CN107723777A - The preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot - Google Patents
The preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot Download PDFInfo
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 94
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 44
- 239000002096 quantum dot Substances 0.000 title claims abstract description 41
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000002071 nanotube Substances 0.000 claims abstract description 98
- 239000010936 titanium Substances 0.000 claims abstract description 35
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 229910001868 water Inorganic materials 0.000 claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 18
- 239000002135 nanosheet Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000007743 anodising Methods 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 4
- 238000003780 insertion Methods 0.000 claims description 4
- 230000037431 insertion Effects 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 238000000151 deposition Methods 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 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 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 44
- 101710116850 Molybdenum cofactor sulfurase 2 Proteins 0.000 description 40
- 238000012986 modification Methods 0.000 description 20
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 17
- 229960000907 methylthioninium chloride Drugs 0.000 description 17
- 229910052961 molybdenite Inorganic materials 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LZOZLBFZGFLFBV-UHFFFAOYSA-N sulfene Chemical compound C=S(=O)=O LZOZLBFZGFLFBV-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/393—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
Abstract
The invention discloses a kind of preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot, carries out cleaning pretreatment to substrate material surface first；Ethylene glycol solution of the preparation containing ammonium fluoride and water is electrolyte, carries out electrochemical anodic oxidation to titanium-based bottom material, and be placed in Muffle furnace and calcine；Again by molybdenum disulfide using infrared tablet press machine by powdered to preparing slabbing；Finally by D.C. regulated power supply, curing molybdenum sheet is anode, and Nano tube array of titanium dioxide carries out electrolysis stripping as electrolyte using double trifluoromethanesulfonimide lithium solution and deposit molybdenum disulfide quantum dot as negative electrode.Nano tube array of titanium dioxide controllable deposition molybdenum disulfide quantum dot, can improve TiO2Photocatalysis efficiency；Light absorpting ability, and p n knots are formed using composite, photocatalytic degradation capability of the electrode pair to organic pollution can be improved when being applied to photocatalysis.
Description
Technical field
The present invention relates to photocatalytic pollutant degradation field of material technology, and in particular to a kind of electro-deposition molybdenum disulfide quantum
The preparation method of the TiO 2 nanotubes modified array of point.
Background technology
The environmental pollution sharply increased with large area of energy demand is the outstanding problem that today's society is faced, and has engine dyeing
Material pollution is distinct issues the most in water pollution now.Titanium dioxide（TiO2）As a kind of new n-type semiconductor,
Because it has the characteristics that chemical stability, photoelectric characteristic, biocompatibility, the corrosion resistance of protrusion, light is had been widely used for
Catalyzing and degrading pollutant, fuel sensitization solar battery, bio-medical material, gas sensor and photolysis water hydrogen etc.,
New approach is provided for the green degraded of organic pollution.
Nano-TiO2Except with the skin effect as common nano material, low dimensional effect, quantum size effect
Outside macro quanta tunnel effect, also with its special property, especially catalytic performance.Compared with TiO2Nano particle, TiO2Nanometer
Pipe array has the advantages that specific surface area is big, surface energy is high, the rate of load condensate in easy to be recycled and electronics and hole is relatively low, by
People's more concern and research.But TiO2Nano-tube array limits it at many aspects there are still some shortcomings
Application：(1)TiO2Energy gap it is wider (anatase is 3.2 eV, and rutile is 3.0 eV), 3 ~ 5% can only be absorbed too
Solar ray energy (nm of λ ＜ 387), utilization rate is low；(2)TiO2The recombination rate of the photo-generate electron-hole pair of nanotube is still higher, and light is urged
It is low to change activity.
In view of the above-mentioned problems, doping metals, nonmetallic and semi-conductor nano particles and TiO by all means2Nanometer
Pipe array combines, to improve TiO2The PhotoelectrocatalytiPerformance Performance of nano-tube array turns into the focus studied at present.On the one hand, noble metal
Nano particle is dispersed in TiO2Nanotube surface can assist to capture light induced electron, accelerate the separation of electron hole, and then suppress light
Raw electronics and hole-recombination.On the other hand, noble metal granule can improve TiO by surface resonance effect2The visible ray of nanotube
Absorbability.
Molybdenum disulfide, a kind of new two-dimensional material, is widely used in lubricant, catalyst, coating material nearly ten years
With electron probe, solar cell, photoelectric device etc..As a kind of p-type transient metal sulfide semiconductor, molybdenum disulfide
Energy gap is 1.73ev, with TiO2After compound, p-n heterojunction is formd, makes TiO2The photoresponse region of nano-tube array is from purple
To visual field direction red shift occurs for outskirt, so as to improve the utilization rate to solar energy；On the other hand, because the forbidden band of the two is wide
Difference is spent, light induced electron and hole can be enable to efficiently separate, therefore improve photoelectric transformation efficiency.In recent years, two sulphur
Change the method that molybdenum is prepared using hydro-thermal more with composite titania material, have technique cumbersome mostly, complicated condition, expend the time
The shortcomings of long.
