CN106315750B - Visible light catalyst molybdenum disulfide carried titanium dioxide nanotube electrode and its preparation method and application - Google Patents
Visible light catalyst molybdenum disulfide carried titanium dioxide nanotube electrode and its preparation method and application Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000002071 nanotube Substances 0.000 title claims abstract description 57
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 54
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 47
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 claims abstract description 15
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- 239000003792 electrolyte Substances 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 19
- 238000004070 electrodeposition Methods 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000007605 air drying Methods 0.000 claims description 11
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 11
- 229910052724 xenon Inorganic materials 0.000 claims description 11
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005498 polishing Methods 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 239000000975 dye Substances 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- -1 thio ammonium molybdate Chemical compound 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000000593 degrading effect Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 239000010919 dye waste Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanotube electrodes and its preparation method and application.The visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanotube electrode prepared in the present invention has apparent visible absorption performance, while having apparent photocurrent response.Visible light catalyst molybdenum disulfide carried titanium dioxide nanotube electrode degrading organic dye waste water prepared by the present invention, shows good visible light photoelectric catalytically active.The beneficial effects of the invention are as follows simple processes, and catalyst is easy recycling, can be used for large-scale industrial production, higher to the degradation efficiency of organic dye waste water in visible-range, have very high practical value and application prospect.
Description
Technical field
The invention belongs to the photocatalysis technology field in environmental improvement, it is related to a kind of preparation method of photochemical catalyst and its answers
With being related specifically to a kind of visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanotube electrode and preparation method thereof and answer
With.
Background technique
21st century global environmental pollution and energy crisis become the mankind and have to face two big realistic problems.Light is urged
Be turned to a kind of Green Chemical Technology, with the research of persistence organic pollutant difficult to degrade in this method removal environment at
For the hot spot of people's research.TiO2It as most representative, while being also the typical photochemical catalyst of most application prospect, especially
TiO with one-dimensional ordered structure2Nano-tube array more due to its with unique oldered array structure, high specific surface area with
And preferably charge transfer performance and cause the extensive concern of people.However, Detitanium-ore-type TiO2Forbidden bandwidth be
3.2eV, excitation wavelength 387.5nm, belongs to ultraviolet region.And for solar spectrum, main energetic concentrates on 460nm-
600nm wave-length coverage, so ultraviolet light proportion is less than 5%, therefore TiO2To accounting for, the most visible light of solar spectrum is sharp
It is lower with rate.In addition, TiO2The photogenerated charge generated under light illumination and hole are easy to occur in crystals compound, lead to its amount
Sub- efficiency is relatively low.Both of these problems limit TiO2Application in practice.
Summary of the invention
Goal of the invention: in view of the above-mentioned problems, visible-light photocatalyst molybdenum disulfide carried titanium dioxide prepared by the present invention
Nanotube electrode passes through to TiO2The modification of nano-tube array can make its optical response range successfully be extended to visible light region, and
And the separative efficiency in light induced electron and hole can be effectively improved.By TiO2Compound with narrow-band semiconductor is to improve its visible light to live
A kind of effective method of modifying of property.One kind provided by the invention is pollution-free, the simple visible-light photocatalyst curing of step
The catalyst of the preparation method of molybdenum carried titanium dioxide nanotube electrode, preparation method synthesis has good visible absorption
Performance and visible light photocurrent response.There is good Visible Light Induced Photocatalytic effect to organic dye waste water simultaneously.
