CN105506710A - Method for preparing titanium dioxide nanotube arrays with CuS nanoparticles sensitized - Google Patents
Method for preparing titanium dioxide nanotube arrays with CuS nanoparticles sensitized Download PDFInfo
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- CN105506710A CN105506710A CN201510934334.0A CN201510934334A CN105506710A CN 105506710 A CN105506710 A CN 105506710A CN 201510934334 A CN201510934334 A CN 201510934334A CN 105506710 A CN105506710 A CN 105506710A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002071 nanotube Substances 0.000 title claims abstract description 50
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 40
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000003491 array Methods 0.000 title abstract 6
- 239000000243 solution Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 27
- 239000010936 titanium Substances 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000002048 anodisation reaction Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 claims description 3
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 206010070834 Sensitisation Diseases 0.000 abstract description 44
- 230000008313 sensitization Effects 0.000 abstract description 44
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000005416 organic matter Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000007605 air drying Methods 0.000 abstract 2
- 238000005406 washing Methods 0.000 abstract 2
- 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 abstract 1
- 229940021013 electrolyte solution Drugs 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000005498 polishing Methods 0.000 abstract 1
- 229910052955 covellite Inorganic materials 0.000 description 30
- 230000001699 photocatalysis Effects 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 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 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000006037 cell lysis Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for preparing titanium dioxide nanotube arrays with CuS nanoparticles sensitized. The method comprises the steps of 1, sequentially carrying out metallographic abrasive paper sanding and chemical polishing on a titanium sheet, washing the titanium sheet through distilled water and air-drying the titanium sheet; 2, carrying out anodic oxidation twice in electrolyte solutions composed of deionized water, phosphoric acid, ammonium fluoride and ethanediol through the anodic oxidation method for preparing the titanium dioxide nanotube arrays; 3, immersing the titanium sheet with the titanium dioxide nanotube arrays in the mixed solutions of a Cu source precursor solution and a S source precursor solution, carrying out water thermo-sensitive treatment in a reaction still at 100 DEG C, washing the titanium sheet repeatedly through the deionized water and absolute ethyl alcohol repeatedly and air-drying the titanium sheet at the indoor temperature for obtaining the titanium dioxide nanotube arrays with the CuS nanoparticles sensitized. The method has the advantages of being simple, practicable, free of pollution in the preparation process, and capable of effectively improving the photoelectric conversion efficiency and the light-assisted organic matter degradation ability of the titanium dioxide nanotube arrays after sensitization.
Description
Technical field
The present invention relates to nano science, surface chemistry and photocatalysis field, particularly the preparation method of the nanoparticle sensitized Nano tube array of titanium dioxide of a kind of CuS.
Background technology
TiO
2the preparation method that nano-tube array is conventional has several as follows: a template, b hydrothermal synthesis method, c anonizing etc.Because anonizing is simple to operate, experiment condition is easy to control, gained nano-tube array is comparatively all first-class, therefore adopts anonizing to prepare Nano tube array of titanium dioxide in this patent.Because of TiO
2nano-tube array structure is orderly, size is controlled, specific surface area is high, shows higher electricity conversion and photocatalysis performance as light anode, therefore can be used for solar cell and photocatalysis to degrade organic matter, but because of TiO
2energy gap (3.0-3.2eV) is wider, as: Anatase (anatase) is 3.2eV, Rutile Type is 3.0eV.Only respond ultraviolet region (accounting for 5% of sunlight), absorption is not produced to visible region.Therefore regulate TiO
2energy gap, widen spectral response range, raising photoelectric transformation efficiency and catalytic activity are seemed particularly important.Regulate TiO
2the method of nanotube energy gap mainly contains doped transition metal ions, noble metal loading, nonmetal doping, organic dye sensitized and quantum dot sensitized etc.And nontoxic CuS nano particle has and can be in harmonious proportion relatively narrow energy gap, can produce visible ray and obviously absorb, and nanotube hollow tubular structure makes its specific surface area large, high adsorption capacity, is more easily combined with CuS nano particle, thus realizes TiO
2to the absorption of visible ray.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of preparation method of the Nano tube array of titanium dioxide nanoparticle sensitized for the CuS of solar cell or photocatalysis to degrade organic matter is provided, this method is simple, pollution-free, for suitability for industrialized production provides an approach.
