CN108993470A - A kind of preparation and application of the double array structure catalysis materials of titanium dioxide/graphene/zinc oxide - Google Patents
A kind of preparation and application of the double array structure catalysis materials of titanium dioxide/graphene/zinc oxide Download PDFInfo
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- CN108993470A CN108993470A CN201810870674.5A CN201810870674A CN108993470A CN 108993470 A CN108993470 A CN 108993470A CN 201810870674 A CN201810870674 A CN 201810870674A CN 108993470 A CN108993470 A CN 108993470A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 80
- 239000011787 zinc oxide Substances 0.000 title claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 11
- 229910021389 graphene Inorganic materials 0.000 title claims description 7
- 239000004408 titanium dioxide Substances 0.000 title claims description 3
- 239000002071 nanotube Substances 0.000 claims abstract description 20
- 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 claims abstract description 20
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 50
- 229910052719 titanium Inorganic materials 0.000 claims description 50
- 239000010936 titanium Substances 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 23
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000000712 assembly Effects 0.000 claims description 6
- 238000000429 assembly Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002484 cyclic voltammetry Methods 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- VWTSXINFCUODBJ-UHFFFAOYSA-L zinc methanol diacetate Chemical compound [Zn++].CO.CC([O-])=O.CC([O-])=O VWTSXINFCUODBJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002073 nanorod Substances 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000007743 anodising Methods 0.000 abstract 1
- 239000000356 contaminant Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000004246 zinc acetate Substances 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses TiO2The preparation of the bis- array structure catalysis materials of/RGO/ZnO and its application of photocatalytically degradating organic dye rhodamine B.TiO is prepared by two-step electrochemical anodizing method2Nano-tube array simultaneously deposits growth site of the RGO thin layer as ZnO nanorod on its surface, rear to construct TiO by being condensed back vertical-growth ZnO nano-rod array2The bis- array structures of/RGO/ZnO.Under ultraviolet-visible light irradiation, which shows the activity and stability of excellent photocatalytically degradating organic dye rhodamine B.Since preparation method is simple, reaction condition is mild, recycling can be efficiently separated and reused, which has important practical application value in technical field of material and environmental contaminants degradation field, is conducive to the sustainable development of environment and the energy.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to TiO2The bis- array structure catalysis materials of/RGO/ZnO
Preparation and its photocatalytically degradating organic dye rhodamine B application.
Background technique
In face of energy crisis and problem of environmental pollution, developing and using green sustainable energy is people's all the time unremitting
It pursues.Wherein, it is considered as a promising project that design construction, which has the catalysis material of high-efficiency solar transformation efficiency,
With important scientific research meaning.Due to microstructure and pattern factor (such as size, shape, crystal face and hetero-junctions)
Have a great impact to the photocatalysis performance of material, therefore its light is urged come tuning for the structure by regulating and controlling catalysis material and pattern
Change extensive concern of the activity by researcher.
One-dimentional structure has electronics directional transmissions, and higher specific surface area is conducive to the advantages such as light absorption and scattering, is answered extensively
It is a kind of promising function of tool for fields such as electronic device, solar battery, photocatalysis, photoelectrocatalysis and lithium batteries
Material.At present in research, one-dimensional TiO2 nanostructure (such as: nano wire, nanotube, nanobelt, nanometer rods) is in point of charge
Absorption depth aspect from transfer and light shows itself superiority.The TiO2 of titanium sheet is grown on especially by anodic oxidation
Nano-tube array possesses the TiO2 nanotube of high-sequential vertical arrangement, all shows in photocatalysis, photoelectrocatalysis application
Excellent performance.Equally, ZnO nano-rod array also obtains very big concern in energy conversion field.On the other hand, graphene has
There are two-dimensional film structure and excellent electric conductivity, can provide the separation of charge in a large amount of growth site and promotion system
With transfer.By in one-dimentional structure the characteristics of the conduction of electronics orientation and the synergistic effect of the excellent electric conductivity of graphene promotes
The separation of charge is shifted and inhibits the compound of electron-hole pair in system, is expected to realize effectively improving for photocatalysis performance.