Technical solution: the present invention provides the systems of visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanotube electrode
Preparation Method, comprising the following steps:
1) HF and HNO solution allocation: are taken3It is dissolved in deionized water, obtains mixed acid solution；Take NH4F and deionization are water-soluble
Solution obtains the electrolyte of anodic oxidation in ethylene glycol；Four thio ammonium molybdate and anhydrous sodium sulfate is taken to be dissolved in deionized water,
And maintaining nitrogen purge 10-20 minutes, dissolved oxygen is excluded, electro-deposition electrolyte is obtained；
2) preparation of titanium dioxide nanotube array electrode: the sand paper of titanium sheet different meshes is polishing to respectively it is smooth,
Titanium sheet after polishing is placed in mixed acid solution and is etched, is then cleaned by ultrasonic respectively through ethyl alcohol and deionized water, then in anode
Working electrode is made with the titanium sheet after being cleaned by ultrasonic in the electrolyte of oxidation, platinum plate electrode is made to be connected respectively to direct current to electrode
The positive and negative polarities in source are slowly forced into 50-80V, at room temperature after anodic oxidation reactions 20-50min, after anodic oxidation reactions
Electrode take out and clean, the electrode after cleaning is placed in natural air drying in air, and the electrode after natural air drying is placed in vacuum type
It is calcined in Fiber tube type furnace, obtains titanium dioxide nanotube array electrode；
3) preparation of molybdenum disulfide carried titanium dioxide nanotube electrode: by nano titania in electro-deposition electrolyte
For pipe array electrode as cathode, platinum electrode applies the DC voltage of -0.2~-0.5V as anode, at the same using xenon lamp as
Light irradiation cathode after electro-deposition 10-20min, is sufficiently rinsed with deionized water, and naturally dry obtains molybdenum disulfide load titanium dioxide
Titanium nanotube electrode.
Wherein, above-mentioned steps 1) in mixed acid solution preparation in, the additional amount of HF is 1-10ml, HNO3Additional amount be 4-
40ml, the additional amount of deionized water are 5-50ml.
Wherein, above-mentioned steps 1) in anodic oxidation electrolyte preparation in, NH4The additional amount of F is 0.1-0.5g, is gone
The additional amount of ionized water is 0.5-2ml, and the additional amount of ethylene glycol is 70-90ml.
Wherein, above-mentioned steps 1) in electro-deposition electrolyte preparation in, the additional amount of four thio ammonium molybdate is 0.01-
0.1g, anhydrous sodium sulfate additional amount be 0.05-0.2g, the additional amount of deionized water is 40-60ml.
The visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanotube electrode that above-mentioned preparation method is prepared.
Above-mentioned visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanotube electrode is in degrading organic dye waste water
In application.
Above-mentioned organic dyestuff is methylene blue.Visible light catalyst molybdenum disulfide carried titanium dioxide nanotube of the invention
Electrode can be applied in degrading organic dye waste water, and specific technical solution is as follows: in a homemade quartz reactor
In, when the organic dyestuff photoelectrocatalysis such as degradation of methylene blue reacts, use the xenon lamp of 500W as light source, xenon lamp is from reactor
Distance is 25cm, and filtering off wavelength with optical filtering is 410nm ultraviolet light below；In container bottom plus magnetic agitation, it will be seen that light
Catalyst molybdenum disulfide carried titanium dioxide nanotube electrode is used as working electrode, platinum electrode to electrode, is saturated sweet common-battery
Reference electrode is made in pole, applies the bias of 0.6V；It can be dense to detect solution with the absorbance of 721 type spectrophotometric determination solution
The variation of degree.
The utility model has the advantages that the present invention has following advantages referring now to the prior art:
(1) preparation process of the present invention is simple, does not need expensive equipment, can be not only used for experimental implementation, and can be industrially big
Large-scale production.
(2) the visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanotube electrode prepared in the present invention has bright
Aobvious visible absorption performance, while there is apparent photocurrent response.
(3) visible light catalyst molybdenum disulfide carried titanium dioxide nanotube electrode degradating organic dye prepared by the present invention
Waste water shows good visible light photoelectric catalytically active.
(4) the beneficial effects of the invention are as follows simple process, catalyst is easy recycling, can be used for large-scale industrial production,
It is higher to the degradation efficiency of organic dye waste water in visible-range, there is very high practical value and application prospect.
