CN105457621B - The preparation method of the rear-earth-doped vanadate composite nano fiber catalysis material of heterojunction type titanium dioxide - Google Patents
The preparation method of the rear-earth-doped vanadate composite nano fiber catalysis material of heterojunction type titanium dioxide Download PDFInfo
- Publication number
- CN105457621B CN105457621B CN201510821944.XA CN201510821944A CN105457621B CN 105457621 B CN105457621 B CN 105457621B CN 201510821944 A CN201510821944 A CN 201510821944A CN 105457621 B CN105457621 B CN 105457621B
- Authority
- CN
- China
- Prior art keywords
- earth
- titanium dioxide
- doped vanadate
- composite nano
- type titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002121 nanofiber Substances 0.000 title claims abstract description 44
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 229920000620 organic polymer Polymers 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 238000010792 warming Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 3
- 238000009938 salting Methods 0.000 claims abstract description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 19
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 19
- 230000001699 photocatalysis Effects 0.000 claims description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 238000007146 photocatalysis Methods 0.000 claims description 10
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000010041 electrostatic spinning Methods 0.000 claims description 6
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 11
- 229910009372 YVO4 Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- -1 compound rare-earth Chemical class 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 229920002239 polyacrylonitrile Polymers 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 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
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- FIDZUVLGQPMOIN-UHFFFAOYSA-N sodium oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Na+] FIDZUVLGQPMOIN-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
-
- B01J35/39—
-
- B01J35/58—
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
Abstract
The invention discloses a kind of preparation method of the rear-earth-doped vanadate composite nano fiber catalysis material of heterojunction type titanium dioxide, comprise the following steps：(1) polyvinylpyrrolidone is dissolved into the mixed solution of absolute ethyl alcohol and deionized water, stirs 4h, be configured to organic polymer colloidal sol；Metatitanic acid salting liquid is added dropwise thereto, and continues to be transferred to ptfe autoclave after stirring 0.5h；Freshly prepd rear-earth-doped Vanadate nanofiber is added in reactor, 160 180 DEG C, the 3MPa of control pressure 2.5, the 16h of constant temperature 12 are warming up to；(2) reaction system is naturally cooled to room temperature, sample is taken out and filtered, first with washes of absolute alcohol 35 times, then cleaned after 23 times with deionized water, 12h is dried at 80 DEG C, the rear-earth-doped vanadate composite nano fiber of heterojunction type titanium dioxide is made.Synthesis technique of the present invention is simple, can obtain structure-controllable, excellent performance, the near infrared light catalysis material with heterojunction structure, market prospects are boundless.
Description
Technical field
The present invention relates to a kind of heterojunction type titanium dioxide-rear-earth-doped vanadate composite nano fiber catalysis material
Preparation method.
Background technology
The research origin of the photochemical catalytic oxidation Fujishima and Honda Japanese in 1972 exist《Nature》Sent out on magazine
One paper of table, it indicates that multiphase photocatalysis research has started a New Times.Carey et al. under ultraviolet light,
Successfully degraded using titanium dioxide extremely toxic substance Polychlorinated biphenyls, so as to open up conductor photocatalysis in environmental pollution treatment
Using.Among numerous conductor photocatalysis materials, titanium dioxide is because its photocatalytic activity is high, ultraviolet-shielding type is strong, heat
The property led is good, good dispersion and the advantages of inexpensive, nontoxic, non-secondary pollution and as a kind of most valued photocatalytic semiconductor material
Material.But in actual application, because titanium dioxide powder is suspended in Pollution System, not only hinder light to propagate, reduction
Light transmission, more easy in inactivation are reunited, it is difficult to recycling.Therefore, other are constructed using method physically or chemically
On carrier, titanium dioxide composite Nano catalysis material system is formed, it is easily isolated, reclaimed in pollutant catalytic degradation
And recycling, the industrial applications process of photocatalysis material of titanium dioxide can be effectively pushed.In addition, pure phase titanium dioxide is typical case
Wide band gap semiconducter, its energy gap is about 3.2eV (Anatase), is only capable of by the ultraviolet light (≤387.5nm) of short wavelength
Excite.Due to only containing about 7% energy in the ultraviolet band of solar spectrum, and in the energy in visible ray and near infrared light region
50% and 43% are accounted for, therefore, optically catalytic TiO 2 how is improved for visible and near infrared band luminous energy absorption simultaneously
Thus over-all quantum efficiency is improved, is a significantly research topic.