Summary of the invention
The purpose of the present invention is to provide a kind of TiO2The preparation method of the bis- array structure catalysis materials of/RGO/ZnO and
The application of its photocatalytically degradating organic dye rhodamine B.Prepared catalyst has excellent photocatalytic degradation rhodamine B
Activity and stability, can efficiently separate recycling and reuse.
To achieve the above object, the present invention adopts the following technical scheme:
It is a kind of to prepare TiO as described above2The preparation method of the bis- array structure catalysis materials of/RGO/ZnO, including following step
It is rapid:
(1) TiO2The preparation of nano-tube array:
Using two electrode assemblies carry out anodic oxidation, using titanium sheet as anode, an equal amount of graphite flake be cathode, two electrodes away from
From for 3 cm.Electrolyte is the ethylene glycol solution containing 0.3 wt% ammonium fluoride and 2 vol% deionized waters.First time anodic oxidation
Process carries out 2 h under 50 V voltages, and nitrogen (N will be used after 10 min of titanium sheet ultrasound2) drying.By the titanium sheet under 50 V voltages
30 min are reacted, second of anodic oxidation is carried out.Hereafter, titanium plate surface, naturally dry, in 450 DEG C of items are rinsed with deionized water
1 h is calcined under part, obtains TiO2Nano-tube array；
(2) TiO2The preparation of/RGO:
The process uses three-electrode system, uses saturated calomel electrode for reference electrode, by the resulting growth TiO of step (1)2It receives
For the titanium sheet of mitron array as working electrode, platinum electrode is to electrode.Electrolyte is 1.0 mgmL−1Graphene oxide (GO)
Aqueous solution.Using cyclic voltammetry, for test voltage range from 1.5 V to 1 V, scanning speed is 50 mVs−1, carry out 10 times
Circulation.Hereafter, titanium plate surface is rinsed well with deionized water, air drying obtains TiO2/ RGO compound system；
(3) preparation of ZnO seed liquor:
The 0.01 M zinc acetate methanol solution of 125 mL is vigorously stirred at 60 DEG C, and the 0.03 of 65 mL is added dropwise thereto
M potassium hydroxide methanol solution.After being added dropwise, solution continuation stirs 2 h at 60 DEG C and obtains ZnO seed liquor；
(4) TiO2The preparation of/RGO/ZnO
TiO will be grown obtained by step (2)2The titanium sheet of/RGO is immersed in ZnO seed liquor obtained by step (3) after 15 min, is taken out
And air drying, ZnO seed is deposited on TiO at this time2On/RGO.It prepares 150 mL and contains 0.02 M zinc nitrate and 0.02 M six
The aqueous solution of methenamine in a round bottom flask, stirs evenly.The titanium sheet is placed in behind round-bottomed flask bottom cold at 90 DEG C
Solidifying reflux.Titanium sheet is taken out, is rinsed with ethyl alcohol and deionized water, drying obtains TiO2/ RGO/ZnO composite catalyst.
Specific step is as follows for photocatalytically degradating organic dye rhodamine B:
(1) the 5 ppm rhodamine B aqueous solutions of 3 mL are added into the silica dish that specification is the cm × 4 of 1 cm × 1 cm, it will
Specification is the cm of 1 cm × 2 and growth has the titanium sheet of catalyst to submerge vertically wherein.
(2) device is put into 30 min in dark situation and carries out adsorption equilibrium.
(3) reaction system is irradiated using ultraviolet-visible light.The irradiation interval of every 10 min, with UV, visible light spectrophotometric
The concentration of rhodamine B in measurement examination solution.
Remarkable advantage of the invention is:
(1) of the invention by a kind of TiO2The bis- array structure catalysis materials of/RGO/ZnO are applied to the light of organic dyestuff rhodamine B
Catalytic degradation reaction, catalyst photocatalysis efficiency with higher, is conducive to the sustainable development of environment and the energy.
