CN106179316B - A kind of preparation method and application of titanate nanotube array - Google Patents
A kind of preparation method and application of titanate nanotube array Download PDFInfo
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- CN106179316B CN106179316B CN201610538481.0A CN201610538481A CN106179316B CN 106179316 B CN106179316 B CN 106179316B CN 201610538481 A CN201610538481 A CN 201610538481A CN 106179316 B CN106179316 B CN 106179316B
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- 239000002071 nanotube Substances 0.000 title claims abstract description 44
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000009415 formwork Methods 0.000 claims abstract description 46
- 230000002146 bilateral effect Effects 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 14
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052712 strontium Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 7
- 238000000280 densification Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 5
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 abstract description 5
- 235000013339 cereals Nutrition 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 5
- 235000009566 rice Nutrition 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 12
- 229910002113 barium titanate Inorganic materials 0.000 description 12
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 8
- 229910002115 bismuth titanate Inorganic materials 0.000 description 7
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000000120 microwave digestion Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/39—
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention belongs to nanocomposite and photocatalysis technology field, more particularly to a kind of preparation method and application of titanate nanotube array.Bilateral porous alumina formwork is inserted vertically into reactor center and is fixed, Ti (OC are separately added into template both sides4H9)4Solution and nitrate solution adjust pH value and stand reaction；Template is taken out into drying, annealing, washing, obtains titanate nanotube array.Titanate nanotube array is dispersed in water to obtain suspension, and with bismuth nitrate and Ti (OC4H9)4Precursor sol mixing carry out hydro-thermal reaction, obtaining area load has the titanate nanotube array of bismuth sodium titanate rice grain.
Description
Technical field
The invention belongs to nanocomposite and photocatalysis technology field, more particularly to a kind of titanate nanotube array
Preparation method and application.
Background technology
Photocatalysis technology is to absorb sunlight using light responsive material to generate electron-hole pair, to be generated with the external world
Oxidation-reduction reaction.From after Fujishima in 1972 and Honda have found titanium dioxide electrodes glazing electrocatalytic decomposition aquatic products oxygen,
Luminous energy is converted solar energy into using Photocatalitic Technique of Semiconductor and chemical energy has been a hot spot of research.But titanium dioxide
That there are energy gaps is larger for itself, it is seen that the problems such as light utilization efficiency is low, and recycling is difficult.So designing and preparing novel visible
The photocatalysis of response has important application value.
In recent years, Photocatalitic Technique of Semiconductor is efficiently to utilize solar energy and curb environmental pollution to provide a kind of effectively way
Diameter.In the photocatalytic process, ABO3Lacking oxygen present in type perovskite material structure can as light induced electron trap and
Electronics is captured, the compound of electronics-hole pair is can effectively stop.Meanwhile as typical ferroelectric material, barium titanate, strontium titanates
There is spontaneous polarization effect when less than Curie temperature with calcium titanate, and spontaneous polarization strength can be inverted with external electric field,
Small electrical field is established in intra-die.Electrons and holes detach under the electric field driven, and can more effectively migrate to catalyst
Electronics in the process and the recombination rate in hole are reduced in surface, improve the efficiency of light energy utilization.
