CN106423117B - A kind of TiO2It is classified the preparation method of mixed crystal material - Google Patents
A kind of TiO2It is classified the preparation method of mixed crystal material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000013078 crystal Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 239000000047 product Substances 0.000 claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 230000001550 time effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of TiO2It is classified the preparation method of mixed crystal material, includes the following steps: that (1) NaOH aqueous solution is added into the aqueous suspension of titanium dioxide P25, adds H2O2After carry out hydro-thermal reaction；(2) acid soak is used after washing the reaction product of step (1)；(3) product after impregnating step (2) washs again, calcines after drying.Preparation method of the invention is simple, and energy consumption is small, and product raw material is wide, and yield is high, use easy to spread.
Description
Technical field
The invention belongs to inorganic semiconductor photocatalysis fields, and in particular to a kind of TiO2It is classified the preparation side of mixed crystal material
Method.
Background technique
TiO2Property is stablized, nontoxic, and catalytic activity is high, is able to use solar energy depth degradation organic matter, without secondary pollution,
Reaction condition is mild, cheap, is to study more nano photocatalyst catalytic material at present.Nano-TiO2With good photocatalysis
Performance, antibacterial, deodorization, sewage treatment, in terms of hold out broad prospects.TiO2Performance shape with itself
Looks, size, different crystal forms etc. have positive connection.
TiO2There are three types of crystalline forms, are anatase, rutile and brockite respectively, wherein anatase and rutile are tetragonals
System, brockite is rhombic system.Anatase, rutile mixed crystal can be prepared by different raw materials, control reaction condition.Usually
Think, Anatase is higher than the photocatalytic activity of Rutile Type, the study found that the mixed crystal TiO containing anatase and rutile2Than
Pure Anatase TiO2With higher catalytic activity.Catalytic activity is also related with pattern, has big reference area, then favorably
In absorption of the increase to organic pollutant, and enhance photocatalysis efficiency.
TiO2Preparation method have vapor phase method and liquid phase method, wherein liquid phase method includes sol-gel method, microemulsion method, water
Thermal method, liquid-phase precipitation method, ionic liquid chemical synthesis.
Hydro-thermal method is a kind of common reaction method, is carried out by the water of the pressure and temperature and predecessor that control solution anti-
It answers, is carried out in water heating kettle mostly, temperature is higher than 100 DEG C, and pressure is more than 101.3kPa, and most common presoma is metatitanic acid more
Four butyl esters, solution and temperature in kettle determine its pressure.The crystallinity of reaction temperature and time effects product.Hydro-thermal method can be straight
The powder for meeting obtained well-crystallized is not required to do high-temperature process, avoids the powder hard aggregation being likely to form in the process, and
By changing process conditions, it can be achieved that control to characteristics such as diameter of particle, crystal forms, meanwhile, powder purity obtained is high.But
The preparation method yield of the prior art is lower, energy consumption is larger, is unfavorable for large-scale production.
Summary of the invention
One of the objects of the present invention is to provide a kind of TiO2It is classified the preparation method of mixed crystal material.The present invention utilizes hydro-thermal
Method is prepared for a kind of three-dimensional classification mixed crystal being made of one-dimensional nano line by control temperature, time, the amount of pattern controlling agent
TiO2Classification mixed crystal material, regular appearance, size are uniform.Preparation method of the invention is simple, and energy consumption is small, and product raw material is wide, produces
Rate is high, use easy to spread.
To achieve this purpose, the present invention adopts the following technical scheme:
A kind of TiO2It is classified the preparation method of mixed crystal material, is included the following steps:
(1) NaOH aqueous solution is added into the aqueous suspension of titanium dioxide P25, adds H2O2After carry out hydro-thermal reaction；
(2) acid soak is used after washing the reaction product of step (1)；
(3) product after impregnating step (2) washs again, calcines after drying.