(2) TiO2The cycle performance of the bis- array structure catalysis materials of/RGO/ZnO is good, simple production process, environment are friendly
It gets well and can realize and efficiently separate and recycle.
Detailed description of the invention
Fig. 1 is TiO2Nano-tube array, TiO2/RGO、TiO2The scanning electron microscope (SEM) photograph of/RGO/ZnO；Wherein A figure is TiO2It receives
Mitron array, B figure are TiO2/ RGO, C figure are TiO2/RGO/ZnO。
Fig. 2 is ZnO nano-rod array, TiO2Nano-tube array, TiO2/RGO、TiO2/ZnO、TGZ-2h、TGZ-3h、TGZ-
The activity figure of 4h photocatalytic degradation rhodamine B.
Fig. 3 is TiO2The stability diagram of the rhodamine B degradation of the bis- array structure catalysis materials of/RGO/ZnO.
Specific embodiment
The present invention is further illustrated by the following examples, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
Using two electrode assemblies carry out anodic oxidation, using titanium sheet as anode, an equal amount of graphite flake be cathode, two electrodes away from
From for 3 cm.Electrolyte is the ethylene glycol solution containing 0.3 wt% ammonium fluoride and 2 vol% deionized waters.First time anodic oxidation
Process carries out 2 h under 50 V voltages, will use N after 10 min of titanium sheet ultrasound2Drying.The titanium sheet is reacted 30 under 50 V voltages
Min carries out second of anodic oxidation.Hereafter, titanium plate surface is rinsed with deionized water, naturally dry is calcined under the conditions of 450 DEG C
1 h, obtains TiO2Nano-tube array.
The 5 ppm rhodamine B aqueous solutions of 3 mL are added into the silica dish that specification is the cm × 4 of 1 cm × 1 cm, it will
Specification is the cm of 1 cm × 2 and growth has TiO2The titanium sheet of nano-tube array is submerged wherein vertically.The device is put into dark situation
In 30 min carry out adsorption equilibrium.Reaction system is irradiated using ultraviolet-visible light.The irradiation interval of every 10 min, with it is ultraviolet can
See the concentration of rhodamine B in spectrophotometer test solution.
Embodiment 2
Using two electrode assemblies carry out anodic oxidation, using titanium sheet as anode, an equal amount of graphite flake be cathode, two electrodes away from
From for 3 cm.Electrolyte is the ethylene glycol solution containing 0.3 wt% ammonium fluoride and 2 vol% deionized waters.First time anodic oxidation
Process carries out 2 h under 50 V voltages, will use N after 10 min of titanium sheet ultrasound2Drying.The titanium sheet is reacted 30 under 50 V voltages
Min carries out second of anodic oxidation.Hereafter, titanium plate surface is rinsed with deionized water, naturally dry is forged under the conditions of 450 DEG C
1 h is burnt, TiO is obtained2Nano-tube array.By 1.0 mgmL−1GO aqueous solution be electrolyte, use three-electrode system, use
Saturated calomel electrode is reference electrode, will grow TiO2The titanium sheet of nano-tube array is working electrode, and platinum electrode is to electrode.Make
With cyclic voltammetry, for test voltage range from 1.5 V to 1 V, scanning speed is 50 mVs−1, carry out 10 circulations.Hereafter,
Titanium plate surface is rinsed well with deionized water, air drying obtains TiO2/ RGO compound system.
The 5 ppm rhodamine B aqueous solutions of 3 mL are added into the silica dish that specification is the cm × 4 of 1 cm × 1 cm, it will
Specification is the cm of 1 cm × 2 and growth has TiO2The titanium sheet of/RGO is submerged wherein vertically.The device is put into 30 in dark situation
Min carries out adsorption equilibrium.Reaction system is irradiated using ultraviolet-visible light.The irradiation interval of every 10 min, is divided with UV, visible light
Photometer tests the concentration of rhodamine B in solution.