Invention content
Present invention firstly provides a kind of preparation method of titanate nanotube array, concrete operations are：
(1) bilateral porous alumina formwork is inserted vertically into reactor center and fixed, make template that reactor to be isolated
Two-way reaction device is formed at equal two parts, ensures that the reactant of both sides is only mutually expanded by bilateral porous alumina formwork
It dissipates；It is separately added into Ti (OC in template both sides4H9)4The pH value of solution and nitrate solution, control both sides solution is 4~6, in
2~6 hours are stood under room temperature (25 DEG C),
Using both sides, infiltration method makes Ti (OC simultaneously in this step4H9)4The phase counterdiffusion in template duct with nitrate, hair
Biochemical reaction generates titanate,
Wherein, the aperture of bilateral porous alumina formwork is 50~200nm, and the preparation method of template is：By anodic oxidation
Aluminum alloy pattern plate removes the alumina barrier layer of bottom densification with 5wt% phosphoric acid dips, obtains bilateral porous alumina formwork,
A concentration of 0.01-0.1M of nitrate solution, nitrate are barium nitrate, strontium nitrate or calcium nitrate, Ti (OC4H9)4It is molten
A concentration of 0.012~0.12M of liquid can be when shorter by bilateral porous alumina formwork using both sides while infiltration method
The interior phase counterdiffusion for realizing ion in template duct, avoids alumina formwork and caves in, is broken；But pass through bilateral at present
The yield and purity of the both sides of the foraminous die plate obtained target product of infiltration method simultaneously are all very low, need to carry out product complicated
Purification operations and considerably increase raw material input, cause cost high,
And for this technological deficiency, the present invention appreciates the both sides of bilateral foraminous die plate first while infiltration method is led
The basic reason that efficiency of pcr product is few, purity is low is caused to be：Diffusion rates of the different cations in template duct have differences and
Lead to final product nonstoichiometry ratio, therefore the present invention just controls the concentration ratio of different cations when feeding intake consciously
Example, finally makes reaction carry out just right,
(2) by by step (1) reaction after bilateral porous alumina formwork take out, by template surface wiped clean and
It is dried under infrared lamp, then rising to 750 DEG C in Muffle furnace with 5 DEG C of heating rates per minute keeps the temperature 1 hour, finally uses
The NaOH solution of 2mol/L is washed, and titanate nanotube battle array is obtained after removing bilateral porous alumina formwork extra in product
Row,
The present invention also provides a kind of applications of the above-mentioned titanate nanotube array being prepared：
A, titanate nanotube array powder ultrasonic is scattered in deionized water and obtains metatitanic acid salt suspensioning liquid,
A concentration of 0.5g/L~2g/L of titanate in gained suspension；
B, bismuth nitrate solution is prepared, and is slowly dropped into Ti (OC into bismuth nitrate solution4H9)4It is formed uniform, stable, transparent
Precursor sol, gained colloidal sol is mixed and is stirred by ultrasonic with the metatitanic acid salt suspensioning liquid prepared by step a,
Wherein, a concentration of 0.005M~0.2M of the bismuth nitrate solution of preparation,
Colloidal sol is with the metatitanic acid salt suspensioning liquid prepared by step a according to mass ratio 1:5~1:10 mixing；
C, the mixture of the colloidal sol and suspension that are obtained in step b is packed into the hydrothermal reaction kettle with polytetrafluoroethyllining lining
In, adding deionized water makes the compactedness of reaction vessel be 60~80%, and the pH value for adjusting mixture carries out after being 11~13
Hydro-thermal reaction,
Wherein, the pH value of mixture is adjusted using the NaOH solution of 1.0M,
Hydrothermal temperature is 120~160 DEG C, and the reaction time is 2~6 hours；
D, by the reaction system cooled and filtered of step c, washing, under high pure nitrogen atmosphere being dried to obtain area load has
The titanate nanotube array of bismuth sodium titanate rice grain,
Wherein, washing operation is specifically, for several times using the HCl of 0.1M, deionized water, washes of absolute alcohol.
The present invention is based on nano-tube array structure titanate, in its body structure surface composite titanic acid bismuth nano particle, institute
Obtaining composite photo-catalyst both can be such that electric charge carrier diffusion path is elongated, and overcome conventional metal oxides light induced electron and sky
Compound disadvantage easily occurs for cave, and the high visible light catalysis activity of bismuth titanates is utilized and is imitated far above the light quantum of titanium oxide
Catalytic activity is extended to visible region by rate.
Description of the drawings
Fig. 1 is the XRD diagram of Characterization of Barium Titanate Nanotubes array/bismuth titanates composite photo-catalyst prepared by embodiment 1.