The content of the invention
It is an object of the present invention to provide a kind of preparation of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot
Method, solve the above problems.
The technical scheme is that：
A kind of preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot, this method include following step
Suddenly：
(1) pretreatment of titanium sheet：Titanium sheet substrate is cleaned by ultrasonic；
(2) anodizing prepares TiO2Nano-tube array：Using the titanium sheet substrate as anode, using platinum plate electrode as negative electrode, will
The anode and negative electrode insert simultaneously contains NH4F and H2In O ethylene glycol solution, applying voltage makes the anodic oxidation, is made
TiO2Nano-tube array, then by the TiO2Nano-tube array is calcined, and makes the TiO2Nano-tube array is from unformed state
TiO2Nano-tube array is transformed into the TiO of anatase2Nano-tube array；
(3) molybdenum disulfide powder is made to the molybdenum disulfide nano sheet of solid sheet with infrared tablet press machine；
(4) using the molybdenum disulfide nano sheet as anode, the TiO2Nano-tube array is as negative electrode, double fluoroform sulphonyl
The imine lithium aqueous solution is powered as electrolyte, modifies titanium dioxide with water rinsing, drying, obtained electro-deposition molybdenum disulfide quantum dot
Titanium nano-tube array.
Further, the material of titanium sheet described in step (1) is pure titanium or titanium alloy, and size is 1.5cm × 3.0cm.
Further, it is cleaned by ultrasonic described in step (1) to be cleaned by ultrasonic 20 using acetone, ethanol and deionized water successively
~30min.
Further, NH is contained described in step (2)4F and H2In O ethylene glycol solution, NH4F mass percent concentration
For 0.1~1.0wt%, H2O concentration of volume percent is 1.0~5.0v%.
Further, the voltage of anodic oxidation described in step (2) is 40~60V, and the time is 1 ~ 2h.
Further, calcining is to calcine in atmosphere described in step (2), and the temperature of calcining is 400~500 DEG C, calcining
Time be 1~3h, the heating of calcining and rate of temperature fall are 3~5 DEG C/min.
Further, molybdenum disulfide powder described in step (3) is 400~500mg, the pressure that the infrared tablet press machine applies
Power is 15~20Mpa, and the time of pressure is 45s~60s.
Further, the concentration of double trifluoromethanesulfonimide lithiums is 0.1wt%~0.5wt% described in step (4).
Further, the voltage of application of being powered described in step (4) is 4~6V, and conduction time is respectively 0.5h, 1h, 2h,
It is described to be rinsed with water to be cleaned 3 times with absolute ethyl alcohol and deionized water after energization every time.
Further, the temperature dried described in step (4) is 50~60 DEG C.
The invention provides a kind of preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot,
Solve many conventional method complex procedures, the problems such as time-consuming, stability difference, have simple process easy to operate, can control
The advantages of scattered and size of molybdenum disulfide.The Nano tube array of titanium dioxide of nanometer MOS 2 particle modification is on the one hand
The light absorpting ability of compound can be improved；On the other hand its photoresponse can be expanded to visible region, improves the utilization of sunshine
Rate.With not compound TiO2Compare, the TiO of obtained composite molybdenum disulfide nano particle2Nano-tube array photochemical catalyst is in purple
The 10mg/L methylene blue of being degraded under outer light is 3.2 times of unmodified titania nanotube photocatalytic speed, photocatalytic degradation
The efficiency of pollutant significantly improves, and has good chemical stability and recuperability, and low cost, large-scale industry can be achieved
Change application.This method is peeled off molybdenum disulfide using electricity and is deposited on simultaneously under electric field driven on Nano tube array of titanium dioxide, work
Skill is simple and easy to operate, realize molybdenum disulfide quantum dot on the nanotube with inside it is dispersed, effectively increase photocatalysis
The efficiency of degradation of methylene blue, there is good chemical stability and recuperability, low cost, heavy industrialization can be achieved
Using.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill of field, without having to pay creative labor, it can also be obtained according to these accompanying drawings other
Accompanying drawing.Wherein,
Fig. 1 is that the flow of the preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot of the present invention is shown
It is intended to；
Fig. 2 is anode in the preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot of the present invention
Aoxidize the TiO of the high-sequential of 2 h preparations2The TEM shape appearance figures of nano-tube array；
Fig. 3 is two sulphur in the preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot of the present invention
Change the nano-particle modified TiO of molybdenum2The TEM shape appearance figures of nano-tube array；
Fig. 4 is two sulphur in the preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot of the present invention
Change the nano-particle modified TiO of molybdenum2SAED, HRTEM and EDS spectrogram of nano-tube array；
Fig. 5 is unmodified TiO2The TiO of 450 DEG C of nano-tube array calcining, molybdenum disulfide and nanometer MOS 2 particle modification2Receive
The Raman spectrogram of mitron array；
Fig. 6 is unmodified TiO2The TiO of 450 DEG C of nano-tube array calcining, molybdenum disulfide and nanometer MOS 2 particle modification2Receive
The XRD spectra of mitron array；
Fig. 7 is unmodified TiO2Nano-tube array and the TiO of nanometer MOS 2 particle modification2The XPS spectrum figure of nano-tube array；
Fig. 8 is unmodified TiO2The ultraviolet-visible light diffusing reflection collection of illustrative plates (a) and nanometer MOS 2 particle of nano-tube array are modified
TiO2The fluorescence pattern (b) of nano-tube array；
Fig. 9 is unmodified TiO2Nano-tube array and the TiO of nanometer MOS 2 particle modification2The photoelectricity flow graph of nano-tube array
Spectrum；
Figure 10 is unmodified TiO2Nano-tube array and the TiO of nanometer MOS 2 particle modification2The photocatalysis of nano-tube array
Design sketch (a) and kinetics equation figure (b)；
Figure 11 is unmodified TiO2Nano-tube array and the TiO of nanometer MOS 2 particle modification2Nano-tube array is by for several times
Photocatalysis efficiency figure after circulation light Catalysis experiments.