Technical scheme of the present invention:
A preparation method for the nanoparticle sensitized Nano tube array of titanium dioxide of CuS, step is as follows:
1) preparation of Nano tube array of titanium dioxide
A) pre-treatment of technical pure titanium sheet: technical pure titanium sheet is carried out surface finish process with 800#, 1000#, 1200# abrasive paper for metallograph successively, then successively with acetone, ethanol, deionized water ultrasonic cleaning to remove its surperficial grease, be the salpeter solution of 65wt% and concentration by distilled water, concentration be again that the mixing solutions of the hydrofluoric acid solution of 40wt% is to its chemical rightenning, the volume ratio of distilled water in mixing solutions, concentration to be the salpeter solution of 65wt% and concentration the be hydrofluoric acid solution of 40wt% is 5:4:1, finally air-dry rear for subsequent use with distilled water flushing;
B) anodic oxidation: adopt two electrodes system, respectively with pretreated titanium sheet and graphite flake for anode and negative electrode, under 55-65V constant voltage DC, anodic oxidation 4-8 hour is carried out in the electrolytic solution be made up of deionized water, phosphoric acid, Neutral ammonium fluoride and ethylene glycol, in electrolytic solution, the volume percent of each component is deionized water 3%, phosphatase 24 %, the concentration of Neutral ammonium fluoride is 0.6g/mL, ethylene glycol is surplus, then take out titanium sheet, be placed in the film in deionized water for ultrasonic cleaning removing titanium sheet;
C) two-step anodization: the titanium sheet after b) processing is carried out second time anodic oxidation under the condition identical with an anodic oxidation, oxidization time is 7-10 hour, then ultrasonic cleaning 10-20min in dehydrated alcohol, after drying at 550 DEG C cycle annealing 3 hours, then in air atmosphere, room temperature is naturally cooled to, obtained Nano tube array of titanium dioxide;
2) preparation of the Nano tube array of titanium dioxide that CuS is nanoparticle sensitized
Above-mentioned Nano tube array of titanium dioxide being immersed volume ratio is in the Cu source precursor solution of 1:1 and the mixing solutions of S source precursor solution, CuSO in the precursor solution of Cu source
4be Na in the precursor solution of 0.01g:5mL, S source with the amount ratio of deionized water
2s
2o
3be 0.01g:5mL with the amount ratio of deionized water, hydro-thermal sensitized treatment 6-14 hour at 100 DEG C in a kettle., to be cooledly to take out to room temperature, repeatedly rinse 6-10 time with deionized water and dehydrated alcohol, dry under room temperature, the Nano tube array of titanium dioxide that obtained CuS is nanoparticle sensitized.
The invention has the beneficial effects as follows: compared with prior art, preparation process is simple, pollution-free, can be mass-produced.To have studied before and after sensitization Nano tube array of titanium dioxide to the degradation effect of rhodamine B solution simultaneously, find that its photoelectrocatalysis successful after sensitization CuS nano particle strengthens, known according to pertinent literature, low energy gap nano particle and the combination of the Nano tube array of titanium dioxide of broad stopband facilitate the compound being separated, avoiding electronics and hole in electronics and hole, and then improve its photoelectric properties.For the preparation method of the nanoparticle sensitized Nano tube array of titanium dioxide of the CuS of solar cell or photocatalysis to degrade organic matter, can effective organic dye in photocatalytic degradation sewage, belong to nano science, surface chemistry and photocatalysis field.