Fig. 2 is that titanate nanotube array/bismuth titanates composite photo-catalyst prepared by embodiment 1,2,3 is right under light illumination
The degradation rate schematic diagram of rhodamine B.
Specific implementation mode
Embodiment 1
(1) alumina barrier layer that anodic oxidation aluminium formwork is removed to bottom densification with 5wt% phosphoric acid dips, obtains aperture
For the bilateral porous alumina formwork of 100nm,
The bilateral porous alumina formwork is inserted vertically into reactor center and is fixed, template is made to be isolated into reactor
Equal two parts form two-way reaction device, ensure the reactant of both sides only by bilateral porous alumina formwork phase counterdiffusion；
Ti (the OC of isometric 0.018M are separately added into template both sides4H9)4The barium nitrate solution of solution and 0.01M, adjusts and controls
The pH value of both sides solution is 6, and stands 4 hours under room temperature (25 DEG C)；
(2) by by step (1) reaction after bilateral porous alumina formwork take out, by template surface wiped clean and
It is dried under infrared lamp, then rising to 750 DEG C using 5 DEG C of heating rates per minute in Muffle furnace keeps the temperature 1 hour as at annealing
Reason finally wash with the NaOH solution of 2mol/L and obtains barium titanate after extra bilateral porous alumina formwork in removing product and receive
Mitron array；By prepared Characterization of Barium Titanate Nanotubes array using progress discharge plasma atom light after Microwave Digestion processing
(ICP) test is composed, the atomic ratio for obtaining the Ti and Ba of Characterization of Barium Titanate Nanotubes array is 1:1.
A, the Characterization of Barium Titanate Nanotubes array powder ultrasonic of above-mentioned preparation is scattered in deionized water and obtains barium titanate concentration
For the suspension of 1g/L；
B, the bismuth nitrate solution of 0.05M is prepared, and is slowly dropped into Ti (OC into the bismuth nitrate solution4H9)4Until being formed equal
One, stable, transparent precursor sol, by the suspension prepared by gained colloidal sol and step a according to mass ratio 1:8 mix and surpass
Sound stirs 60 minutes；
C, the mixture of the colloidal sol and suspension that are obtained in 100ml steps b is taken to be packed into the hydro-thermal with polytetrafluoroethyllining lining
In reaction kettle, adding deionized water makes the compactedness of reaction vessel be 75%, with the pH of the NaOH solution regulation system of 1.0M
After value is 13, hydro-thermal reaction 1 hour at 140 DEG C；
D, it by the reaction system cooled and filtered of step c, is washed successively with the HCl of 0.1M, deionized water, absolute ethyl alcohol,
Area load is dried to obtain under high pure nitrogen atmosphere has the Characterization of Barium Titanate Nanotubes array of bismuth sodium titanate rice grain, i.e. barium titanate to receive
Mitron array/bismuth titanates composite photo-catalyst (XRD testing results are as shown in Fig. 1).
Embodiment 2
(1) alumina barrier layer that anodic oxidation aluminium formwork is removed to bottom densification with 5wt% phosphoric acid dips, obtains aperture
For the bilateral porous alumina formwork of 100nm,
The bilateral porous alumina formwork is inserted vertically into reactor center and is fixed, template is made to be isolated into reactor
Equal two parts form two-way reaction device, ensure the reactant of both sides only by bilateral porous alumina formwork phase counterdiffusion；
Ti (the OC of isometric 0.015M are separately added into template both sides4H9)4The strontium nitrate solution of solution and 0.01M is adjusted and is controlled
The pH value of both sides solution is 6, and stands 4 hours under room temperature (25 DEG C)；
(2) by by step (1) reaction after bilateral porous alumina formwork take out, by template surface wiped clean and
It is dried under infrared lamp, then rising to 750 DEG C using 5 DEG C of heating rates per minute in Muffle furnace keeps the temperature 1 hour as at annealing
Reason finally wash with the NaOH solution of 2mol/L and obtains strontium titanates after extra bilateral porous alumina formwork in removing product and receive
Mitron array；By prepared strontium titanates nano-tube array using progress discharge plasma atom light after Microwave Digestion processing
(ICP) test is composed, the atomic ratio for obtaining the Ti and Sr of strontium titanates nano-tube array is 1:1.