The content of the invention
It is an object of the invention to provide a kind of heterojunction type titanium dioxide-rear-earth-doped vanadate composite nano fiber light
The preparation method of catalysis material, can obtain structure-controllable, excellent performance, the titanium dioxide with heterojunction structure by this method and answer
Close nanofiber catalysis material.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of heterojunction type titanium dioxide-rear-earth-doped vanadate composite nano fiber catalysis material,
It is characterised in that it includes following steps：
(1) polyvinylpyrrolidone is dissolved into the mixed solution of absolute ethyl alcohol and deionized water, stirs 4h, be configured to
Organic polymer colloidal sol；Metatitanic acid salting liquid is added dropwise thereto, and continues to be transferred to ptfe autoclave after stirring 0.5h；
Freshly prepd rear-earth-doped Vanadate nanofiber is added in reactor, 160-180 DEG C is warming up to, control pressure is 2.5-
3MPa, constant temperature 12-16h；
(2) question response system naturally cools to room temperature, and sample is taken out and filtered, and first with washes of absolute alcohol 3-5 times, then uses
After deionized water is cleaned 2-3 times, 12h is dried at 80 DEG C, obtained heterojunction type titanium dioxide-rear-earth-doped vanadate is compound to be received
Rice fiber.
In the above-mentioned methods, the rear-earth-doped vanadate is the Yttrium Orthovanadate or vanadic acid of Rare earth element ytterbium and thulium codope
Lanthanum；The titanate is titanium tetrachloride or titanium tetrafluoride.
In the above-mentioned methods, it is preferable that absolute ethyl alcohol and the volume ratio V of deionized water in the step (1)Ethanol∶VWater=4:
1.In the organic polymer colloidal sol prepared in the step (1) mass percentage content of polyvinylpyrrolidone for 5~
5.5%.In the step (1), the amount ratio of titanate and the material of rear-earth-doped Vanadate nanofiber is 1: 5.
In the above-mentioned methods, the rear-earth-doped Vanadate nanofiber is made of electrostatic spinning technique.
In the above-mentioned methods, rear-earth-doped Vanadate nanofiber and the reactant in solution, in the hydro-thermal of HTHP
Titanate is progressively hydrolyzed to form into titanium dioxide nanocrystalline in environment, as the titanium dioxide that the continuous progress of reaction is generated is dense
Degree gradually increases, and when concentration reaches saturation, titanium dioxide starts crystallization precipitation, due to using the dilute of electrostatic spinning technique preparation
Native adulterated vanadate nanofiber has three-dimensional open structure, high porosity and bigger serface, in organic polymer
Under the synergy of polyvinylpyrrolidone, the titanium dioxide nanocrystalline separated out, using rear-earth-doped Vanadate nanofiber as
Matrix growth in situ, finally makes titanium dioxide nanocrystalline original position construct in rare-earth vanadium-doped silicate nanometer fiber surface, is made two
The compound rare-earth vanadium-doped silicate nanometer fiber catalysis material of titanium oxide.
In the above-mentioned methods, by changing response parameter (such as：Reaction temperature, reactant concentration and reaction time), can be with
Effectively the control pattern of titanium dioxide sodium rice crystal grain, particle size and its in coverage density of fiber surface etc..
The advantage of the invention is that：
The present invention is being fully understood by and grasped rear-earth-doped Vanadate nanofiber and titanate according to hydro-thermal reaction feature
On the basis of hydrothermal reaction process and reaction mechanism, have by regulating and controlling the factors such as reaction temperature, reactant concentration and reaction time
Pattern, particle size and the coverage density in fiber surface of effect control anatase phase titanium dioxide nanocrystal, so as to obtain
Structure-controllable, excellent performance, the dioxide composite nanofiber catalysis material with heterojunction structure.
