CN106423117A - Preparation method of TiO2 graded mixed crystal material - Google Patents
Preparation method of TiO2 graded mixed crystal material Download PDFInfo
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- CN106423117A CN106423117A CN201610827392.8A CN201610827392A CN106423117A CN 106423117 A CN106423117 A CN 106423117A CN 201610827392 A CN201610827392 A CN 201610827392A CN 106423117 A CN106423117 A CN 106423117A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000013078 crystal Substances 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007900 aqueous suspension Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 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
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 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
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011160 research 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
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 238000004140 cleaning Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005755 formation reaction 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
- 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
- 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
- 238000012360 testing method Methods 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
-
- 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)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation method of a TiO2 graded mixed crystal material. The preparation method comprises the following steps: (1) adding a NaOH water solution into titanium dioxide P25 water turbid liquid, and adding H2O2 to generate hydrothermal reaction; (2) washing reactants in the step (1), and soaking the reactants with acid; and (3) rewashing the soaked products in the step (2), drying, and calcining. The preparation method is simple and easy to generalize and use, the energy consumption is low, the product raw materials are wide in source, and the yield is high.
Description
Technical field
The invention belongs to inorganic semiconductor photocatalysis field is and in particular to a kind of TiO2The preparation side of classification mixed crystal material
Method.
Background technology
TiO2Stable in properties, nontoxic, catalysis activity is high, can use solar energy depth degradation organic matter, non-secondary pollution,
Reaction condition is gentle, cheap, is the more nano photocatalyst catalytic material of current research.Nano-TiO2There is good photocatalysis
Performance, it holds out broad prospects at aspects such as antibacterial, deodorant, sewage disposal, air cleanings.TiO2Performance shape with itself
Looks, size, different crystal forms etc. have positive connection.
TiO2Have three kinds of crystalline forms, be respectively anatase, rutile and brockite, wherein anatase and rutile be tetragonal
System, brockite is rhombic system.By different raw materials, control reaction condition can prepare anatase, rutile mixed crystal.Generally
Think, Anatase is higher than the photocatalytic activity of Rutile Type, research finds, the mixed crystal TiO containing anatase and rutile2Than
Pure Anatase TiO2There is higher catalysis activity.Catalysis activity is also relevant with pattern, has big reference area, then favorably
In the absorption to organic pollution for the increase, and strengthen photocatalysis efficiency.
TiO2Preparation method have vapor phase method and liquid phase method, wherein liquid phase method includes sol-gel process, microemulsion method, water
Hot method, liquid-phase precipitation method, ionic liquid chemical synthesis.
Hydro-thermal method is a kind of conventional reaction method, is carried out instead by controlling the pressure and temperature of solution and the water of predecessor
Should, mostly carry out in water heating kettle, be higher than 100 DEG C its temperature, pressure is metatitanic acid more than 101.3kPa, the most frequently used presoma more
Four butyl esters, the solution in kettle and temperature determine its pressure.Reaction temperature and the crystallinity of time effects product.Hydro-thermal method can be straight
Connect the powder of prepared well-crystallized, be not required to do high-temperature process, it is to avoid the powder hard aggregation that is likely to form in the process, and
By changing process conditions, can achieve the control to characteristics such as diameter of particle, crystal formations, meanwhile, prepared powder purity is high.But
The preparation method yield of prior art is relatively low, energy consumption is larger, is unfavorable for large-scale production.
Content of the invention
An object of the present invention is to provide a kind of TiO2The preparation method of classification mixed crystal material.The present invention utilizes hydro-thermal
Method is passed through to control temperature, time, the amount of pattern controlling agent, is prepared for a kind of three-dimensional classification mixed crystal being made up of one-dimensional nano line
TiO2Classification mixed crystal material, regular appearance, size is homogeneous.The preparation method of the present invention is simple, and energy consumption is little, and product raw material is wide, produces
Rate height is it is easy to promote the use of.
For reaching this purpose, the present invention employs the following technical solutions：
A kind of TiO2The preparation method of classification mixed crystal material, comprises the steps：
(1) add the NaOH aqueous solution in the aqueous suspension of titanium dioxide P25, add H2O2After carry out hydro-thermal reaction；
(2) use acid soak by after the product washing of step (1)；
(3) product after step (2) immersion is washed again, calcine after drying.