Embodiment
Referring to Fig. 1, Fig. 1 is the system of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot of the present invention
The schematic flow sheet of Preparation Method.Received as shown in figure 1, the present invention provides a kind of electro-deposition molybdenum disulfide quantum dot modified titanic oxide
The preparation method of mitron array, comprises the following steps：
The pretreatment of titanium sheet；
Anodizing prepares TiO2Nano-tube array；
Molybdenum disulfide powder is made to the molybdenum disulfide nano sheet of solid sheet with infrared tablet press machine；
Using the molybdenum disulfide nano sheet as anode, the TiO2Nano-tube array is sub- as negative electrode, double fluoroform sulphonyl
The TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot is made as electrolyte in the amine lithium aqueous solution.
In order to facilitate the understanding of the purposes, features and advantages of the present invention, with reference to embodiment
The present invention is further detailed explanation.
A kind of preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot, including：
Step 1：The pretreatment of titanium sheet；
In one embodiment, the step can be with execution specific as follows：Titanium sheet substrate is cleaned by ultrasonic.Wherein, titanium sheet
Material is pure titanium or titanium alloy, and size is 1.5cm × 3.0cm.It is clear to titanium sheet ultrasound using acetone, ethanol and deionized water successively
Wash 20~30min.
Step 2：Anodizing prepares TiO2Nano-tube array；
In one embodiment, the step can be with execution specific as follows：Using the titanium sheet substrate as anode, using platinum plate electrode as
Negative electrode, the anode and negative electrode are inserted simultaneously and contain NH4F and H2It is described to contain NH in O ethylene glycol solution4F and H2O second
In glycol solution, NH4F mass percent concentration is 0.1~1.0wt%, H2O concentration of volume percent be 1.0~
5.0v%, apply 40~60V, 1 ~ 2h of voltage, make the anodic oxidation, TiO is made2Nano-tube array, then by the TiO2Nanometer
Pipe array is calcined in atmosphere, and the temperature of calcining is 400~500 DEG C, and time of calcining is 1~3h, the heating and cooling of calcining
Speed is 3~5 DEG C/min, makes the TiO2TiO of the nano-tube array from unformed state2Nano-tube array is transformed into rutile titania
The TiO of ore deposit2Nano-tube array.
Step 3：Molybdenum disulfide powder is made to the molybdenum disulfide nano sheet of solid sheet with infrared tablet press machine；
In one embodiment, the step can be with execution specific as follows：With infrared tablet press machine to 400~500mg molybdenum disulphide powders
The pressure that end applies is 15~20Mpa, and the time of pressure is 45s~60s, and the molybdenum disulfide nano sheet of solid sheet is made.
Step 4：Using the molybdenum disulfide nano sheet as anode, the TiO2Nano-tube array is as negative electrode, double trifluoros
The sulfonyl methane imine lithium aqueous solution is powered, repaiied with water rinsing, drying, obtained electro-deposition molybdenum disulfide quantum dot as electrolyte
Adorn Nano tube array of titanium dioxide.
In one embodiment, the step can be with execution specific as follows：Using the molybdenum disulfide nano sheet as anode, institute
State TiO2Nano-tube array as negative electrode, double trifluoromethanesulfonimide lithium aqueous solution as electrolyte, wherein, double trifluoros
The concentration of sulfonyl methane imine lithium is 0.1wt%~0.5wt%, and application voltage is 4~6V, conduction time be respectively 0.5h, 1h,
2h, cleaned 3 times with absolute ethyl alcohol and deionized water after being powered every time, it is therefore an objective to wash impurity off, be then 50~60 in temperature
Dried under conditions of DEG C, the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot is made.
After aforementioned four step, complete to make the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot.
After this four steps, structure can also be tested.