Catalysis material prepared by the present invention, synthesis technique is simple；Using organic dirt near infrared light degraded environment
Contaminate thing；Photocatalytic activity is high, easily separated recovery and recycling；Energy-conservation, non-secondary pollution, have a wide range of application, environmental protection；City
Field prospect is boundless.
Brief description of the drawings
Fig. 1 is Rare earth element ytterbium made from the embodiment of the present invention and thulium codope Yttrium Orthovanadate (YVO4：Yb, Tm) nanofiber
Scanning electron microscope (SEM) photograph.
Fig. 2 is heterojunction type titanium dioxide made from the embodiment of the present invention and Rare earth element ytterbium and thulium codope Yttrium Orthovanadate
(TiO2-YVO4：Yb, Tm) composite nano fiber scanning electron microscope (SEM) photograph.
Embodiment
The present invention will be further described by the following examples, but the embodiment of the present invention is not limited in
This.
Because titanium dioxide is typical n-type semiconductor, often with Anatase, Rutile Type, the equal a variety of crystalline substances of brockite
Type is present, wherein, anatase phase titanium dioxide has good photocatalytic activity.The present invention is by selecting suitable material and most
Preferably it is combined both good reaction condition is favourable, the nanocrystalline original position of anatase phase titanium dioxide is constructed in rear-earth-doped vanadate
Nanofiber surface, makes the two effectively combine closely, so as to prepare the titanium dioxide near infrared light catalytic performance-dilute
Native adulterated vanadate composite nano fiber catalysis material.
In the present invention, it is that driving force prepares organic polymer Nanowire by high-pressure electrostatic using electrostatic spinning technique
Dimension, then through high-temperature roasting technique, prepares the rear-earth-doped alum salts nanofiber with Upconversion luminescence, in conjunction with
The nanofiber surface is constructed in the titanium dioxide nanocrystalline original position for reacting generation by hydro-thermal method, and being formed has heterojunction structure dioxy
Change titanium composite nano fiber catalysis material.Rare earth up-conversion luminescent material is mutually combined with titanium dioxide optical catalyst, is conducive to
The raising of photocatalytic activity and the utilization rate of sunshine.First, the rare earth ion with Upconversion luminescence is present in vanadic acid
In the lattice of salt crystal, the relatively low near infrared light of energy in sunshine can be converted into the ultraviolet light of high-energy；Second, passing through
Upper converted ultraviolet light can effectively excite titanium dioxide optical catalyst through heterojunction boundary, form specific Strong oxdiative energy
The light induced electron of strength and hole；Third, the compound titanium dioxide nanocrystalline grain of fiber surface can protect luminous base well
Body, improves its stability and luminous efficiency；Finally, titanium dioxide is combined with rear-earth-doped vanadate and ensure that catalysis material
Purity, it is to avoid the unnecessary photoproduction electricity caused by the defect or impurity caused by the rare earth ion doped lattice to titanium dioxide
Sub- hole is to compound.
Embodiment
1st, material requested and test instrument：
Yittrium oxide (Y2O3), ytterbium oxide (Yb2O3), thulium oxide (Tm2O3) purity be 99.99%, the wide profit in Ganzhou is high-new
Technologic material Co., Ltd produces；Ammonium metavanadate (NH4VO3), analyze pure, the careless bio tech ltd's production in Guangzhou green hundred；N-
N-dimethylformamide (DMF), polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP), chemistry are pure, the sharp fine chemistry of Beijing benefit
Product Co., Ltd produces；Titanium tetrachloride (TiCl4), titanium tetrafluoride (TiF4), it is that analysis is pure, Shanghai elder brother's row chemical science and technology is limited
Company produces；Absolute ethyl alcohol, analyzes pure, Beijing Chemical Plant's production.