P25 hydrophily is relatively good, is preferably dispersed in water to contribute to P25, improves the uniformity of product, as excellent
Choosing, in the aqueous suspension of step (1) titanium dioxide P25, titanium dioxide P25 and the mass volume ratio of water are 1:100～200g/ml,
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 1:150～200g/ml, more preferably 1:150～180g/ml.
Preferably, the aqueous suspension of titanium dioxide P25 stirs ultrasonic more than 2 minutes when preparing, preferably 3-20 minute.
Preferably, the NaOH aqueous solution of addition and the volume ratio of aqueous suspension are 0.5～10:1, for example, 0.8:1、2:1、
6:1、9:1 etc., preferably 1～5:1.
Preferably, the concentration of described NaOH is 5～20mol/L, preferably 10mol/L.
Preferably, stir after adding the NaOH aqueous solution, preferably stir more than 10 minutes, more preferably 20-40 minute.
Preferably, the H of addition2O2Volume ratio with aqueous suspension is 1:0.3～10, for example, 1:0.4、1:0.9、1:3、
1:6、1:8 etc., preferably 1:0.5～5.
Preferably, add H2O2After stir, preferably stir more than 10 minutes, more preferably 20-40 minute.
Preferably, described 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, carry out 5～8 hours under 192 DEG C etc., for example, 5.2 hours, 5.8 hours, 6.3 hours, 6.9 hours, 7.5 hours etc., preferably
Carry out 4～6 hours in 150 DEG C～180 DEG C declines.The present invention, under lower temperature conditions, is prepared directly by one step hydro thermal method
The classification mixed crystal TiO in about 1.5-2 μm of footpath2.
Preferably, described hydro-thermal reaction is carried out in air dry oven.
Preferably, washing deionized water described in step (2) is carried out, preferably carry out more than 2 times.
Preferably, described acid soak uses HNO3Carry out.
Preferably, the time of described acid soak is more than 5 hours, preferably 12 hours.
Preferably, described HNO3Concentration be 0.05～0.2mol/L, preferably 0.1mol/L.
Preferably, washing deionized water described in step (3), ethanol are carried out successively.
Preferably, it is washed with deionized to neutrality.
Preferably, more than 2 times are washed with ethanol.
Preferably, the temperature of described drying is 40～100 DEG C, preferably 70 DEG C, time of described drying be 5 hours with
On, preferably 10 hours.
Preferably, the time of described calcining is 300～600 DEG C, preferably 400 DEG C, time of described calcining be 1 hour with
On, preferably 2 hours.
Preferably, described calcining when heating rate 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 little, and product raw material is wide, and synthetic quantity is big, and yield height is it is easy to promote the use of；It is micro- that the nano wire of present invention preparation is constituted
Meter level TiO2Classification mixed crystal size is big, and specific surface area is big, high adsorption capacity, high catalytic efficiency, and catalytic performance is good.
Brief description
Fig. 1 is the TiO that the embodiment of the present invention one is obtained2Classification mixed crystal SEM figure；
Fig. 2 is the TiO that the embodiment of the present invention one is obtained2Classification mixed crystal XRD；
Fig. 3 is the TiO that the embodiment of the present invention one is obtained2Classification mixed crystal degraded MB figure.
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or restriction the scope of the present invention, protection scope of the present invention is defined by claims.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
For the present invention is better described, readily appreciate technical scheme, the present invention's is typical but non-limiting
Embodiment is as follows：
Embodiment one
(1) 0.1g titanium dioxide P25 is added in 18ml deionized water, stirs ultrasonic 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 42ml NaOH
(10M), stir 30 minutes.
(3) add 15ml H again toward in the reactant in step (2)2O2, stir 30 minutes, 150 DEG C are reacted 5 hours, cooling
To room temperature.
(4) the product deionized water in step (3), constantly washing, until close neutral, then uses 5ml0.1M HNO3
Soak 12 hours, then deionized water be washed till neutrality,
(5) the product ethanol in step (4) is washed twice, 70 DEG C are dried 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours for 400 DEG C in Muffle furnace, 5 DEG C/min of heating rate.
The TiO that Fig. 1 is obtained for the present embodiment2Classification mixed crystal SEM figure；The TiO that Fig. 2 is obtained for the present embodiment2Classification mixed crystal
XRD.
TiO obtained by the present embodiment as can be seen from Figure 22The three-dimensional hierarchical structure that material is made up of one-dimensional nano line, by
Anatase and two kinds of crystalline phase compositions of rutile, obtained TiO as can be seen from Figure 121.8 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, stirs ultrasonic 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 42ml NaOH
(10M), stir 30 minutes.