P25 hydrophily is relatively good, is preferably dispersed in water to facilitate P25, the uniformity of product is improved, as excellent
It selecting, the mass volume ratio of titanium dioxide P25 and water is 1:100~200g/ml in the aqueous suspension of step (1) titanium dioxide P25,
For example, 1:103g/ml, 1:110g/ml, 1:115g/ml, 1:126g/ml, 1:135g/ml, 1:148g/ml, 1:160g/ml,
1:180g/ml, 1:194g/ml etc., preferably 1:150~200 g/ml, more preferably 1:150~180g/ml.
Preferably, stirring ultrasound 2 minutes or more, preferably 3-20 minutes when the aqueous suspension of titanium dioxide P25 is prepared.
Preferably, the volume ratio of the NaOH aqueous solution and aqueous suspension of addition is 0.5~10:1, for example, 0.8:1,2:
1,6:1,9:1 etc., preferably 1~5:1.
Preferably, the concentration of the NaOH is 5~20mol/L, preferably 10mol/L.
Preferably, it is stirred after NaOH aqueous solution being added, preferably stir 10 minutes or more, it is 20-40 minutes more preferable.
Preferably, the H of addition2O2Be 1:0.3~10 with the volume ratio of aqueous suspension, for example, 1:0.4,1:0.9,1:3,
1:6,1:8 etc., preferably 1:0.5~5.
Preferably, H is added2O2After stir, preferably stir 10 minutes or more, it is 20-40 minutes more preferable.
Preferably, the hydro-thermal reaction is at 150 DEG C~200 DEG C, for example, 155 DEG C, 162 DEG C, 170 DEG C, 178 DEG C, 186
DEG C, 192 DEG C etc. it is lower carry out 5~8 hours, for example, 5.2 hours, 5.8 hours, 6.3 hours, 6.9 hours, 7.5 hours etc., preferably
It is carried out 4~6 hours in 150 DEG C~180 DEG C declines.The present invention is prepared directly under lower temperature conditions by one step hydro thermal method
About 1.5-2 μm of diameter of classification mixed crystal TiO2。
Preferably, the hydro-thermal reaction carries out in air dry oven.
Preferably, washing described in step (2) is carried out with deionized water, preferably carry out 2 times or more.
Preferably, the acid soak uses HNO3It carries out.
Preferably, the time of the acid soak is 5 hours or more, preferably 12 hours.
Preferably, the HNO3Concentration be 0.05~0.2mol/L, preferably 0.1mol/L.
Preferably, washing deionized water, ethyl alcohol described in step (3) successively carry out.
Preferably, it is washed with deionized to neutrality.
Preferably, with ethanol washing 2 times or more.
Preferably, the temperature of the drying is 40~100 DEG C, preferably 70 DEG C, time of the drying be 5 hours with
On, preferably 10 hours.
Preferably, the time of the calcining is 300~600 DEG C, and preferably 400 DEG C, the time of the calcining is 1 hour
More than, preferably 2 hours.
Preferably, the heating rate when calcining be 2~10 DEG C/min, for example, 3 DEG C/min, 6 DEG C/min, 9 DEG C/
Min etc., preferably 5 DEG C/min.
Compared with prior art, the present invention at least has the advantages that preparation method is simple, the reaction time
Short, energy consumption is small, and product raw material is wide, and synthetic quantity is big, and yield is high, use easy to spread；Nano wire prepared by the present invention is constituted micro-
Meter level TiO2Classification mixed crystal size is big, and large specific surface area, adsorption capacity is strong, high catalytic efficiency, and catalytic performance is good.
Detailed description of the invention
Fig. 1 is TiO made from the embodiment of the present invention one2It is classified mixed crystal SEM figure；
Fig. 2 is TiO made from the embodiment of the present invention one2It is classified mixed crystal XRD diagram；
Fig. 3 is TiO made from the embodiment of the present invention one2It is classified mixed crystal degradation MB figure.
The present invention is described in more detail below.But following examples is only simple example of the invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Embodiment one
(1) 0.1g titanium dioxide P25 is added in 18ml deionized water, stirring ultrasound 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 42ml NaOH
(10M) is stirred 30 minutes.
(3) 15ml H is added into the reactant in step (2) again2O2, stir 30 minutes, 150 DEG C are reacted 5 hours, cooling
To room temperature.