The FM1206 types electrostatic of Beijing Fu Youma Science and Technology Ltd.s production visits silk device；Rigaku Motor Corporation produces
Rigaku D/max types powder x-ray diffractions (XRD)；The S-4800 Flied emissions scanning electricity of Japanese Hitachi companies production
Sub- microscope (SEM)；The JEL-1400 types of JEOL companies of JEOL production and the Tecnai G2 of Dutch FEI Co.'s production
F20S-TWIN types transmission electron microscope (HR-TEM)；The analyzer ratios of TriStar II 3020 of U.S. Micromeritics productions
Surface area apparatus；The U-4100 ultraviolet-uisible spectrophotometers with integrating sphere accessory of Japanese Hitachi companies production.
2、YVO4：The preparation of Yb, Tm nanofiber：
Accurately weigh Y2O3(0.795mmol)、Yb2O3(0.2mmol)、Tm2O3(0.005mmol) is added to HNO3Solution
In, stirring and dissolving is evaporated obtained rare earth nitrades.By 0.234g NH4VO3It is dissolved in 10mL H2In O, the dense HNO of 0.5mL are added dropwise3
The rare earth nitrades newly prepared are added afterwards, and stirring is completely dissolved it, and rare earth Yttrium Orthovanadate solution is made.2.0g PAN are taken to be dissolved in
In 12mL DMF, 3h is stirred at room temperature, PAN colloidal sols are made.1.5mL rare earth Yttrium Orthovanadate solution and 10mL ethanol is taken to be added to
In PAN colloidal sols, continuously stir 2h and transparent spinning solution is made.
YVO is prepared using electrostatic spinning technique4：Yb, Tm nanofiber.The electrostatic spinning apparatus mainly has three part groups
Into：Electrostatic high-pressure power supply, fluid Supplying apparatus, fiber reception device.By appropriate spinning solution injection fluid Supplying apparatus (injection
Device) in, metal electrode is probeed into the capillary of front end.Syringe angle of inclination is adjusted about with the horizontal 48 °.Capillary tip
Distance with receiver board is 18cm, applies 15kV voltage.The reception time is 5h, obtains one layer of fibrofelt.Put it into vacuum
After drying box 12h, 700 DEG C of annealing 2h under nitrogen protection atmosphere.
It is as shown in Figure 1 obtained ytterbium ion and the Yttrium Orthovanadate (YVO of thulium ion codope4：Yb, Tm) nanofiber sweeps
Electron microscope is retouched, as seen from the figure, fiber surface is more smooth, without the attachment of other species, its a diameter of 200~300nm.
3、TiO2-YVO4：The preparation of Yb, Tm composite nano fiber
1g PVP are dissolved into the mixed solution (V of 22mL (19g) ethanol and deionized waterEthanol∶VWater=4: in 1), stirring
4h, is configured to the clarification polymeric sol that PVP mass fractions are 5%.The TiCl that 1mL concentration is 0.1mol/L is added dropwise4It is molten
Liquid (is dissolved in hydrochloric acid solution), continues to be transferred to ptfe autoclave after stirring 0.5h；Take the freshly prepd YVO of 0.102g4：
Yb, Tm nanofiber are added in reactor, are warming up to 180 DEG C, constant temperature 14h.Reaction system is set to naturally cool to room temperature, by sample
Take out, first with washes of absolute alcohol 4 times, then clean after 2 times with deionized water, be dried in vacuo 12h at 80 DEG C, obtained hetero-junctions
Type titanium dioxide and Rare earth element ytterbium and thulium codope Yttrium Orthovanadate composite nano fiber.
It is illustrated in figure 2 heterojunction type titanium dioxide made from the present embodiment and Rare earth element ytterbium and thulium codope Yttrium Orthovanadate
(TiO2-YVO4：Yb, Tm) composite nano fiber scanning electron microscope (SEM) photograph, high-visible sample still keeps original fiber shape from figure
State, but surface is no longer smooth, there is many TiO2It is nanocrystalline equably to construct in fiber surface, without agglomeration, fibre diameter
It is increased slightly compared with fibrillation.
Reacted by pattern of the decolored degradation of rhodamine B, investigated the near infrared light catalytic performance of sample obtained by embodiment.