A, the strontium titanates nano-tube array powder ultrasonic of above-mentioned preparation is scattered in deionized water and obtains strontium titanates concentration
For the suspension of 1g/L；
B, the bismuth nitrate solution of 0.05M is prepared, and is slowly dropped into Ti (OC into the bismuth nitrate solution4H9)4Until being formed equal
One, stable, transparent precursor sol, by the suspension prepared by gained colloidal sol and step a according to mass ratio 1:8 mix and surpass
Sound stirs 60 minutes；
C, the mixture of the colloidal sol and suspension that are obtained in 100ml steps b is taken to be packed into the hydro-thermal with polytetrafluoroethyllining lining
In reaction kettle, adding deionized water makes the compactedness of reaction vessel be 75%, with the pH of the NaOH solution regulation system of 1.0M
After value is 13, hydro-thermal reaction 1 hour at 140 DEG C；
D, it by the reaction system cooled and filtered of step c, is washed successively with the HCl of 0.1M, deionized water, absolute ethyl alcohol,
Area load is dried to obtain under high pure nitrogen atmosphere has the strontium titanates nano-tube array of bismuth sodium titanate rice grain, i.e. strontium titanates to receive
Mitron array/bismuth titanates composite photo-catalyst.
Embodiment 3
(1) alumina barrier layer that anodic oxidation aluminium formwork is removed to bottom densification with 5wt% phosphoric acid dips, obtains aperture
For the bilateral porous alumina formwork of 100nm,
The bilateral porous alumina formwork is inserted vertically into reactor center and is fixed, template is made to be isolated into reactor
Equal two parts form two-way reaction device, ensure the reactant of both sides only by bilateral porous alumina formwork phase counterdiffusion；
Ti (the OC of isometric 0.012M are separately added into template both sides4H9)4The calcium nitrate solution of solution and 0.01M is adjusted and is controlled
The pH value of both sides solution is 6, and stands 4 hours under room temperature (25 DEG C)；
(2) by by step (1) reaction after bilateral porous alumina formwork take out, by template surface wiped clean and
It is dried under infrared lamp, then rising to 750 DEG C using 5 DEG C of heating rates per minute in Muffle furnace keeps the temperature 1 hour as at annealing
Reason finally wash with the NaOH solution of 2mol/L and obtains calcium titanate after extra bilateral porous alumina formwork in removing product and receive
Mitron array；By prepared calcium titanate nano-tube array using progress discharge plasma atom light after Microwave Digestion processing
(ICP) test is composed, the atomic ratio for obtaining the Ti and Ca of calcium titanate nano-tube array is 1:1.
A, the calcium titanate nano-tube array powder ultrasonic of above-mentioned preparation is scattered in deionized water and obtains metatitanic acid calcium concentration
For the suspension of 1g/L；
B, the bismuth nitrate solution of 0.05M is prepared, and is slowly dropped into Ti (OC into the bismuth nitrate solution4H9)4Until being formed equal
One, stable, transparent precursor sol, by the suspension prepared by gained colloidal sol and step a according to mass ratio 1:8 mix and surpass
Sound stirs 60 minutes；
C, the mixture of the colloidal sol and suspension that are obtained in 100ml steps b is taken to be packed into the hydro-thermal with polytetrafluoroethyllining lining
In reaction kettle, adding deionized water makes the compactedness of reaction vessel be 75%, with the pH of the NaOH solution regulation system of 1.0M
After value is 13, hydro-thermal reaction 1 hour at 140 DEG C；
D, it by the reaction system cooled and filtered of step c, is washed successively with the HCl of 0.1M, deionized water, absolute ethyl alcohol,
Area load is dried to obtain under high pure nitrogen atmosphere has the calcium titanate nano-tube array of bismuth sodium titanate rice grain, i.e. calcium titanate to receive
Mitron array/bismuth titanates composite photo-catalyst.