Detailed description of the invention
Fig. 1 is the X-ray diffraction of molybdenum disulfide carried titanium dioxide nanotube electrode prepared by the embodiment of the present invention 1~4
(XRD) figure.Abscissa is twice of the angle of diffraction (2 θ), and ordinate is the intensity (cps) of diffraction maximum.In figure: MoS2: JCODS
NO.65-0160；TiO2: JCODS NO.21-1272；
Fig. 2 is the energy dissipation X of molybdenum disulfide carried titanium dioxide nanotube electrode prepared by the embodiment of the present invention 1~4
Ray (EDX) spectrogram；
Fig. 3 is the UV-vis DRS figure of the molybdenum disulfide carried titanium dioxide nanotube electrode of Examples 1 to 4 preparation
(UV-Vis-DRS).Abscissa is light excitation wavelength (nm), and ordinate is absorbance；
Fig. 4 is that the molybdenum disulfide carried titanium dioxide nanotube electrode photoelectric catalysis degrading of Examples 1 to 4 preparation has engine dyeing
Expect the schematic diagram of methylene blue.Abscissa is reaction time (min), and ordinate is the concentration (mg L-1) of methylene blue；Figure
In: the photoelectric catalysis degrading process of-■-titanium dioxide；The photoelectrocatalysis of ●-molybdenum disulfide carried titanium dioxide nanotube drops
Solution preocess.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies specific material proportion, process conditions and its result described in example and is merely to illustrate the present invention, without that should will not limit
The present invention described in detail in claims processed.
The preparation of 1 visible light catalyst molybdenum disulfide carried titanium dioxide nanotube electrode of embodiment
Take 5ml HF and 20ml HNO3It is dissolved in 25ml deionized water, obtains mixed acid solution.Titanium sheet is used into difference respectively
The sand paper of mesh number is polishing to smooth, and electrode slice is placed in mixed acid solution and is etched, after it is clear through ethyl alcohol and deionized water ultrasound respectively
It washes.Take 0.2g NH4F and 1.6ml deionized water dissolving obtains the electrolyte of anodic oxidation in 78ml ethylene glycol.Made with titanium sheet
For working electrode, platinum plate electrode is used as to electrode, is connected respectively to the positive and negative polarities of DC power supply, is slowly forced into 60V, in room
After warm anodic oxygenization reaction 30min, titanium sheet is taken out, the electrode after cleaning is placed in natural air drying in air, by anodic oxidation
Electrode after reaction is placed in vacuum type Fiber tube type furnace and calcines, and obtains titanium dioxide nanotube array electrode.
It takes 0.013g four thio ammonium molybdate and 0.071g anhydrous sodium sulfate to be dissolved in 50ml deionized water, and persistently leads to nitrogen
Gas 15 minutes, exclude dissolved oxygen.For titanium dioxide nanotube array electrode as cathode, platinum electrode applies -0.4V as anode
DC voltage after electro-deposition 20min, sufficiently rinsed with deionized water, dried in the air naturally while using xenon lamp as light irradiation cathode
Do to obtain molybdenum disulfide carried titanium dioxide nanotube electrode.
The preparation of 2 visible light catalyst molybdenum disulfide carried titanium dioxide nanotube electrode of embodiment
1) 1mlHF and 4mlHNO solution allocation: are taken3It is dissolved in 5ml deionized water, obtains mixed acid solution；Take 0.1g
NH4F and 0.5ml deionized water dissolving obtains the electrolyte of anodic oxidation in 70ml ethylene glycol；Take 0.01g tetrathio molybdic acid
Ammonium and 0.05g anhydrous sodium sulfate are dissolved in 40ml deionized water, and maintaining nitrogen purge 10-20 minutes, are excluded dissolved oxygen, are obtained electric
Deposited electrolyte；
2) preparation of titanium dioxide nanotube array electrode: the sand paper of titanium sheet different meshes is polishing to respectively it is smooth,
Titanium sheet after polishing is placed in mixed acid solution and is etched, is then cleaned by ultrasonic respectively through ethyl alcohol and deionized water, then in anode
Working electrode is made with the titanium sheet after being cleaned by ultrasonic in the electrolyte of oxidation, platinum plate electrode is made to be connected respectively to direct current to electrode
The positive and negative polarities in source are slowly forced into 50-80V, at room temperature after anodic oxidation reactions 20-50min, after anodic oxidation reactions
Electrode take out and clean, the electrode after cleaning is placed in natural air drying in air, and the electrode after natural air drying is placed in vacuum type
It is calcined in Fiber tube type furnace, obtains titanium dioxide nanotube array electrode；
3) preparation of molybdenum disulfide carried titanium dioxide nanotube electrode: by nano titania in electro-deposition electrolyte
For pipe array electrode as cathode, platinum electrode applies the DC voltage of -0.2~-0.5V as anode, at the same using xenon lamp as
Light irradiation cathode after electro-deposition 10-20min, is sufficiently rinsed with deionized water, and naturally dry obtains molybdenum disulfide load titanium dioxide
Titanium nanotube electrode.