Accompanying drawing explanation
Fig. 1 is the SEM comparison diagram of TNTAs before and after sensitization: before (a) sensitization, (b) sensitization 10h.
Fig. 2 is the impact of different sensitization time on TNTAs crystal formation: (a) non-sensitization (b) sensitization 6h (c) sensitization 10h (d) sensitization 14h (e) CuS nano particle.
Fig. 3 is the UV-Vis absorption spectrum of TNTAs under different sensitization time: TNTAs (c) sensitization 6h (d) sensitization 10h (e) the sensitization 14h of the non-sensitization of pure titanium sheet (b) after the process of (a) physical chemistry.
Fig. 4 is that the ultraviolet absorpting spectrum of RhB changes (A); The contrast experiment (B) of the CuS/TNTAs Visible Light Induced Photocatalytic rhodamine B of sensitization different time: (a) RhB stoste (b) 0min (c) 6h (d) 10h (e) 14h.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
Embodiment 1:
A preparation method for the nanoparticle sensitized Nano tube array of titanium dioxide of CuS, step is as follows:
1) preparation of Nano tube array of titanium dioxide
A) pre-treatment of technical pure titanium sheet: technical pure titanium sheet is carried out surface finish process with 800#, 1000#, 1200# abrasive paper for metallograph successively, then successively with acetone, ethanol, deionized water ultrasonic cleaning to remove its surperficial grease, be the salpeter solution of 65wt% and concentration by distilled water, concentration be again that the mixing solutions of the hydrofluoric acid solution of 40wt% is to its chemical rightenning, the volume ratio of distilled water in mixing solutions, concentration to be the salpeter solution of 65wt% and concentration the be hydrofluoric acid solution of 40wt% is 5:4:1, finally air-dry rear for subsequent use with distilled water flushing;
B) anodic oxidation: adopt two electrodes system, respectively with pretreated titanium sheet and graphite flake for anode and negative electrode, under 60V constant voltage DC, anodic oxidation 6 hours is carried out in the electrolytic solution be made up of deionized water, phosphoric acid, Neutral ammonium fluoride and ethylene glycol, in electrolytic solution, the volume percent of each component is deionized water 3%, phosphatase 24 %, the concentration of Neutral ammonium fluoride is 0.6g/mL, ethylene glycol is surplus, then takes out titanium sheet, is placed in the film in deionized water for ultrasonic cleaning removing titanium sheet;
C) two-step anodization: the titanium sheet after b) processing is carried out second time anodic oxidation under the condition identical with an anodic oxidation, oxidization time is 8 hours, then ultrasonic cleaning 10min in dehydrated alcohol, after drying at 550 DEG C cycle annealing 3 hours, then in air atmosphere, room temperature is naturally cooled to, obtained Nano tube array of titanium dioxide;
2) preparation of the Nano tube array of titanium dioxide that CuS is nanoparticle sensitized
Above-mentioned Nano tube array of titanium dioxide being immersed volume ratio is in the Cu source precursor solution of 1:1 and the mixing solutions of S source precursor solution, CuSO in the precursor solution of Cu source
4be Na in the precursor solution of 0.01g:5mL, S source with the amount ratio of deionized water
2s
2o
3be 0.01g:5mL with the amount ratio of deionized water, hydro-thermal sensitized treatment 6 hours at 100 DEG C in a kettle., to be cooledly takes out to room temperature, repeatedly rinses 6 times with deionized water and dehydrated alcohol, dry under room temperature, the Nano tube array of titanium dioxide that obtained CuS is nanoparticle sensitized.
Embodiment 2:
The preparation method of the nanoparticle sensitized Nano tube array of titanium dioxide of a kind of CuS, step is substantially the same manner as Example 1, difference is: step 2) in hydro-thermal sensitized treatment 10 hours at 100 DEG C in a kettle., the Nano tube array of titanium dioxide that obtained CuS is nanoparticle sensitized.