As a result show：TiO2-YVO4：Yb, Tm composite nano fiber, in 980nm near infrared light 8h, the degradation rate of rhodamine B reaches
57.8%；Under the same terms, YVO4：The degradation rate of Yb, Tm nanofiber is only 5.3%；And pure TiO2Nano-powder is in near-infrared
Without catalytic action under light irradiation.Light-catalyzed reaction mechanism is that sample is under the irradiation of 980nm laser, and near infrared light passes through hetero-junctions
The TiO of structure outer layer2Enter YVO4：In Yb, Tm nanofiber lattice, wherein the Yb adulterated3+Ions Absorption accumulation near infrared light
Energy, and pass it to Tm3+Ion, Tm3+Ion is excited, and launches ultraviolet light.Then, UV light permeability heterojunction boundary
By the Anatase TiO of outer layer2It is nanocrystalline to be absorbed, produce photo-generate electron-hole pair.Then, photo-generate electron-hole is to transfer
The reaction generation high mars free radical such as water, oxygen into catalyst surface, with liquid phase (OH).Finally, high mars free radical enters
Simulation organic pollution rhodamine B is attacked, the inorganic molecules such as water and carbon dioxide are degraded into.TiO prepared by the present invention2-
YVO4：Yb, Tm composite nano fiber show good photocatalytic activity in the case where near infrared light is excited, and have reached raising sunshine
The purpose of design of utilization rate.
Claims (6)
1. a kind of preparation method of heterojunction type titanium dioxide-rear-earth-doped vanadate composite nano fiber catalysis material, its
It is characterised by, comprises the following steps：
(1) polyvinylpyrrolidone is dissolved into the mixed solution of absolute ethyl alcohol and deionized water, stirs 4h, be configured to organic
Polymeric sol；Metatitanic acid salting liquid is added dropwise thereto, and continues to be transferred to ptfe autoclave after stirring 0.5h；Will be new
The rear-earth-doped Vanadate nanofiber prepared is added in reactor, is warming up to 160-180 DEG C, control pressure is 2.5-3MPa,
Constant temperature 12-16h；The rear-earth-doped vanadate is the Yttrium Orthovanadate or vanadic acid lanthanum of Rare earth element ytterbium and thulium codope；
(2) question response system naturally cools to room temperature, and sample is taken out and filtered, first with washes of absolute alcohol 3-5 times, then spend from
After sub- water is cleaned 2-3 times, 12h is dried at 80 DEG C, heterojunction type titanium dioxide-rear-earth-doped vanadate composite Nano is made fine
Dimension.
2. heterojunction type titanium dioxide according to claim 1-rear-earth-doped vanadate composite nano fiber photocatalysis material
The preparation method of material, it is characterised in that the titanate is titanium tetrachloride or titanium tetrafluoride.
3. heterojunction type titanium dioxide according to claim 1-rear-earth-doped vanadate composite nano fiber photocatalysis material
The preparation method of material, it is characterised in that absolute ethyl alcohol and the volume ratio V of deionized water in the step (1)Ethanol:VWater=4:1.
4. heterojunction type titanium dioxide according to claim 1-rear-earth-doped vanadate composite nano fiber photocatalysis material
The preparation method of material, it is characterised in that the matter of polyvinylpyrrolidone in the organic polymer colloidal sol prepared in the step (1)
Amount degree is 5-5.5%.
5. heterojunction type titanium dioxide according to claim 1-rear-earth-doped vanadate composite nano fiber photocatalysis material
The preparation method of material, it is characterised in that in the step (1), titanate and the material of rear-earth-doped Vanadate nanofiber
Amount ratio be 1:5.