Step 5：Methylene blue solution is added in test tube, by the TiO2 nanotube bases of the molybdenum disulfide quantum dot of deposition
Bottom is put into solution, and lucifuge reaches adsorption equilibrium for a period of time, after taking-up using the illumination of photochemical reaction instrument for a period of time, i.e.,
Degradable methylene blue.
Wherein, the volume of the methyl orange solution is 10~15 ml, and concentration is 8~12 mg/L, and pH value is 8~10.Institute
It is 45~60 min to state the lucifuge time, and light application time is 0~150 min.
As shown in figure 1, titanium sheet is by being self-assembly of TiO2Nano-tube array, molybdenum disulfide is then formed by electro-deposition
The TiO of nano-particles reinforcement2Nanotube, under light illumination catalytic degradation methylene blue make its decolouring.
Referring to Fig. 2, Fig. 2 is the system of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot of the present invention
In Preparation Method, the TiO of high-sequential prepared by anodic oxidation 2h2The TEM shape appearance figures of nano-tube array.As shown in Fig. 2 do not repaiied
The TiO2 nano-tube arrays of decorations show what is uniformly unified, the close consistent shape characteristic of tube wall arrangement.
In order to facilitate the understanding of the purposes, features and advantages of the present invention, with reference to the accompanying drawings and examples
Further illustrate technical scheme.But the invention is not restricted to listed embodiment, it should also be included in institute of the present invention
It is required that interest field in other any known change.
First, " one embodiment " or " embodiment " referred to herein refers to may be included at least one realization side of the present invention
Special characteristic, structure or characteristic in formula." in one embodiment " that different places occur in this manual not refers both to
Same embodiment, nor the single or selective embodiment mutually exclusive with other embodiment.
Secondly, the present invention is described in detail using structural representation etc., when the embodiment of the present invention is described in detail, for ease of saying
Bright, schematic diagram can disobey general proportion and make partial enlargement, and the schematic diagram is example, and it should not limit the present invention herein
The scope of protection.In addition, the three dimensions of length, width and depth should be included in actual fabrication.
In addition, the letter said in the present invention is referred to as, it is that this area is fixed referred to as, which part letter text is explained such as
Under：SEM schemes：Electron scanning imaging figure；TEM schemes：Transmitted electron surface sweeping imaging figure；HRTEM schemes：High-resolution transmitted electron is swept
Face imaging figure；EDS schemes：Energy spectrum diagram；XRD：X-ray diffractogram；XPS spectrum figure：X-ray photoelectron spectroscopic analysis spectrogram；SAED
Figure：Selected diffraction figure；LITFSI:Double trifluoromethanesulfonimide lithiums.In addition, MoS in Figure of description in the present invention2@TiO2-
0.5h represents electro-deposition nanometer MOS 2 particle 0.5h, MoS2@TiO2- 1h represents electro-deposition nanometer MOS 2 particle 1h,
MoS2@TiO2- 2h represents electro-deposition nanometer MOS 2 particle 2h.
Embodiment 1
The implementation case shows a kind of TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot as follows
Preparation method：
(1) pretreatment of titanium sheet：20min is cleaned by ultrasonic to pure titanium sheet substrate acetone, absolute ethyl alcohol.Using platinum plate electrode as the moon
Pole, while insertion contains 98v% ethylene glycol（Ammonium fluoride 0.5wt%）In the electrolyte solution of+2v% water, apply 50V ultors
2h is aoxidized, TiO is made2Nano-tube array, then 450 DEG C of calcining 2h, make it be transformed into anatase from unformed state.
(2) electro-deposition method is used, prepares the compound Nano tube array of titanium dioxide of nanometer MOS 2 particle.Prepare
The aqueous solution of 0.1wt% double trifluoromethanesulfonimide lithiums, solution are used as electrolyte after being uniformly dispersed, utilize infrared tablet press machine
The pressure that 500mg molybdenum disulfide is applied to 15Mpa prepares slabbing, is received molybdenum disulfide nano sheet as anode, titanium dioxide
Mitron array as negative electrode, apply voltage 5V half an hours take out sample after all use absolute ethyl alcohol and deionized water rinsing titanium sheet three
It is secondary, 60 DEG C of dryings in baking oven, that is, obtain the compound TiO of nanometer MOS 2 particle2Nano-tube array.
(3) the TiO 2 nanotubes modified array photo catalysis degradation of methylene blue of nanometer MOS 2 particle：In test tube
Methylene blue solution 15ml is poured into, by the compound TiO of nanometer MOS 2 particle2Nanotube substrate is put into solution, at lucifuge
Reason 60min reaches adsorption equilibrium, after illumination 120min, tests the efficiency of its photocatalytic degradation methylene blue.