Embodiment 3:
The preparation method of the nanoparticle sensitized Nano tube array of titanium dioxide of a kind of CuS, step is substantially the same manner as Example 1, difference is: step 2) in hydro-thermal sensitized treatment 14 hours at 100 DEG C in a kettle., the Nano tube array of titanium dioxide that obtained CuS is nanoparticle sensitized.
Embodiment 4:
The preparation method of the nanoparticle sensitized Nano tube array of titanium dioxide of a kind of CuS, step is substantially the same manner as Example 1, difference is: step 1) in b) once anodised parameter be: 65V constant voltage DC anodic oxidation 4 hours, c) parameter of two-step anodization was: 55V current stabilization vertical compression anodic oxygenization 10 hours, the Nano tube array of titanium dioxide that obtained CuS is nanoparticle sensitized.
Embodiment 5:
The preparation method of the nanoparticle sensitized Nano tube array of titanium dioxide of a kind of CuS, step is substantially the same manner as Example 1, difference is: step 1) in b) once anodised parameter be: 55V constant voltage DC anodic oxidation 8 hours, c) parameter of two-step anodization was: 65V current stabilization vertical compression anodic oxygenization 7 hours, the Nano tube array of titanium dioxide that obtained CuS is nanoparticle sensitized.
Fig. 1 is the SEM comparison diagram of TNTAs before and after sensitization: before (a) sensitization, (b) sensitization 10h.Show in figure: the titania nanotube smooth surface before sensitization, without CuS nano particle; And after sensitization 10h, titania nanotube surface irregularity, this causes on Nano tube array of titanium dioxide because CuS is nanoparticle sensitized.
Fig. 2 is the impact of different sensitization time on TNTAs crystal formation: (a) non-sensitization (b) sensitization 6h (c) sensitization 10h (d) sensitization 14h (e) CuS nano particle.Show in figure: the crystal formation of the titania nanotube of non-sensitization is amorphous state, the only diffraction peak of the pure titanium of display substrate, along with the increase of sensitization time, engender the diffraction peak of Detitanium-ore-type in the sample to which, increase along with sensitization time is described, the crystal formation of titania nanotube changes Detitanium-ore-type into from amorphous state gradually; Then start the diffraction peak having occurred covellite type CuS after sensitization 10h, illustrate that, after 10 hours, CuS sensitization is on titania nanotube.。
Fig. 3 is the UV-Vis absorption spectrum of TNTAs under different sensitization time: TNTAs (c) sensitization 6h (d) sensitization 10h (e) the sensitization 14h of the non-sensitization of pure titanium sheet (b) after the process of (a) physical chemistry.Show in figure: five samples all have very wide absorption band in Visible-to-Near InfaRed region, have wider strong absorption region at 350nm-900nm; The sample of the more non-sensitization of the sample after sensitization has stronger absorption intensity.
Fig. 4 is that the ultraviolet absorpting spectrum of RhB changes (A); The contrast experiment (B) of the CuS/TNTAs Visible Light Induced Photocatalytic rhodamine B of sensitization different time: (a) RhB stoste (b) 0min (c) 6h (d) 10h (e) 14h.Show in figure: the sample of non-sensitization does not have degradation effect to rhodamine B substantially, and sensitization time to be the sample degradation rate of 10h the highest, can more than 70% be reached after 60min, be the sample of 6h, 14h higher than sensitization time, illustrate that sensitization time is best to the degradation effect of rhodamine B when 10min.