The photocatalytic degradation that composite photo-catalyst prepared by the above various embodiments is applied to rhodamine B is tested, specifically
Process and steps are as follows：
Each titanate nanotube array/bismuth titanates composite photo-catalysts of 100mg are scattered in the rhodamine B of 100ml respectively
In solution (a concentration of 1mg/ml), uniformly mixed dispersion liquid continues stirring and reaches adsorption equilibrium for a period of time；It will mix again equal
Even dispersion liquid is transferred in xenon lamp light-catalyzed reaction instrument, carries out catalysis degeneration experiment, it is small that entire catalysis degeneration experiment continues 3
When.After light-catalyzed reaction starts, extracted and 4ml samples and be transferred in centrifuge tube every 30 minutes, by the sample in centrifuge tube from
The heart detaches, and the supernatant liquor isolated measures absorbance with ultraviolet-visible spectrophotometer, and the complex light for obtaining each embodiment is urged
For agent to the photocatalytic degradation effect of rhodamine B under the different light-catalyzed reaction times, concrete outcome is as shown in Fig. 2.
Comparative example 1
(1) alumina barrier layer that anodic oxidation aluminium formwork is removed to bottom densification with 5wt% phosphoric acid dips, obtains aperture
For the bilateral porous alumina formwork of 100nm,
The bilateral porous alumina formwork is inserted vertically into reactor center and is fixed, template is made to be isolated into reactor
Equal two parts form two-way reaction device, ensure the reactant of both sides only by bilateral porous alumina formwork phase counterdiffusion；
Ti (the OC of isometric 0.01M are separately added into template both sides4H9)4The barium nitrate solution of solution and 0.01M, adjusts and controls
The pH value of both sides solution is 6, and stands 4 hours under room temperature (25 DEG C)；
(2) by by step (1) reaction after bilateral porous alumina formwork take out, by template surface wiped clean and
It is dried under infrared lamp, then rising to 750 DEG C using 5 DEG C of heating rates per minute in Muffle furnace keeps the temperature 1 hour as at annealing
Reason finally wash with the NaOH solution of 2mol/L and obtains barium titanate after extra bilateral porous alumina formwork in removing product and receive
Mitron array；By prepared Characterization of Barium Titanate Nanotubes array using progress discharge plasma atom light after Microwave Digestion processing
(ICP) test is composed, the atomic ratio for obtaining the Ti and Ba of Characterization of Barium Titanate Nanotubes array is 0.56:1.
Comparative example 2
(1) alumina barrier layer that anodic oxidation aluminium formwork is removed to bottom densification with 5wt% phosphoric acid dips, obtains aperture
For the bilateral porous alumina formwork of 100nm,
The bilateral porous alumina formwork is inserted vertically into reactor center and is fixed, template is made to be isolated into reactor
Equal two parts form two-way reaction device, ensure the reactant of both sides only by bilateral porous alumina formwork phase counterdiffusion；
Ti (the OC of isometric 0.01M are separately added into template both sides4H9)4The strontium nitrate solution of solution and 0.01M is adjusted and is controlled
The pH value of both sides solution is 6, and stands 4 hours under room temperature (25 DEG C)；
(2) by by step (1) reaction after bilateral porous alumina formwork take out, by template surface wiped clean and
It is dried under infrared lamp, then rising to 750 DEG C using 5 DEG C of heating rates per minute in Muffle furnace keeps the temperature 1 hour as at annealing
Reason finally wash with the NaOH solution of 2mol/L and obtains strontium titanates after extra bilateral porous alumina formwork in removing product and receive
Mitron array；By prepared strontium titanates nano-tube array using progress discharge plasma atom light after Microwave Digestion processing
(ICP) test is composed, the atomic ratio for obtaining the Ti and Sr of strontium titanates nano-tube array is 0.63:1.