The specific conclusion of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot obtained by above-described embodiment
It is as follows：
Fig. 3 and Fig. 4 are referred to, Fig. 3 is the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot of the present invention
In preparation method, the TiO of nanometer MOS 2 particle modification2The TEM shape appearance figures of nano-tube array, the electricity that Fig. 4 is the present invention sink
In the preparation method of the TiO 2 nanotubes modified array of product molybdenum disulfide quantum dot, the TiO of nanometer MOS 2 particle modification2
SAED, HRTEM and EDS spectrogram of nano-tube array.As seen from Figure 3,2~5nm nanometer MOS 2 particle equably deposits
In nanotube surface and inside；From fig. 4, it can be seen that TEM results further demonstrate that nanometer MOS 2 particle is evenly distributed on TiO2
Nanotube surface；HRTEM figures show TiO2Detitanium-ore-type (101) crystal face spacing of lattice is 0.352nm, MoS2(100) interplanar
Away from for 0.27 nm；(103) interplanar distance is 0.227nm.To composite material surface carry out EDS analyses, mainly contain Ti, O, Mo,
S elements, and Mo contents are 1.16at%, further confirm MoS2The presence of nano particle.
Fig. 5 to Fig. 8 is referred to, Fig. 5 to Fig. 8 is the performance of the TiO 2 nanotubes modified array of nanometer MOS 2 particle
Characterize.Fig. 5 is unmodified TiO2The TiO of 450 DEG C of nano-tube array calcining, molybdenum disulfide and nanometer MOS 2 particle modification2Receive
The Raman spectrogram of mitron array；Fig. 6 is unmodified TiO2450 DEG C of nano-tube array calcining, molybdenum disulfide and molybdenum disulfide nano
The TiO of particle modification2The XRD spectra of nano-tube array；Fig. 7 is unmodified TiO2Nano-tube array and nanometer MOS 2 particle
The TiO of modification2The XPS spectrum figure of nano-tube array；Fig. 8 is unmodified TiO2The ultraviolet-visible light diffusing reflection collection of illustrative plates of nano-tube array
(a) TiO modified with nanometer MOS 2 particle2The fluorescence pattern (b) of nano-tube array.As shown in fig. 6, blank TiO2Nanometer
Pipe is mainly made up of anatase and Ti substrates, and the peak value of 25.3 °, 37.9 °, 48.0 ° and 53.9 ° appearance corresponds to anatase respectively
(101), (004), (200) and (105) crystal face.In TiO2After nano-tube array deposition nanometer MOS 2 particle, due to
Dispersed and particle is smaller（Below 10nm）, occur relatively low peak value, corresponding MoS at 32 °2(100) crystal face, with Fig. 4
Middle TEM results are consistent.As shown in fig. 7, (a) is except O 1s (532.4 eV), Ti 2p (458.9 eV) and C 1s
(284.5 eV) peak, the presence at Mo 3d and S 2p peaks demonstrate Bi2O3Nano-particle modified TiO2Nano-tube array.From Mo
It can be seen that in 3d high-resolution XPS collection of illustrative plates (b), Mo 3d5/2(229.2 eV) and Mo 3d5/2(232.2 eV) peak value, it was demonstrated that Mo
Ion is existing in the form of+4 valencys.S 2p XPS spectrum figure (c), Ti 2p XPS spectrum figure (d).As shown in figure 8, can from a figures
Find out, unmodified TiO2Nanotube reflects greater than modification MoS to light2After nano particle, reflection is absorbed at 400-700 nm
Reduce, absorptivity improves.Modify the TiO of nanometer MOS 2 particle2The fluorescence intensity ratio of nano-tube array is the TiO of modification2
Nano-tube array is low, it is meant that electron transition can be occurred by obtaining relatively low energy level, promoted the separation of electron hole pair, enhanced
Photocatalysis efficiency.
Referring to Fig. 9, Fig. 9 is unmodified TiO2Nano-tube array and the TiO of nanometer MOS 2 particle modification2Nanotube
The photoelectric current collection of illustrative plates of array.As shown in figure 9, MoS2@TiO2- 0.5h represents be powered deposition 0.5h, MoS2@TiO2- 1h represents to be powered
Deposit 1h, MoS2@TiO2- 2h represents the deposition 2h that is powered.Using 0.1 M sodium sulphate as electrolyte solution, xenon lamp is as light source, light source
Distance to beaker is 15 cm, and intensity of illumination is 100 mW/cm2, passed through under CHI660D electrochemical workstation three-electrode systems
Row photoelectricity current test.MoS2@TiO2- 0.5,1,2h photoelectric current be 0.43 mA/ cm2, 0.59 mAcm2, 0.3 mA/cm2, point
It is not unmodified TiO2The photoelectric current of nanotube（0.2 mA/cm2）2.15 times, 2.95 times, 1.5 times, represent TiO2Nanotube battle array
Row modification MoS2The separative efficiency of electron hole pair is improved after particle.