(4) product in step (3) is constantly washed with deionized water until then using 5ml 0.1M close to neutrality
HNO3It impregnates 12 hours, then is washed with deionized water to neutrality,
(5) the product in step (4) with ethanol washing twice, 70 DEG C dry 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours at 400 DEG C of Muffle furnace, 5 DEG C/min of heating rate.
Fig. 1 is TiO made from the present embodiment2It is classified mixed crystal SEM figure；Fig. 2 is TiO made from the present embodiment2It is classified mixed crystal
XRD diagram.
TiO obtained by the present embodiment as can be seen from Figure 22The three-dimensional hierarchical structure that material is made of one-dimensional nano line, by
Two kinds of crystal phases of anatase and rutile form, as can be seen from Figure 1 obtained TiO21.8 μm of the size average out to of material, light is urged
Change performance test Fig. 3.
Embodiment two
(1) 0.1g titanium dioxide P25 is added in 15ml deionized water, stirring ultrasound 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 42ml NaOH
(10M) is stirred 30 minutes.
(3) 15ml H is added into the reactant in step (2) again2O2, stir 30 minutes, 150 DEG C are reacted 5 hours, cooling
To room temperature.
(4) product in step (3) is constantly washed with deionized water until then using 5ml 0.1M close to neutrality
HNO3It impregnates 12 hours, then is washed with deionized water to neutrality,
(5) the product in step (4) with ethanol washing twice, 70 DEG C dry 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours at 400 DEG C of Muffle furnace, 5 DEG C/min of heating rate.
TiO obtained by the present embodiment2Material contains the three-dimensional hierarchical structure being largely made of one-dimensional nano line, by anatase
It is formed with two kinds of crystal phases of rutile, 1.7 μm of size average out to.
Embodiment three
(1) 0.1g titanium dioxide P25 is added in 18ml deionized water, stirring ultrasound 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 40ml NaOH
(10M) is stirred 30 minutes.
(3) 15ml H is added into the reactant in step (2) again2O2, stir 30 minutes, 150 DEG C are reacted 5 hours, cooling
To room temperature.
(4) product in step (3) is constantly washed with deionized water until then using 5ml 0.1M close to neutrality
HNO3It impregnates 12 hours, then is washed with deionized water to neutrality,
(5) the product in step (4) with ethanol washing twice, 70 DEG C dry 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours at 400 DEG C of Muffle furnace, 5 DEG C/min of heating rate.
TiO obtained by the present embodiment2Material contains the three-dimensional hierarchical structure being largely made of one-dimensional nano line, by anatase
It is formed with two crystal phase of rutile kind, 1.7 μm of size average out to.
Example IV
(1) 0.1g titanium dioxide P25 is added in 18ml deionized water, stirring ultrasound 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 42ml NaOH
(10M) is stirred 30 minutes.
(3) 15ml H is added into the reactant in step (2) again2O2, stir 30 minutes, 180 DEG C are reacted 8 hours, cooling
To room temperature.
(4) product in step (3) is constantly washed with deionized water until then using 5ml 0.1M close to neutrality
HNO3It impregnates 12 hours, then is washed with deionized water to neutrality,
(5) the product in step (4) with ethanol washing twice, 70 DEG C dry 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours at 400 DEG C of Muffle furnace, 5 DEG C/min of heating rate.
TiO obtained by the present embodiment2Material contains the three-dimensional hierarchical structure being largely made of one-dimensional nano line, by anatase
It is formed with two kinds of crystal phases of rutile, 1.9 μm of size average out to.
Embodiment five
(1) 0.1g titanium dioxide P25 is added in 18ml deionized water, stirring ultrasound 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 42ml NaOH
(10M) is stirred 30 minutes.
(3) 10ml H is added into the reactant in step (2) again2O2, stir 30 minutes, 150 DEG C are reacted 5 hours, cooling
To room temperature.
(4) product in step (3) is constantly washed with deionized water until then using 5ml 0.1M close to neutrality
HNO3It impregnates 12 hours, then is washed with deionized water to neutrality,
(5) the product in step (4) with ethanol washing twice, 70 DEG C dry 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours at 400 DEG C of Muffle furnace, 5 DEG C/min of heating rate.