Embodiment 3
Using two electrode assemblies carry out anodic oxidation, using titanium sheet as anode, an equal amount of graphite flake be cathode, two electrodes away from
From for 3 cm.Electrolyte is the ethylene glycol solution containing 0.3 wt% ammonium fluoride and 2 vol% deionized waters.First time anodic oxidation
Process carries out 2 h under 50 V voltages, will use N after 10 min of titanium sheet ultrasound2Drying.The titanium sheet is reacted 30 under 50 V voltages
Min carries out second of anodic oxidation.Hereafter, titanium plate surface is rinsed with deionized water, naturally dry is calcined under the conditions of 450 DEG C
1 h, obtains TiO2Nano-tube array.By 1.0 mgmL−1GO aqueous solution be electrolyte, using three-electrode system, using full
It is reference electrode with calomel electrode, TiO will be grown2The titanium sheet of nano-tube array is working electrode, and platinum electrode is to electrode.It uses
Cyclic voltammetry, for test voltage range from 1.5 V to 1 V, scanning speed is 50 mVs−1, carry out 10 circulations.Hereafter, will
Titanium plate surface is rinsed well with deionized water, and air drying obtains TiO2/ RGO compound system.The 0.01 M zinc acetate of 125 mL
Methanol solution is vigorously stirred at 60 DEG C, and the 0.03 M potassium hydroxide methanol solution of 65 mL is added dropwise thereto.It drips
Bi Hou, solution continuation stir 2 h at 60 DEG C and obtain ZnO seed liquor.TiO will be grown2The titanium sheet of/RGO is immersed in ZnO seed liquor
In after 15 min, take out and air drying, ZnO seed is deposited on TiO at this time2On/RGO.It prepares 150 mL and contains 0.02 M
The aqueous solution of zinc nitrate and 0.02 M hexa in a round bottom flask, stirs evenly.The titanium sheet is placed in round-bottomed flask
It is condensed back at 90 DEG C behind bottom.Titanium sheet is taken out, is rinsed with ethyl alcohol and deionized water, drying obtains TiO2/ RGO/ZnO is multiple
Close catalyst.
The 5 ppm rhodamine B aqueous solutions of 3 mL are added into the silica dish that specification is the cm × 4 of 1 cm × 1 cm, it will
Specification is the cm of 1 cm × 2 and growth has TiO2The titanium sheet of/RGO/ZnO is submerged wherein vertically.The device is put into dark situation
30 min carry out adsorption equilibrium.Reaction system is irradiated using ultraviolet-visible light.The irradiation interval of every 10 min, uses UV, visible light
Spectrophotometer tests the concentration of rhodamine B in solution.
Embodiment 4
Using two electrode assemblies carry out anodic oxidation, using titanium sheet as anode, an equal amount of graphite flake be cathode, two electrodes away from
From for 3 cm.Electrolyte is the ethylene glycol solution containing 0.3 wt% ammonium fluoride and 2 vol% deionized waters.First time anodic oxidation
Process carries out 2 h under 50 V voltages, will use N after 10 min of titanium sheet ultrasound2Drying.The titanium sheet is reacted 30 under 50 V voltages
Min carries out second of anodic oxidation.Hereafter, titanium plate surface is rinsed with deionized water, naturally dry is calcined under the conditions of 450 DEG C
1 h, obtains TiO2Nano-tube array.The 0.01 M zinc acetate methanol solution of 125 mL is vigorously stirred at 60 DEG C, and thereto
The 0.03 M potassium hydroxide methanol solution of 65 mL is added dropwise.After being added dropwise, solution continuation is stirred 2 h at 60 DEG C and is obtained
ZnO seed liquor.TiO will be grown2The titanium sheet of nano-tube array is immersed in ZnO seed liquor after 15 min, takes out simultaneously air drying,
ZnO seed is deposited on TiO at this time2On nano-tube array.It prepares 150 mL and contains six methylene of 0.02 M zinc nitrate and 0.02 M
The aqueous solution of urotropine in a round bottom flask, stirs evenly.The titanium sheet is placed in behind round-bottomed flask bottom and is condensed back at 90 DEG C
Stream.Titanium sheet is taken out, is rinsed with ethyl alcohol and deionized water, drying obtains TiO2/ ZnO composite catalyst.