Claims (1)
1. a preparation method for the nanoparticle sensitized Nano tube array of titanium dioxide of CuS, is characterized in that step is as follows:
1) preparation of Nano tube array of titanium dioxide
A) pre-treatment of technical pure titanium sheet: technical pure titanium sheet is carried out surface finish process with 800#, 1000#, 1200# abrasive paper for metallograph successively, then successively with acetone, ethanol, deionized water ultrasonic cleaning to remove its surperficial grease, be the salpeter solution of 65wt% and concentration by distilled water, concentration be again that the mixing solutions of the hydrofluoric acid solution of 40wt% is to its chemical rightenning, the volume ratio of distilled water in mixing solutions, concentration to be the salpeter solution of 65wt% and concentration the be hydrofluoric acid solution of 40wt% is 5:4:1, finally air-dry rear for subsequent use with distilled water flushing;
B) anodic oxidation: adopt two electrodes system, respectively with pretreated titanium sheet and graphite flake for anode and negative electrode, under 55-65V constant voltage DC, anodic oxidation 4-8 hour is carried out in the electrolytic solution be made up of deionized water, phosphoric acid, Neutral ammonium fluoride and ethylene glycol, in electrolytic solution, the volume percent of each component is deionized water 3%, phosphatase 24 %, the concentration of Neutral ammonium fluoride is 0.6g/mL, ethylene glycol is surplus, then take out titanium sheet, be placed in the film in deionized water for ultrasonic cleaning removing titanium sheet;
C) two-step anodization: the titanium sheet after b) processing is carried out second time anodic oxidation under the condition identical with an anodic oxidation, oxidization time is 7-10 hour, then ultrasonic cleaning 10-20min in dehydrated alcohol, after drying at 550 DEG C cycle annealing 3 hours, then in air atmosphere, room temperature is naturally cooled to, obtained Nano tube array of titanium dioxide;
2) preparation of the Nano tube array of titanium dioxide that CuS is nanoparticle sensitized
Above-mentioned Nano tube array of titanium dioxide being immersed volume ratio is in the Cu source precursor solution of 1:1 and the mixing solutions of S source precursor solution, CuSO in the precursor solution of Cu source
4be Na in the precursor solution of 0.01g:5mL, S source with the amount ratio of deionized water
2s
2o
3be 0.01g:5mL with the amount ratio of deionized water, hydro-thermal sensitized treatment 6-14 hour at 100 DEG C in a kettle., to be cooledly to take out to room temperature, repeatedly rinse 6-10 time with deionized water and dehydrated alcohol, dry under room temperature, the Nano tube array of titanium dioxide that obtained CuS is nanoparticle sensitized.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106064093A (en) * | 2016-05-20 | 2016-11-02 | 辽宁石油化工大学 | A kind of preparation method of fabricated in situ CuS/WO3 heterojunction photocatalyst |
| CN107670673A (en) * | 2017-09-27 | 2018-02-09 | 湖北工业大学 | A kind of TiO2The preparation method of/CuS composite Nano array photoelectrics pole material |
| CN109055918A (en) * | 2018-07-24 | 2018-12-21 | 北京石油化工学院 | A kind of CdS/TiO2Nano-tube array hetero-junctions and preparation method thereof |
| CN109324011A (en) * | 2018-09-19 | 2019-02-12 | 曾小敏 | The method for detecting bacterium living based on nano material |
| CN113583355A (en) * | 2021-07-30 | 2021-11-02 | 浙江元通线缆制造有限公司 | Rubber material for one-to-two vulcanization production line and preparation method thereof |
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| CN102776513A (en) * | 2012-07-13 | 2012-11-14 | 西南交通大学 | Preparation process of TiO2 nanotube/PbS/CuS nanocomposite |
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| CN109055918A (en) * | 2018-07-24 | 2018-12-21 | 北京石油化工学院 | A kind of CdS/TiO2Nano-tube array hetero-junctions and preparation method thereof |
| CN109055918B (en) * | 2018-07-24 | 2020-07-28 | 北京石油化工学院 | CdS/TiO2Nanotube array heterojunction and preparation method thereof |
| CN109324011A (en) * | 2018-09-19 | 2019-02-12 | 曾小敏 | The method for detecting bacterium living based on nano material |
| CN113583355A (en) * | 2021-07-30 | 2021-11-02 | 浙江元通线缆制造有限公司 | Rubber material for one-to-two vulcanization production line and preparation method thereof |
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