TiO obtained by the present embodiment2Material contains the three-dimensional hierarchical structure being largely made of one-dimensional nano line, by anatase
It is formed with two kinds of crystal phases of rutile, 1.6 μm of size average out to.
Embodiment six
(1) 0.1g titanium dioxide P25 is added in 18ml deionized water, stirring ultrasound 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 42ml NaOH
(10M) is stirred 30 minutes.
(3) 5ml H is added into the reactant in step (2) again2O2, stir 30 minutes, 150 DEG C are reacted 5 hours, cooling
To room temperature.
(4) product in step (3) is constantly washed with deionized water until then using 5ml 0.1M close to neutrality
HNO3It impregnates 12 hours, then is washed with deionized water to neutrality,
(5) the product in step (4) with ethanol washing twice, 70 DEG C dry 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours at 400 DEG C of Muffle furnace, 5 DEG C/min of heating rate.
TiO obtained by the present embodiment2Material contains the three-dimensional hierarchical structure being largely made of one-dimensional nano line, by anatase
It is formed with two kinds of crystal phases of rutile, 1.5 μm of size average out to.
Embodiment seven
Embodiment seven is TiO made from the embodiment of the present invention one2It is classified mixed crystal degradation of methylene blue (MB) solution, specific side
Method are as follows: take 10mg TiO2It is distributed in the MB solution of 100ml 10mg/L, it is small secretly to absorb 1 under dark surrounds for ultrasound 1 minute
When, then with high pressure xenon lamp ultraviolet lighting, every 5 minutes sampling 4ml, 8000r/min was centrifuged 4 minutes, take supernatant it is ultraviolet can
See in spectrophotometer and test, the characteristic absorption peak of methylene blue is at 665nm, when taking the absorption value and photocatalysis at 665nm
Between in origin do figure, obtain Fig. 3.
This example demonstrates that the method for the present invention resulting materials have good Photocatalytic Degradation Property.
The Applicant declares that the present invention is explained by the above embodiments detailed construction feature of the invention, but the present invention is simultaneously
It is not limited to above-mentioned detailed construction feature, that is, does not mean that the present invention must rely on above-mentioned detailed construction feature and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of component selected by the present invention
And increase, selection of concrete mode of accessory etc., all of which fall within the scope of protection and disclosure of the present invention.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (32)
1. a kind of TiO2It is classified the preparation method of mixed crystal material, which comprises the steps of:
(1) NaOH aqueous solution is added into the aqueous suspension of titanium dioxide P25, adds H2O2After carry out hydro-thermal reaction；
(2) acid soak is used after washing the reaction product of step (1)；
(3) product after impregnating step (2) washs again, calcines after drying；
In the aqueous suspension of step (1) the titanium dioxide P25 mass volume ratio of titanium dioxide P25 and water be 1:100~
200g/ml；The NaOH aqueous solution of addition and the volume ratio of aqueous suspension are 0.5~10:1；The concentration of the NaOH be 5~
20mol/L；The H of addition2O2Volume ratio with aqueous suspension is 1:0.3~10；
The acid soak uses HNO3It carries out.
2. preparation method according to claim 1, which is characterized in that two in the aqueous suspension of step (1) titanium dioxide P25
The mass volume ratio of titanium oxide P25 and water is 1:150~200g/ml.
3. preparation method according to claim 2, which is characterized in that dioxy in the aqueous suspension of the titanium dioxide P25
The mass volume ratio for changing titanium P25 and water is 1:150~180g/ml.
4. preparation method according to claim 1, which is characterized in that when the aqueous suspension of the titanium dioxide P25 is prepared
Stirring ultrasound 2 minutes or more.
5. the preparation method according to claim 4, which is characterized in that when the aqueous suspension of the titanium dioxide P25 is prepared
Stirring ultrasound 3-20 minutes.
6. preparation method according to claim 1, which is characterized in that the NaOH aqueous solution and water being added in step (1) are outstanding
1~5:1 of volume ratio of turbid.
7. preparation method according to claim 1, which is characterized in that the concentration of the NaOH is 10mol/L.