Referring to Fig. 10, Figure 10 is unmodified TiO2Nano-tube array and the TiO of nanometer MOS 2 particle modification2Nanometer
The photocatalysis effect figure (a) and kinetics equation figure (b) of pipe array.As shown in Figure 10,300W mercury lamps are as light source, light source and sample
The distance of product is 12cm, and the concentration of degradation of methylene blue is 10mg/L, volume 15ml, pH 8.5.MoS2@TiO2- 0.5h tables
Show energization deposition 0.5h, MoS2@TiO2- 1h represents be powered deposition 1h, MoS2@TiO2- 2h represents the deposition 2h that is powered.Illumination 60min
Afterwards, unmodified TiO2Nanotube degrades 48.1% MoS2/TiO2NTA depositions 0.5h, 1h and 2h degrade 70% respectively, 80% He
68%.Utilize kinetics equation formula：Ln (C0/Ct)=kt, you can calculate MoS2/TiO2NTA deposits 0.5h, 1h and 2h, MoS2
The kinetic coefficient of particle is respectively 0.0116,0.0141,0.0108 min-1, degraded certainly far above methylene blue
（0.00166 min-1）With unmodified TiO2Nanotube（0.00416 min-1）.MoS2And TiO2Formed p-n heterojunction is effective
Photocatalysis efficiency is improved, it follows that the photocatalysis performance of the deposition nanometer MOS 2 particle of one hour is best, it is not repair
Adorn titania nanotube 3.2 times.
Figure 11 is referred to, Figure 11 is unmodified TiO2Nano-tube array and the TiO of nanometer MOS 2 particle modification2Nanometer
Photocatalysis efficiency figure of the pipe array after circulation light Catalysis experiments for several times.As shown in figure 11, after 5 cyclic tests,
The TiO of nanometer MOS 2 particle modification2Nano pipe photochemical catalyst efficiency is still considerable, illustrates to have very strong stability and can return
The property received.
Embodiment 2
The implementation case shows a kind of TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot as follows
Preparation method：
(1) pretreatment of titanium sheet：20min is cleaned by ultrasonic to pure titanium sheet substrate acetone, absolute ethyl alcohol.Using platinum plate electrode as the moon
Pole, while insertion contains 98v% ethylene glycol（Ammonium fluoride 0.5%）In the electrolyte solution of+2% water, apply the oxidation of 50V ultors
2h, TiO is made2Nano-tube array, then 450 DEG C of calcining 2h, make it be transformed into anatase from unformed state.
(2) electro-deposition method is used, prepares the compound Nano tube array of titanium dioxide of nanometer MOS 2 particle.Prepare
The aqueous solution of 0.1wt% double trifluoromethanesulfonimide lithiums, solution are used as electrolyte after being uniformly dispersed, utilize infrared tablet press machine
The pressure that 500mg molybdenum disulfide is applied to 15Mpa prepares slabbing, is received molybdenum disulfide nano sheet as anode, titanium dioxide
Mitron array all uses absolute ethyl alcohol and deionized water rinsing titanium sheet three as negative electrode after applying mono- hour taking-up sample of voltage 5V
It is secondary, 50 DEG C of dryings in baking oven, that is, obtain the compound TiO of nanometer MOS 2 particle2Nano-tube array.
(3) the TiO 2 nanotubes modified array photo catalysis degradation of methylene blue of nanometer MOS 2 particle：In test tube
Methylene blue solution 15ml is poured into, by the compound TiO of nanometer MOS 2 particle2Nanotube substrate is put into solution, at lucifuge
Reason 60min reaches adsorption equilibrium, after illumination 120min, tests the efficiency of its photocatalytic degradation methylene blue.
Embodiment 3
The implementation case shows a kind of TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot as follows
Preparation method：
(1) pretreatment of titanium sheet：30min is cleaned by ultrasonic to pure titanium sheet substrate acetone, absolute ethyl alcohol.Using platinum plate electrode as the moon
Pole, while insertion contains 98v% ethylene glycol（Ammonium fluoride 0.5wt%）In the electrolyte solution of+2v% water, apply 50V ultors
2h is aoxidized, TiO is made2Nano-tube array, then 450 DEG C of calcining 2h, make it be transformed into anatase from unformed state.
(2) electro-deposition method is used, prepares the compound Nano tube array of titanium dioxide of nanometer MOS 2 particle.Prepare
The aqueous solution of 0.1wt% double trifluoromethanesulfonimide lithiums, solution are used as electrolyte after being uniformly dispersed, utilize infrared tablet press machine
The pressure that 500mg molybdenum disulfide is applied to 15Mpa prepares slabbing, is received molybdenum disulfide nano sheet as anode, titanium dioxide
Mitron array all uses absolute ethyl alcohol and deionized water rinsing titanium sheet three as negative electrode after applying two hours taking-up samples of voltage 5V
It is secondary, 60 DEG C of dryings in baking oven, that is, obtain the compound TiO of nanometer MOS 2 particle2Nano-tube array.