Claims (9)
1. a kind of preparation method of titanate nanotube array, it is characterised in that：The method is,
(1) bilateral porous alumina formwork is inserted vertically into reactor center and fixed, make template that reactor is isolated into phase
Deng two parts formed two-way reaction device, ensure both sides reactant only by bilateral porous alumina formwork phase counterdiffusion；
Template both sides are separately added into Ti (OC4H9)4Solution and nitrate solution, the nitrate be barium nitrate, strontium nitrate or calcium nitrate,
Control Ti (OC4H9)4Solution and different cationic concentration ratio in nitrate solution, so as to get titanate nanotube array
Ti and Ba, Ti and Sr or Ti and Ca atomic ratio be 1:1, it adjusts pH value and stands reaction；
(2) it will be taken out by the bilateral porous alumina formwork after step (1) reaction, by template surface wiped clean and infrared
It dries under lamp, is then made annealing treatment, finally washing obtains titanium after removing bilateral porous alumina formwork extra in product
Silicate nanometer pipe array.
2. the preparation method of titanate nanotube array as described in claim 1, it is characterised in that：Described in step (1)
The aperture of bilateral porous alumina formwork is 50~200nm, and the preparation method of the template is to use anodic oxidation aluminium formwork
5wt% phosphoric acid dips remove the alumina barrier layer of bottom densification, obtain bilateral porous alumina formwork.
3. the preparation method of titanate nanotube array as described in claim 1, it is characterised in that：In step (1), nitrate
A concentration of 0.01-0.1M of solution, Ti (OC4H9)4A concentration of 0.012~0.12M of solution.
4. a kind of application for the titanate nanotube array being prepared such as any one of claims 1 to 3 the method, feature
It is：The application is,
A, titanate nanotube array ultrasonic is scattered in deionized water and obtains metatitanic acid salt suspensioning liquid；
B, bismuth nitrate solution is prepared, and instills Ti (OC into bismuth nitrate solution4H9)4Form uniform, stable, transparent presoma
Gained colloidal sol is mixed and is stirred by ultrasonic with the metatitanic acid salt suspensioning liquid prepared by step a by colloidal sol；
C, the mixture of the colloidal sol obtained in step b and suspension is fitted into hydrothermal reaction kettle, adds deionized water and adjusted
Hydro-thermal reaction is carried out after section pH value；
D, by the reaction system cooled and filtered of step c, washing, under high pure nitrogen atmosphere being dried to obtain area load has metatitanic acid
The titanate nanotube array of bismuth nano particle.
5. the application of titanate nanotube array as claimed in claim 4, it is characterised in that：In suspension described in step a
A concentration of 0.5g/L~2g/L of titanate.
6. the application of titanate nanotube array as claimed in claim 4, it is characterised in that：In step b, the bismuth nitrate of preparation
Solution concentration is 0.005M~0.2M.
7. the application of titanate nanotube array as claimed in claim 4, it is characterised in that：In step b, colloidal sol and step a
Prepared metatitanic acid salt suspensioning liquid is according to mass ratio 1:5~1:10 mixing.
8. the application of titanate nanotube array as claimed in claim 4, it is characterised in that：In step c, using 1.0M's
NaOH solution adjusts after pH value is 11~13 and carries out hydro-thermal reaction, and hydrothermal temperature is 120~160 DEG C, and the reaction time is 2~
6 hours.
9. the application of titanate nanotube array as claimed in claim 4, it is characterised in that：Washing in step d specifically,
HCl solution, deionized water and the absolute ethyl alcohol washing of 0.1M are used successively.
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