The preparation of 3 visible light catalyst molybdenum disulfide carried titanium dioxide nanotube electrode of embodiment
1) 10mlHF and 40mlHNO solution allocation: are taken3It is dissolved in 50ml deionized water, obtains mixed acid solution；Take 0.5g
NH4F and 2ml deionized water dissolving obtains the electrolyte of anodic oxidation in 90ml ethylene glycol；Take 0.013g four thio ammonium molybdate
It is dissolved in 50ml deionized water with 0.071g anhydrous sodium sulfate, and maintaining nitrogen purge 10-20 minutes, excludes dissolved oxygen, obtain electric
Deposited electrolyte；
2) preparation of titanium dioxide nanotube array electrode: the sand paper of titanium sheet different meshes is polishing to respectively it is smooth,
Titanium sheet after polishing is placed in mixed acid solution and is etched, is then cleaned by ultrasonic respectively through ethyl alcohol and deionized water, then in anode
Working electrode is made with the titanium sheet after being cleaned by ultrasonic in the electrolyte of oxidation, platinum plate electrode is made to be connected respectively to direct current to electrode
The positive and negative polarities in source are slowly forced into 50-80V, at room temperature after anodic oxidation reactions 20-50min, after anodic oxidation reactions
Electrode take out and clean, the electrode after cleaning is placed in natural air drying in air, and the electrode after natural air drying is placed in vacuum type
It is calcined in Fiber tube type furnace, obtains titanium dioxide nanotube array electrode；
3) preparation of molybdenum disulfide carried titanium dioxide nanotube electrode: by nano titania in electro-deposition electrolyte
For pipe array electrode as cathode, platinum electrode applies the DC voltage of -0.2~-0.5V as anode, at the same using xenon lamp as
Light irradiation cathode after electro-deposition 10-20min, is sufficiently rinsed with deionized water, and naturally dry obtains molybdenum disulfide load titanium dioxide
Titanium nanotube electrode.
The preparation of 4 visible light catalyst molybdenum disulfide carried titanium dioxide nanotube electrode of embodiment
1) 6mlHF and 25mlHNO solution allocation: are taken3It is dissolved in 25ml deionized water, obtains mixed acid solution；Take 0.3g
NH4F and 1.25ml deionized water dissolving obtains the electrolyte of anodic oxidation in 85ml ethylene glycol；Take 0.1g tetrathio molybdic acid
Ammonium and 0.2g anhydrous sodium sulfate are dissolved in 60ml deionized water, and maintaining nitrogen purge 10-20 minutes, are excluded dissolved oxygen, are obtained electric
Deposited electrolyte；
2) preparation of titanium dioxide nanotube array electrode: the sand paper of titanium sheet different meshes is polishing to respectively it is smooth,
Titanium sheet after polishing is placed in mixed acid solution and is etched, is then cleaned by ultrasonic respectively through ethyl alcohol and deionized water, then in anode
Working electrode is made with the titanium sheet after being cleaned by ultrasonic in the electrolyte of oxidation, platinum plate electrode is made to be connected respectively to direct current to electrode
The positive and negative polarities in source are slowly forced into 50-80V, at room temperature after anodic oxidation reactions 20-50min, after anodic oxidation reactions
Electrode take out and clean, the electrode after cleaning is placed in natural air drying in air, and the electrode after natural air drying is placed in vacuum type
It is calcined in Fiber tube type furnace, obtains titanium dioxide nanotube array electrode；
3) preparation of molybdenum disulfide carried titanium dioxide nanotube electrode: by nano titania in electro-deposition electrolyte
For pipe array electrode as cathode, platinum electrode applies the DC voltage of -0.2~-0.5V as anode, at the same using xenon lamp as
Light irradiation cathode after electro-deposition 10-20min, is sufficiently rinsed with deionized water, and naturally dry obtains molybdenum disulfide load titanium dioxide
Titanium nanotube electrode.