(3) the TiO 2 nanotubes modified array photo catalysis degradation of methylene blue of nanometer MOS 2 particle：In test tube
Methylene blue solution 15ml is poured into, by the compound TiO of nanometer MOS 2 particle2Nanotube substrate is put into solution, at lucifuge
Reason 60min reaches adsorption equilibrium, after illumination 120min, tests the efficiency of its photocatalytic degradation methylene blue.
To ensure to test preciseness, variable is only controlled in above three embodiment（Sedimentation time is different）, remaining parameter guarantor
Hold identical, the other specification in Claims scope is equally applicable to above-described embodiment mode of operation, will not be repeated here.
Compared with prior art, the beneficial effects of the invention are as follows：The electro-deposition molybdenum disulfide quantum dot modification two of the present invention
The preparation method of titania nanotube array, using the letter of electrochemical stripping molybdenum disulfide electric field deposition nanometer MOS 2 particle
Single controllable method, the advantages of can control the scattered and size of molybdenum disulfide.With not compound TiO2Compare, it is obtained multiple
Close the TiO of nanometer MOS 2 particle2Degradation of methylene blue is unmodified dioxy to nano-tube array photochemical catalyst under ultraviolet light
Change titanium nano pipe photochemical catalyst speed 3.2 times, the efficiency of photocatalytic pollutant degradation significantly improves, and has good chemically stable
Performance and recuperability, while in terms of photodissociation aquatic products hydrogen, energy storage, the field such as solar cell also has a wide range of applications.
It should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferable
The present invention is described in detail embodiment, it will be understood by those within the art that, can be to the technology of the present invention
Scheme is modified or equivalent substitution, and without departing from the spirit and scope of technical solution of the present invention, it all should cover in this hair
Among bright right.
Claims (10)
1. the preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot, it is characterised in that this method
Comprise the following steps：
(1) pretreatment of titanium sheet：Titanium sheet substrate is cleaned by ultrasonic；
(2) anodizing prepares TiO2Nano-tube array：Using the titanium sheet substrate as anode, using platinum plate electrode as negative electrode, by institute
State anode and negative electrode while insertion contains NH4F and H2In O ethylene glycol solution, applying voltage makes the anodic oxidation, is made
TiO2Nano-tube array, then by the TiO2Nano-tube array is calcined, and makes the TiO2Nano-tube array is from unformed state
TiO2Nano-tube array is transformed into the TiO of anatase2Nano-tube array；
(3) molybdenum disulfide powder is made to the molybdenum disulfide nano sheet of solid sheet with infrared tablet press machine；
(4) using the molybdenum disulfide nano sheet as anode, the TiO2Nano-tube array is as negative electrode, double fluoroform sulphonyl
The imine lithium aqueous solution is powered as electrolyte, modifies titanium dioxide with water rinsing, drying, obtained electro-deposition molybdenum disulfide quantum dot
Titanium nano-tube array.
2. the preparation side of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot according to claim 1
Method, it is characterised in that：The material of titanium sheet described in step (1) is pure titanium or titanium alloy, and size is 1.5cm × 3.0cm.
3. the preparation side of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot according to claim 1
Method, it is characterised in that be cleaned by ultrasonic described in step (1) for be cleaned by ultrasonic 20 using acetone, ethanol and deionized water successively~
30min。
4. the preparation side of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot according to claim 1
Method, it is characterised in that：Step contains NH described in (2)4F and H2In O ethylene glycol solution, NH4F mass percent concentration is
0.1~1.0wt%, H2O concentration of volume percent is 1.0~5.0v%.
5. the preparation side of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot according to claim 1
Method, it is characterised in that：The voltage of anodic oxidation described in step (2) is 40~60V, and the time is 1 ~ 2h.
6. the preparation side of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot according to claim 1
Method, it is characterised in that：Calcining is to calcine in atmosphere described in step (2), and the temperature of calcining is 400~500 DEG C, calcining when
Between be 1~3h, the heating of calcining and rate of temperature fall are 3~5 DEG C/min.
7. the preparation side of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot according to claim 1
Method, it is characterised in that：Molybdenum disulfide powder described in step (3) is 400~500mg, the pressure that the infrared tablet press machine applies
For 15~20Mpa, the time of pressure is 45s~60s.
8. the preparation side of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot according to claim 1
Method, it is characterised in that：The concentration of double trifluoromethanesulfonimide lithiums is 0.1wt%~0.5wt% described in step (4).
9. the preparation side of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot according to claim 1
Method, it is characterised in that：The voltage of application of being powered described in step (4) is 4~6V, and conduction time is respectively 0.5h, 1h, 2h, institute
State and rinsed with water to be cleaned 3 times with absolute ethyl alcohol and deionized water after energization every time.