(3) add 15ml H again toward in the reactant in step (2)2O2, stir 30 minutes, 150 DEG C are reacted 5 hours, cooling
To room temperature.
(4) the product deionized water in step (3), constantly washing, until close neutral, then uses 5ml0.1M HNO3
Soak 12 hours, then deionized water be washed till neutrality,
(5) the product ethanol in step (4) is washed twice, 70 DEG C are dried 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours for 400 DEG C in Muffle furnace, 5 DEG C/min of heating rate.
TiO obtained by the present embodiment2Material contains the three-dimensional hierarchical structure being made up of in a large number one-dimensional nano line, by anatase
With two kinds of crystalline phase compositions of rutile, 1.7 μm of size average out to.
Embodiment three
(1) 0.1g titanium dioxide P25 is added in 18ml deionized water, stirs ultrasonic 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 40ml NaOH
(10M), stir 30 minutes.
(3) add 15ml H again toward in the reactant in step (2)2O2, stir 30 minutes, 150 DEG C are reacted 5 hours, cooling
To room temperature.
(4) the product deionized water in step (3), constantly washing, until close neutral, then uses 5ml0.1M HNO3
Soak 12 hours, then deionized water be washed till neutrality,
(5) the product ethanol in step (4) is washed twice, 70 DEG C are dried 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours for 400 DEG C in Muffle furnace, 5 DEG C/min of heating rate.
TiO obtained by the present embodiment2Material contains the three-dimensional hierarchical structure being made up of in a large number one-dimensional nano line, by anatase
With rutile kind two crystalline phase composition, 1.7 μm of size average out to.
Example IV
(1) 0.1g titanium dioxide P25 is added in 18ml deionized water, stirs ultrasonic 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 42ml NaOH
(10M), stir 30 minutes.
(3) add 15ml H again toward in the reactant in step (2)2O2, stir 30 minutes, 180 DEG C are reacted 8 hours, cooling
To room temperature.
(4) the product deionized water in step (3), constantly washing, until close neutral, then uses 5ml0.1M HNO3
Soak 12 hours, then deionized water be washed till neutrality,
(5) the product ethanol in step (4) is washed twice, 70 DEG C are dried 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours for 400 DEG C in Muffle furnace, 5 DEG C/min of heating rate.
TiO obtained by the present embodiment2Material contains the three-dimensional hierarchical structure being made up of in a large number one-dimensional nano line, by anatase
With two kinds of crystalline phase compositions of rutile, 1.9 μm of size average out to.
Embodiment five
(1) 0.1g titanium dioxide P25 is added in 18ml deionized water, stirs ultrasonic 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 42ml NaOH
(10M), stir 30 minutes.
(3) add 10ml H again toward in the reactant in step (2)2O2, stir 30 minutes, 150 DEG C are reacted 5 hours, cooling
To room temperature.
(4) the product deionized water in step (3), constantly washing, until close neutral, then uses 5ml0.1M HNO3
Soak 12 hours, then deionized water be washed till neutrality,
(5) the product ethanol in step (4) is washed twice, 70 DEG C are dried 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours for 400 DEG C in Muffle furnace, 5 DEG C/min of heating rate.
TiO obtained by the present embodiment2Material contains the three-dimensional hierarchical structure being made up of in a large number one-dimensional nano line, by anatase
With two kinds of crystalline phase compositions of rutile, 1.6 μm of size average out to.
Embodiment six
(1) 0.1g titanium dioxide P25 is added in 18ml deionized water, stirs ultrasonic 5 minutes.
(2) dirty solution in step (1) is transferred in 100ml ptfe autoclave, adds 42ml NaOH
(10M), stir 30 minutes.
(3) add 5ml H again toward in the reactant in step (2)2O2, stir 30 minutes, 150 DEG C are reacted 5 hours, cooling
To room temperature.
(4) the product deionized water in step (3), constantly washing, until close neutral, then uses 5ml0.1M HNO3
Soak 12 hours, then deionized water be washed till neutrality,
(5) the product ethanol in step (4) is washed twice, 70 DEG C are dried 10 hours.
(6) sample segment in step (5) is taken to calcine 2 hours for 400 DEG C in Muffle furnace, 5 DEG C/min of heating rate.