Fig. 1 illustrates the visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanometer of the preparation of the embodiment of the present invention 1~4
X-ray diffraction (XRD) figure of pipe electrode, as we can see from the figure MoS2And TiO2Diffraction maximum.Fig. 2 illustrates sheet of the invention
The energy dissipation X-ray of visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanotube prepared by inventive embodiments 1~4
(EDX) spectrogram, the result of Cong Tuzhong can see to be consistent with the result of XRD.UV-vis DRS figure (UV-Vis-
DRS) as shown in figure 3, the visible-light photocatalyst molybdenum disulfide load that as can be seen from the figure prepared by the embodiment of the present invention 1~4
Titania nanotube has stronger absorption in visible region, shows preferable visible light photocatalysis active.
Experimental example
The visible light catalyst molybdenum disulfide carried titanium dioxide nanotube electrode that Examples 1 to 4 is prepared is used for
Degradating organic dye methylene blue.
Using molybdenum disulfide carried titanium dioxide nanotube electrode as working electrode, platinum electrode is used as to electrode, is saturated sweet
Mercury electrode is as reference electrode.It takes the methylene blue solution 100ml that initial concentration is 20mg/L in quartz reactor, is added
0.142g anhydrous sodium sulfate, stirring to dissolution.Apply the bias of 0.6V, first stirs 20min in the dark state, make it in catalyst table
Face starts to carry out photoelectrocatalysis reaction after reaching adsorption equilibrium.Use the xenon lamp of 500W as light source, filters off wavelength with optical filtering
For 410nm ultraviolet light below, photoelectrocatalysis reaction is carried out.721 type spectrophotometrics of 2ml reaction solution are taken to measure every 20min
The absorbance of solution is determined to detect the variation of solution concentration, is persistently stirred in reaction process, after reacting 240min, methylene blue
Degradation rate has reached 60%.And the titania nanotube without loading molybdenum disulfide is only capable of reaching to the degradation efficiency of methylene blue
To 30%.
Photoelectric catalysis degrading organic dyestuff methylene blue effect diagram in Fig. 4 as shown in figure 4, give titanium dioxide
The degradation curve of titanium photoelectric catalysis degrading methylene blue.From fig. 4, it can be seen that under the conditions of visible light shines, molybdenum disulfide load two
TiOx nano pipe electrode is significantly improved than the performance tool of the photoelectric catalysis degrading pollutant of titanium dioxide.