10. the preparation side of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot according to claim 1
Method, it is characterised in that：The temperature dried described in step (4) is 50~60 DEG C.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108525667A (en) * | 2018-04-10 | 2018-09-14 | 苏州大学 | Metal organic frame derives the preparation method of the TiO 2 nanotubes modified array of cobaltosic oxide |
| CN108640154A (en) * | 2018-06-15 | 2018-10-12 | 西南交通大学 | A kind of molybdenum disulfide nano material and preparation method thereof |
| CN109046392A (en) * | 2018-09-11 | 2018-12-21 | 北京邮电大学 | A kind of catalyst and preparation method thereof of photocatalysis Decomposition aquatic products hydrogen |
| CN109967095A (en) * | 2019-04-17 | 2019-07-05 | 南昌航空大学 | A kind of holocrystalline bulk heterojunction catalysis material and its preparation method and application |
| CN112076772A (en) * | 2020-09-01 | 2020-12-15 | 常州工学院 | Metal type molybdenum disulfide quantum dot modified TiN nanotube array composite material and preparation method thereof |
| CN112811523A (en) * | 2020-12-14 | 2021-05-18 | 南昌航空大学 | Preparation method and application of nanocomposite oxygen-doped molybdenum disulfide/titanium dioxide nanotube array |
| CN112827484A (en) * | 2021-01-07 | 2021-05-25 | 中国人民解放***箭军工程大学 | Preparation of composite photoelectric catalytic material and method for treating unsymmetrical dimethylhydrazine wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU908969A1 (en) * | 1980-01-02 | 1982-02-28 | Предприятие П/Я Р-6209 | Electrolyte for anodizing titanium alloys |
| CN106086990A (en) * | 2016-08-04 | 2016-11-09 | 北京工业大学 | A kind of method of the immobilized molybdenum bisuphide of porous titania thin films |
| CN106179415A (en) * | 2016-04-20 | 2016-12-07 | 中国计量大学 | A kind of preparation method of nano titanium oxide/molybdenum bisuphide composite material film |
| CN106315750A (en) * | 2016-11-01 | 2017-01-11 | 江苏科技大学 | Visible light catalyst molybdenum disulfide loaded titanium dioxide nano-tube electrode as well as preparation method and application thereof |
-
2017
- 2017-10-16 CN CN201710960455.1A patent/CN107723777B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU908969A1 (en) * | 1980-01-02 | 1982-02-28 | Предприятие П/Я Р-6209 | Electrolyte for anodizing titanium alloys |
| CN106179415A (en) * | 2016-04-20 | 2016-12-07 | 中国计量大学 | A kind of preparation method of nano titanium oxide/molybdenum bisuphide composite material film |
| CN106086990A (en) * | 2016-08-04 | 2016-11-09 | 北京工业大学 | A kind of method of the immobilized molybdenum bisuphide of porous titania thin films |
| CN106315750A (en) * | 2016-11-01 | 2017-01-11 | 江苏科技大学 | Visible light catalyst molybdenum disulfide loaded titanium dioxide nano-tube electrode as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YUANYUAN TIAN等: "Enhanced photo-assistant electrocatalysis of anodization TiO2 nanotubes via surrounded surface decoration with MoS2 for hydrogen evolution reaction", 《APPLIED SURFACE SCIENCE》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108525667A (en) * | 2018-04-10 | 2018-09-14 | 苏州大学 | Metal organic frame derives the preparation method of the TiO 2 nanotubes modified array of cobaltosic oxide |
| CN108640154A (en) * | 2018-06-15 | 2018-10-12 | 西南交通大学 | A kind of molybdenum disulfide nano material and preparation method thereof |
| CN109046392A (en) * | 2018-09-11 | 2018-12-21 | 北京邮电大学 | A kind of catalyst and preparation method thereof of photocatalysis Decomposition aquatic products hydrogen |
| 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 |
| CN109967095A (en) * | 2019-04-17 | 2019-07-05 | 南昌航空大学 | A kind of holocrystalline bulk heterojunction catalysis material and its preparation method and application |
| CN109967095B (en) * | 2019-04-17 | 2021-05-25 | 南昌航空大学 | Full-crystal heterojunction photocatalytic material and preparation method and application thereof |
| CN112076772A (en) * | 2020-09-01 | 2020-12-15 | 常州工学院 | Metal type molybdenum disulfide quantum dot modified TiN nanotube array composite material and preparation method thereof |
| WO2022048262A1 (en) * | 2020-09-01 | 2022-03-10 | 常州工学院 | Metal type molybdenum disulfide quantum dot-modified tin nanotube array composite material and preparation method therefor |
| CN112811523A (en) * | 2020-12-14 | 2021-05-18 | 南昌航空大学 | Preparation method and application of nanocomposite oxygen-doped molybdenum disulfide/titanium dioxide nanotube array |
| CN112827484A (en) * | 2021-01-07 | 2021-05-25 | 中国人民解放***箭军工程大学 | Preparation of composite photoelectric catalytic material and method for treating unsymmetrical dimethylhydrazine wastewater |
| CN112827484B (en) * | 2021-01-07 | 2023-03-17 | 中国人民解放***箭军工程大学 | Preparation of composite photoelectric catalytic material and method for treating unsymmetrical dimethylhydrazine wastewater |
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