8. preparation method according to claim 1, which is characterized in that stirred after the addition NaOH aqueous solution.
9. preparation method according to claim 8, which is characterized in that stirred after the addition NaOH aqueous solution 10 minutes with
On.
10. preparation method according to claim 9, which is characterized in that described 20-40 points of the stirring of addition NaOH aqueous solution
Clock.
11. preparation method according to claim 1, which is characterized in that the H being added in step (1)2O2With aqueous suspension
Volume ratio is 1:0.5~5.
12. preparation method according to claim 1, which is characterized in that H is added2O2After stir.
13. preparation method according to claim 12, which is characterized in that H is added2O2Stir 10 minutes afterwards or more.
14. preparation method according to claim 13, which is characterized in that H is added2O2It stirs 20-40 minutes afterwards.
15. preparation method according to claim 1, which is characterized in that hydro-thermal reaction described in step (1) 150 DEG C~
It is carried out 5~8 hours at 200 DEG C.
16. preparation method according to claim 15, which is characterized in that hydro-thermal reaction described in step (1) 150 DEG C~
It is carried out 4~6 hours at 180 DEG C.
17. preparation method according to claim 1, which is characterized in that the hydro-thermal reaction carries out in air dry oven.
18. preparation method according to claim 1, which is characterized in that washing deionized water described in step (2) into
Row.
19. preparation method according to claim 18, which is characterized in that washing deionized water described in step (2) into
Row 2 times or more.
20. preparation method according to claim 1, which is characterized in that the time of the acid soak is 5 hours or more.
21. preparation method according to claim 20, which is characterized in that the time of the acid soak is 12 hours.
22. preparation method according to claim 1, which is characterized in that the HNO3Concentration be 0.05~0.2mol/L.
23. preparation method according to claim 22, which is characterized in that the HNO3Concentration be 0.1mol/L.
24. preparation method according to claim 1, which is characterized in that washing deionized water, second described in step (3)
Alcohol successively carries out.
25. preparation method according to claim 24, which is characterized in that step (3) washing is washed with deionized
To neutrality.
26. preparation method according to claim 24, which is characterized in that use ethanol washing 2 times or more.
27. preparation method according to claim 1, which is characterized in that the temperature of drying described in step (3) be 40~
100 DEG C, the time of the drying is 5 hours or more.
28. preparation method according to claim 27, which is characterized in that the temperature of step (3) described drying is 70 DEG C, institute
The time for stating drying is 10 hours.
29. preparation method according to claim 1, which is characterized in that the temperature of calcining described in step (3) be 300~
600 DEG C, the time of the calcining is 1 hour or more.
30. preparation method according to claim 29, which is characterized in that the temperature of calcining described in step (3) is 400
DEG C, the time of the calcining is 2 hours.
31. preparation method according to claim 1, which is characterized in that the heating rate when calcining is 2~10 DEG C/
min。
32. preparation method according to claim 31, which is characterized in that the heating rate when calcining is 5 DEG C/min.
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| CN103570062A (en) * | 2012-08-01 | 2014-02-12 | 国家纳米科学中心 | Three-dimensional flower-like TiO2 microspheres composed of nanowires and preparation method thereof |
| CN103570061A (en) * | 2012-08-01 | 2014-02-12 | 国家纳米科学中心 | Three-dimensional sheet TiO2 material and preparation method and application thereof |
| CN104722302A (en) * | 2015-03-25 | 2015-06-24 | 浙江工业大学 | Acidified mixed crystal TiO2Nanowire supported photocatalyst and preparation and application thereof |
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| CN103570061A (en) * | 2012-08-01 | 2014-02-12 | 国家纳米科学中心 | Three-dimensional sheet TiO2 material and preparation method and application thereof |
| CN103073057A (en) * | 2013-01-29 | 2013-05-01 | 国家纳米科学中心 | Graded mixed crystal TiO2 micro-nanomaterial, preparation method and application of micro-nanomaterial |
| CN104722302A (en) * | 2015-03-25 | 2015-06-24 | 浙江工业大学 | Acidified mixed crystal TiO2Nanowire supported photocatalyst and preparation and application thereof |
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