Claims (5)
1. the preparation method of visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanotube electrode, which is characterized in that including
Following steps:
1) HF and HNO solution allocation: are taken3It is dissolved in deionized water, obtains mixed acid solution；Take NH4F and deionized water dissolving in
In ethylene glycol, the electrolyte of anodic oxidation is obtained；It takes four thio ammonium molybdate and anhydrous sodium sulfate to be dissolved in deionized water, and holds
It is continuous nitrogen 10-20 minutes logical, dissolved oxygen is excluded, electro-deposition electrolyte is obtained；
2) preparation of titanium dioxide nanotube array electrode: the sand paper of titanium sheet different meshes being polishing to respectively smooth, will be beaten
Titanium sheet after mill, which is placed in mixed acid solution, to be etched, and is then cleaned by ultrasonic respectively through ethyl alcohol and deionized water, then in anodic oxidation
Electrolyte in working electrode made with the titanium sheet after being cleaned by ultrasonic, platinum plate electrode is made to be connected respectively to DC power supply to electrode
Positive and negative polarities are slowly forced into 50-80V, at room temperature after anodic oxidation reactions 20-50min, by the electricity after anodic oxidation reactions
Pole is taken out and is cleaned, and the electrode after cleaning is placed in natural air drying in air, and the electrode after natural air drying is placed in vacuum type fiber
It is calcined in tube furnace, obtains titanium dioxide nanotube array electrode；
3) preparation of molybdenum disulfide carried titanium dioxide nanotube electrode: by titania nanotube battle array in electro-deposition electrolyte
Column electrode is as cathode, and platinum electrode applies the DC voltage of -0.2~-0.5V as anode, while using xenon lamp as light source
Cathode is irradiated, after electro-deposition 10-20min, is sufficiently rinsed with deionized water, naturally dry obtains molybdenum disulfide carried titanium dioxide and receives
Mitron electrode；
In the step 1) in the preparation of mixed acid solution, the additional amount of HF is 1-10mL, HNO3Additional amount be 4-40mL, go
The additional amount of ionized water is 5-50mL；
In the preparation of the electrolyte of anodic oxidation in the step 1), NH4The additional amount of F is 0.1-0.5g, and deionized water adds
Entering amount is 0.5-2mL, and the additional amount of ethylene glycol is 70-90mL；
In the preparation of electro-deposition electrolyte in the step 1), the additional amount of four thio ammonium molybdate is 0.01-0.1g, anhydrous sulphur
The additional amount of sour sodium is 0.05-0.2g, the additional amount of deionized water is 40-60mL.
2. the visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanometer that preparation method described in claim 1 is prepared
Pipe electrode.
3. visible-light photocatalyst molybdenum disulfide carried titanium dioxide nanotube electrode as claimed in claim 2 has engine dyeing in degradation
Expect the application in waste water.
4. application according to claim 3, which is characterized in that the organic dyestuff is methylene blue.
5. application according to claim 3, which is characterized in that when degradating organic dye photoelectrocatalysis reacts, use 500W
Xenon lamp as light source, xenon lamp with a distance from reactor be 25cm, with optical filtering filter off wavelength be 410nm ultraviolet light below；
In container bottom plus magnetic agitation, it will be seen that light photochemical catalyst molybdenum disulfide carried titanium dioxide nanotube electrode is as work electricity
Pole, platinum electrode are used as to electrode, and saturated calomel electrode applies the bias of 0.6V as reference electrode.
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| CN107723777B (en) * | 2017-10-16 | 2019-04-16 | 南通纺织丝绸产业技术研究院 | The preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot |
| CN107649154B (en) * | 2017-11-02 | 2019-12-10 | 江苏科技大学 | Visible light photocatalyst loaded titanium dioxide nanotube electrode and preparation method and application thereof |
| CN108455709B (en) * | 2018-04-11 | 2021-06-25 | 北京工业大学 | Preparation method of indium trioxide modified titanium dioxide nanotube array electrode |
| CN108505098B (en) * | 2018-06-14 | 2020-07-24 | 苏州大学 | Preparation method of Pt-loaded sulfur-rich molybdenum disulfide boundary site modified titanium dioxide nanotube array |
| CN109046392B (en) * | 2018-09-11 | 2020-07-21 | 北京邮电大学 | Catalyst for producing hydrogen by photocatalytic water decomposition and preparation method thereof |
| CN109621943B (en) * | 2018-12-24 | 2021-06-29 | 南昌航空大学 | Preparation method and application of 1T-phase molybdenum disulfide-loaded titanium dioxide nanotube array |
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| CN104894627A (en) * | 2015-04-08 | 2015-09-09 | 天津大学 | Molybdenum disulfide-loaded titania nanotube and synthetic method thereof |
| CN105442012A (en) * | 2016-01-07 | 2016-03-30 | 河南工程学院 | Preparation method and application of composite nanometer material MoS2/TiO2 nanotube array |
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