TiO obtained by the present embodiment2Material contains the three-dimensional hierarchical structure being made up of in a large number one-dimensional nano line, by anatase
With two kinds of crystalline phase compositions of rutile, 1.5 μm of size average out to.
Embodiment seven
Embodiment seven is the TiO that the embodiment of the present invention one is obtained2Classification mixed crystal degradation of methylene blue (MB) solution, specifically side
Method is：Take 10mg TiO2It is distributed in the MB solution of 100ml 10mg/L, ultrasonic 1 minute, under dark surrounds, dark absorption 1 is little
When, then use high pressure xenon lamp ultraviolet lighting, sampled 4ml every 5 minutes, 8000r/min is centrifuged 4 minutes, take the supernatant can in ultraviolet
See in spectrophotometer test, the characteristic absorption peak of methylene blue at 665nm, when taking absorption value and the photocatalysis at 665nm
Between do figure in origin, obtain Fig. 3.
This example demonstrates that the inventive method resulting materials have good Photocatalytic Degradation Property.
Applicant states, the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
It is not limited to above-mentioned detailed construction feature, that is, do not mean that the present invention has to 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, the equivalence replacement to part selected by the present invention
And the increase of accessory, selection of concrete mode etc., all fall within protection scope of the present invention and open within the scope of.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The combination of energy no longer separately illustrates.
Additionally, can also be combined between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (10)
1. a kind of TiO2The preparation method of classification mixed crystal material, comprises the steps：
(1) add the NaOH aqueous solution in the aqueous suspension of titanium dioxide P25, add H2O2After carry out hydro-thermal reaction；
(2) use acid soak by after the product washing of step (1)；
(3) product after step (2) immersion is washed again, calcine after drying.
2. preparation method according to claim 1 is it is characterised in that two in the aqueous suspension of step (1) titanium dioxide P25
Titanium oxide P25 is 1 with the mass volume ratio of water:100～200g/ml, preferably 1:150～200g/ml, more preferably 1:150
～180g/ml；
Preferably, the aqueous suspension of titanium dioxide P25 stirs ultrasonic more than 2 minutes when preparing, preferably 3-20 minute.
3. preparation method according to claim 1 and 2 it is characterised in that step (1) in add the NaOH aqueous solution and water
The volume ratio of suspension is 0.5～10:1, preferably 1～5:1；
Preferably, the concentration of described NaOH is 5～20mol/L, preferably 10mol/L；
Preferably, stir after adding the NaOH aqueous solution, preferably stir more than 10 minutes, more preferably 20-40 minute.
4. the preparation method according to any one of claim 1-3 it is characterised in that in step (1) add H2O2Hang with water
The volume ratio of turbid liquid is 1:0.3～10, preferably 1:0.5～5；
Preferably, add H2O2After stir, preferably stir more than 10 minutes, more preferably 20-40 minute.
5. the preparation method according to any one of claim 1-4 is it is characterised in that hydro-thermal reaction described in step (1) exists
Carry out at 150 DEG C～200 DEG C 5～8 hours, preferably carry out 4～6 hours in 150 DEG C～180 DEG C declines；
Preferably, described hydro-thermal reaction is carried out in air dry oven.
6. the preparation method according to any one of claim 1-5 it is characterised in that described in step (2) washing spend from
Sub- water is carried out, and preferably carries out more than 2 times.
7. the preparation method according to any one of claim 1-6 is it is characterised in that acid soak described in step (2) uses
HNO3Carry out；
Preferably, the time of described acid soak is more than 5 hours, preferably 12 hours；
Preferably, described HNO3Concentration be 0.05～0.2mol/L, preferably 0.1mol/L.
8. the preparation method according to any one of claim 1-7 it is characterised in that described in step (3) washing spend from
Sub- water, ethanol are carried out successively；
Preferably, it is washed with deionized to neutrality；
Preferably, more than 2 times are washed with ethanol.
9. the preparation method according to any one of claim 1-8 it is characterised in that described in step (3) dry temperature
For 40～100 DEG C, preferably 70 DEG C, the time of described drying is more than 5 hours, preferably 10 hours.
10. the preparation method according to any one of claim 1-9 it is characterised in that described in step (3) calcining time
For 300～600 DEG C, preferably 400 DEG C, the time of described calcining is more than 1 hour, preferably 2 hours；
Preferably, heating rate during described calcining is 2～10 DEG C/min, preferably 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 |
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| 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 |
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