) crystal face, these two interplanar angles are 82 °, and according to anatase titanium dioxide TiO
2the result of (101) and (011) crystal face constant calculations consistent, it exposes crystal face and is the plane perpendicular to [111] zone axis.
As can be seen from Figure 5, the TiO of embodiment 5, embodiment 2 synthesizeds
2nanocrystalline pattern is bar-shaped.In Fig. 5 (a), spacing
with
correspond respectively to anatase titanium dioxide TiO
2(011) and (101) crystal face.In Fig. 5 (c), spacing
with
correspond respectively to anatase titanium dioxide TiO
2(011) and (101) crystal face.(101) and (011) two interplanar angle be 82 °, and according to anatase titanium dioxide TiO
2the result of (011) and (101) crystal face constant calculations consistent, it exposes crystal face and is the plane perpendicular to [111] zone axis.
Eventually the above, the TiO of synthesized of the present invention
2nanocrystalline exposure crystal face is the plane perpendicular to [111] zone axis.
Three, TiO
2nanocrystalline performance analysis
1, photochemical catalysis experiment
Take the synthetic anatase titanium dioxide TiO of 50mg embodiment 2 and embodiment 5
2nanocrystalline, join respectively in the Erlenmeyer flask of 150mL, then, to the Methylene blue solution that adds 100mL 10mg/L in each Erlenmeyer flask, ultrasonic 2h is so that two samples are dispersed.Before irradiating, by the vigorous stirring 30min in the dark of the suspension in two Erlenmeyer flasks, so that dyestuff reaches and adsorbs/go adsorption equilibrium on titanium dioxide nanocrystalline surface, then under the condition stirring, suspension in two Erlenmeyer flasks is placed under 250W ultraviolet lamp and is irradiated, the emission wavelength 365nm of ultraviolet lamp is 80cm apart from the distance of Methylene blue solution.Every 20min, in two Erlenmeyer flasks, get respectively 3mL suspension, centrifugal to remove titanium dioxide nanocrystalline.The degradation rate of Methylene blue is by being used the change in concentration of TU-1901 spectrophotometric determination ultra violet lamp front and back Methylene blue solution to determine.As a comparison, the Degussa P25 (52.50m that business is used
2/ g, 80% anatase octahedrite and 20% rutile) under same condition, measure.Test result respectively as shown in Figure 6 and Figure 7.
Fig. 6 is the synthetic TiO of embodiment 2
2nanocrystalline degradation efficiency and light application time rational curve, as seen from the figure, in the time of 120 minutes, implement the anatase titanium dioxide TiO of 2 synthesizeds
2nanocrystalline is the degradation efficiency 86% of 94%, P25 to Methylene blue to the degradation efficiency of Methylene blue, therefore, implements the anatase titanium dioxide TiO of 2 synthesizeds
2nanocrystalline to the degradation efficiency of Methylene blue will be far above Degussa P25 the degradation efficiency to Methylene blue.
Fig. 7 is the synthetic TiO of embodiment 5
2nanocrystalline degradation efficiency and light application time rational curve, as seen from the figure, in the time of 120 minutes, implement the anatase titanium dioxide TiO of 5 synthesizeds
2nanocrystalline is the degradation efficiency 86% of 99%, P25 to Methylene blue to the degradation efficiency of Methylene blue, therefore, implements the anatase titanium dioxide TiO of 5 synthesizeds
2nanocrystalline to the degradation efficiency of Methylene blue will be far above Degussa P25 the degradation efficiency to Methylene blue.
In sum, the exposure crystal face of embodiment of the present invention synthesized is perpendicular to the TiO of [111] zone axis
2nanocrystalline, to the equal degradation efficiency to Methylene blue higher than Degussa P25 of the degradation efficiency of Methylene blue.Illustrate that the exposure crystal face of embodiment of the present invention synthesized is perpendicular to the TiO of [111] zone axis
2nanocrystalline have a good photocatalysis performance.
2, photovoltaic performance test
Take the synthetic anatase titanium dioxide TiO of 0.5g embodiment 2 and embodiment 5
2nanocrystalline, and they are joined respectively in vial, and then add 2.5g ethanol in two vials, 2.0g alpha-terpineol, the ethyl cellulose 10 of 1.4g10w% and the ethyl cellulose 45 of 1.1g 10w%, then, to two equal supersound process 5min of vial, at room temperature ball milling is 3 days, finally at vacuum rotary evaporator rotary evaporation, fall ethanol, make the TiO of embodiment 2
2the TiO of slurry and embodiment 5
2slurry.