The 5 ppm rhodamine B aqueous solutions of 3 mL are added into the silica dish that specification is the cm × 4 of 1 cm × 1 cm, it will
Specification is the cm of 1 cm × 2 and growth has TiO2The titanium sheet of/ZnO is submerged wherein vertically.The device is put into 30 in dark situation
Min carries out adsorption equilibrium.Reaction system is irradiated using ultraviolet-visible light.The irradiation interval of every 10 min, is divided with UV, visible light
Photometer tests the concentration of rhodamine B in solution.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (6)
1. a kind of titanium dioxide TiO2The bis- array structure catalysis materials of/graphene RGO/ zinc oxide ZnO, it is characterised in that: described
The structure of compound catalysis material specifically: with TiO2Nano-tube array is substrate and deposits RGO thin layer, ZnO on its surface
Nanometer stick array vertical-growth is in TiO2The top /RGO.
2. a kind of prepare TiO as described in claim 12The method of the bis- array structure catalysis materials of/RGO/ZnO, feature exist
In: the following steps are included:
(1) TiO2The preparation of nano-tube array:
Using two electrode assemblies carry out anodic oxidation, using titanium sheet as anode, an equal amount of graphite flake be cathode, two electrodes away from
From for 3 cm；Electrolyte is the ethylene glycol solution containing 0.3 wt% ammonium fluoride and 2 vol% deionized waters；Carry out first time anode
Then oxidation process will use nitrogen N after 10 min of titanium sheet ultrasound2Drying；The titanium sheet is subjected to second of anodic oxidation；Hereafter,
Titanium plate surface is rinsed with deionized water, naturally dry is calcined, and TiO is obtained2Nano-tube array；
(2) TiO2The preparation of/RGO:
The process uses three-electrode system, uses saturated calomel electrode for reference electrode, by the resulting growth TiO of step (1)2It receives
For the titanium sheet of mitron array as working electrode, platinum electrode is to electrode；Electrolyte is 1.0 mgmL−1Graphene oxide GO water
Solution；Using cyclic voltammetry, for test voltage range from 1.5 V to 1 V, scanning speed is 50 mVs−1, follow for 10 times
Ring；Hereafter, titanium plate surface is rinsed well with deionized water, air drying obtains TiO2/ RGO compound system；
(3) preparation of ZnO seed liquor:
The 0.01 M zinc acetate methanol solution of 125 mL is vigorously stirred at 60 DEG C, and the 0.03 of 65 mL is added dropwise thereto
M potassium hydroxide methanol solution；After being added dropwise, solution continuation stirs 2 h at 60 DEG C and obtains ZnO seed liquor；
(4) TiO2The preparation of/RGO/ZnO
TiO will be grown obtained by step (2)2The titanium sheet of/RGO is immersed in ZnO seed liquor obtained by step (3) after 15 min, is taken out simultaneously
Air drying, ZnO seed is deposited on TiO at this time2On/RGO；It prepares 150 mL and contains six Asia of 0.02 M zinc nitrate and 0.02 M
The aqueous solution of tetramine in a round bottom flask, stirs evenly；The titanium sheet is placed in behind round-bottomed flask bottom and is condensed at 90 DEG C
Reflux；Titanium sheet is taken out, is rinsed with ethyl alcohol and deionized water, drying obtains TiO2/ RGO/ZnO composite catalyst.
3. preparation method according to claim 2, it is characterised in that: step (1) the first time anodic oxidation is 50
2 h are carried out under V voltage；Second of anodic oxidation condition is to react 30 min under 50 V voltages.
4. preparation method according to claim 2, it is characterised in that: step (1) described calcination condition are as follows: in 450 DEG C of items
1 h is calcined under part.
5. preparation method according to claim 2, it is characterised in that: the condensing reflux time described in step (4) is 2 h
~4 h。
6. a kind of TiO as described in claim 12The application of the bis- array structure catalysis materials of/RGO/ZnO, it is characterised in that:
For ultraviolet-visible light photocatalytically degradating organic dye rhodamine B.
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