With deionized water supersound process FTO glass (Aldrich company produces for length * wide * height=50mm * 50mm * 2.2mm, surface resistivity～7 Ω/sq) 5min, and then with ethanol supersound process 5min.The FTO glass having washed is immersed in to 0.1M Ti (OC
3o
7)
4several seconds in organic titanium solution, then in High Temperature Furnaces Heating Apparatus, calcine 60min.Porous titanium dioxide thin-film electrode is used and scrapes the skill in using a kitchen knife in cookery by the TiO of embodiment 2 and embodiment 5
2slurry is coated onto respectively the preparation on glass of FTO conduction band.The thickness of film is by the gauge control of used adhesive tape.By the TiO of embodiment 2 and embodiment 5
2after slurry spreads upon respectively on FTO conductive glass, 315 ℃ of calcining 15min (temperature rise rate is 5 ℃/min) in High Temperature Furnaces Heating Apparatus, so operation is repeatedly until obtain after required thickness, then in High Temperature Furnaces Heating Apparatus 450 ℃ of calcining 30min.Be cooled to after room temperature, be again immersed in 0.1MTi (OC
3o
7)
4several seconds in organic titanium solution, and then in High Temperature Furnaces Heating Apparatus, calcine 60min.When equitemperature is reduced to 80 ℃, taken out, be immersed in rapidly containing 3 * 10
-4in the acetonitrile of mol/L N719 and the mixing solutions of the trimethyl carbinol, in the dark under room temperature, place 24h, so that dyestuff N719 is adsorbed on titanium dioxide electrodes.Pt to electrode by FTO conductive glass being immersed in to the H containing 0.5mM
2ptCl
6aqueous isopropanol in, after several minutes, take out then 400 ℃ of calcining 20min preparation in High Temperature Furnaces Heating Apparatus.Electrolyte solution relies on capillary action to be injected in the space between two electrodes, is assembled into the dye sensitization solar battery of sandwich structure.Electrolyte solution is by containing 0.60mol/L 1-butyl-3-Methylimidazole iodide (1-Butyl-3-methylimidazolium iodide), 0.10mol/L guanidine thiocyanate (Guanidine Thiocyanate), the acetonitrile (Acetonitrile) of 0.50mol/L 4-tert .-butylpyridine (4-tert-Butylpyridine) and the mixing solutions (volume ratio=85%:15%) of valeronitrile (Valeronitrile) form.The Degussa P25TiO being prepared by same method
2photo cathode be assembled into battery, contrast with above-mentioned battery.Test result is as shown in Fig. 8 and Fig. 9.
As shown in Figure 8: when thickness is 19.1 μ m, the preferential exposure crystal face that embodiment 2 synthesizes is perpendicular to the bar-shaped anatase titanium dioxide TiO of [111] zone axis
2nanocrystalline photoelectric current is 11.06mA/cm
2, photoelectricity voltage is 0.745V, and packing factor is 0.606, and transformation efficiency is 4.99%, is better than the photoelectric current 9.80mA/cm of P25 (thickness 19.1 μ m)
2, photoelectricity voltage 0.707V, packing factor 0.572, transformation efficiency 3.96%.
As shown in Figure 9: when thickness is 15.9 μ m, the preferential exposure crystal face that embodiment 5 synthesizes is perpendicular to the bar-shaped anatase titanium dioxide TiO of [111] zone axis
2nano-crystalline photoelectric electric current is 11.5mA/cm
2, transformation efficiency is 4.74%, is better than P25TiO
2(thickness: photoelectric current 10.3mA/cm 16.6 μ m)
2, transformation efficiency 4.37%.
The present invention has synthesized the anatase titanium dioxide TiO of exposure crystal face perpendicular to [111] zone axis
2nanocrystalline, this TiO
2nanocrystalline purity is high, size distribution is even, can be used for degrading in Methylene blue solution and dye sensitization solar battery, and the P25TiO using with business
2compare, catalytic performance and photovoltaic performance are all significantly improved.Meanwhile, the present invention is that the preferential crystal face that exposes is perpendicular to the anatase titanium dioxide TiO of [111] zone axis first
2nanocrystalline synthetic a kind of method that provides, this method cost is low, pollution-free, preparation technology is simple, controllability is strong, with short production cycle, favorable repeatability, is applicable to suitability for industrialized production.
Above to a kind of TiO provided by the present invention
2nanocrystalline and synthetic method is described in detail.Applied specific embodiment herein principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand method of the present invention and clou thereof.It should be pointed out that for the person of ordinary skill of the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a TiO
2nanocrystalline, it is characterized in that, described nanocrystalline be anatase titanium dioxide TiO
2nanocrystalline, it exposes crystal face perpendicular to [111] zone axis.
2. TiO as claimed in claim 1
2nanocrystalline, it is characterized in that described TiO
2nanocrystalline pattern is bar-shaped.
3. TiO as claimed in claim 1 or 2
2nanocrystalline synthetic method, is characterized in that, comprises the following steps:
The four metatitanic acid nanometer sheet colloidal suspension liquids of take are presoma, regulate the pH value of presoma, make its pH value between 1～4; Presoma by pH value between 1～4 carries out hydro-thermal reaction, obtains TiO
2nanocrystalline.
4. method as claimed in claim 3, is characterized in that: hydro-thermal reaction finishes rear separating obtained product, then products therefrom is washed, is filtered and be dried.
5. method as claimed in claim 3, is characterized in that: the presoma by pH value between 1～4 carries out hydro-thermal reaction, is specially:
Presoma by pH value between 1～4 was 160 ℃～200 ℃ microwave radiations 1 hour～2 hours;
Or
PH value is heated to after 140 ℃～200 ℃ at the presoma between 1～4, is incubated 18 hours～30 hours.
6. method as claimed in claim 3, is characterized in that: with the first hydrochloric acid soln and the first tetramethyl ammonium hydroxide solution, regulate the pH value of presoma, the concentration of described the first hydrochloric acid soln is 2mol/L～4mol/L; The concentration of described the first tetramethyl ammonium hydroxide solution is 0.5mol/L～2mol/L.
7. method as claimed in claim 3, is characterized in that, the preparation method of presoma four metatitanic acid nanometer sheet colloidal suspension liquids comprises the following steps:
A) synthetic stratiform potassium tetratitanate: with K
2cO
3with anatase titanium dioxide TiO
2for raw material, by K
2cO
3with anatase titanium dioxide TiO
2after mixing, be warming up to 800 ℃～1000 ℃, react 20 hours～30 hours, the speed of intensification is 2 ℃/min～8 ℃/min, makes stratiform potassium tetratitanate, wherein, and described K
2cO
3with anatase titanium dioxide TiO
2mol ratio be (1～1.1): 4;
B) synthetic four metatitanic acids: by step a) in synthetic potassium tetratitanate be dissolved in the second hydrochloric acid soln, carry out proton-exchange reaction, after reaction finishes, separating obtained product, then washs, filters products therefrom and dry, obtains four metatitanic acids;
C) synthetic four metatitanic acid nanometer sheet colloidal suspension liquids: by step b), four synthetic metatitanic acids join in the second tetramethyl ammonium hydroxide solution, obtain mixed solution, and wherein, the mass ratio of four metatitanic acids and Tetramethylammonium hydroxide is 1:(1.2～3); Described mixed solution is reacted 20 hours～30 hours at 90 ℃～110 ℃, after reaction finishes, gained reactant is mixed with water and stir, static rear filtration, obtains presoma four metatitanic acid nanometer sheet colloidal suspension liquids.
8. method as claimed in claim 7, is characterized in that: step a) in, by K
2cO
3with anatase titanium dioxide TiO
2after mixing, be warming up to before 800 ℃～1000 ℃, also comprising: fully grinding.
9. method as claimed in claim 7, is characterized in that: the concentration of the second hydrochloric acid soln step b) is 0.7mol/L～2mol/L.
10. method as claimed in claim 7, is characterized in that: step b) by step a) in synthetic potassium tetratitanate be dissolved in the second hydrochloric acid soln, carry out proton-exchange reaction, be specially:
By step a) in synthetic potassium tetratitanate be dissolved in the second hydrochloric acid soln, stir 3～5 days, and change the second hydrochloric acid soln every day one time.
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| CN105347392A (en) * | 2015-10-30 | 2016-02-24 | 攀枝花学院 | Controllable nanocrystalline TiO2 particle, and preparation method and use thereof |
| WO2016026340A1 (en) * | 2014-08-20 | 2016-02-25 | 北京师范大学 | Tio2 nanocrystal and synthesis method therefor |
| CN110451559A (en) * | 2019-07-29 | 2019-11-15 | 晋中学院 | A kind of Detitanium-ore-type TiO of [111]-crystal face exposure2Nanocrystalline preparation method and application |
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| CN114311865B (en) * | 2021-12-15 | 2023-08-15 | 佛山(华南)新材料研究院 | Laminated TiO 2 Preparation method of heat conducting material |
| CN115254003B (en) * | 2022-08-29 | 2023-05-30 | 哈尔滨工业大学（威海） | Porous layered K capable of efficiently adsorbing organic dye 2 Ti 8 O 17 Process for preparing nano whisker |
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