6. heterojunction type titanium dioxide according to claim 1-rear-earth-doped vanadate composite nano fiber photocatalysis material
The preparation method of material, it is characterised in that the rear-earth-doped Vanadate nanofiber is made of electrostatic spinning technique.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510821944.XA CN105457621B (en) | 2015-11-24 | 2015-11-24 | The preparation method of the rear-earth-doped vanadate composite nano fiber catalysis material of heterojunction type titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510821944.XA CN105457621B (en) | 2015-11-24 | 2015-11-24 | The preparation method of the rear-earth-doped vanadate composite nano fiber catalysis material of heterojunction type titanium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105457621A CN105457621A (en) | 2016-04-06 |
| CN105457621B true CN105457621B (en) | 2017-11-03 |
Family
ID=55596036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510821944.XA Expired - Fee Related CN105457621B (en) | 2015-11-24 | 2015-11-24 | The preparation method of the rear-earth-doped vanadate composite nano fiber catalysis material of heterojunction type titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105457621B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111809273B (en) * | 2020-07-20 | 2021-10-22 | 大连海事大学 | Preparation method of rare earth ion doped yttrium vanadate nanotube and nanotube |
| CN112387270B (en) * | 2020-12-07 | 2021-11-30 | 清华大学 | Photocatalytic material for eliminating VOCs and ozone and multilayer-hole-plate type photocatalytic reactor |
| CN115382528B (en) * | 2022-08-26 | 2023-10-31 | 上海大学 | Titanium doped cobalt (III) -containing polyacrylate/titanium dioxide composite catalyst and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080105535A1 (en) * | 2004-12-13 | 2008-05-08 | Osaka University | Composite Metal Oxide Photocatalyst Exhibiting Responsibility to Visible Light |
| JP2008221113A (en) * | 2007-03-12 | 2008-09-25 | Osaka Univ | Floating photocatalyst and polluted water treatment method using the same |
| CN101966452B (en) * | 2010-11-03 | 2012-09-05 | 大连理工大学 | Method for preparing visible light-responded LaVO4 and TiO2 composite nanotube |
| CN103464135A (en) * | 2012-06-07 | 2013-12-25 | 中国人民解放军63971部队 | Preparation method of YVO4/TiO2 composite photocatalyst |
| CN103599770B (en) * | 2013-11-19 | 2015-08-26 | 浙江大学 | TiO 2/ InVO 4the preparation method of nanojunction composite material |
-
2015
- 2015-11-24 CN CN201510821944.XA patent/CN105457621B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105457621A (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kallawar et al. | Bismuth titanate based photocatalysts for degradation of persistent organic compounds in wastewater: A comprehensive review on synthesis methods, performance as photocatalyst and challenges | |
| Prakash et al. | Novel rare earth metal–doped one-dimensional TiO2 nanostructures: Fundamentals and multifunctional applications | |
| Reddy et al. | Template-free synthesis of tetragonal Co-doped ZrO2 nanoparticles for applications in electrochemical energy storage and water treatment | |
| Li et al. | Synthesis of rhombic hierarchical YF 3 nanocrystals and their use as upconversion photocatalysts after TiO 2 coating | |
| Banerjee | The design, fabrication, and photocatalytic utility of nanostructured semiconductors: focus on TiO2-based nanostructures | |
| Guo et al. | Near-infrared photocatalysis of β-NaYF 4: Yb 3+, Tm 3+@ ZnO composites | |
| Wan et al. | Effects of catalyst characters on the photocatalytic activity and process of NiO nanoparticles in the degradation of methylene blue | |
| Li et al. | Titanate nanofiber reactivity: fabrication of MTiO3 (M= Ca, Sr, and Ba) perovskite oxides | |
| Yan et al. | Microwave-assisted synthesis of monoclinic–tetragonal BiVO 4 heterojunctions with enhanced visible-light-driven photocatalytic degradation of tetracycline | |
| Xu et al. | Ternary system of ZnO nanorods/reduced graphene oxide/CuInS2 quantum dots for enhanced photocatalytic performance | |
| Harish et al. | Synthesis of ZnO/SrO nanocomposites for enhanced photocatalytic activity under visible light irradiation | |
| Adhyapak et al. | Effect of preparation parameters on the morphologically induced photocatalytic activities of hierarchical zinc oxide nanostructures | |
| Siddique et al. | Solution combustion synthesis: the relevant metrics for producing advanced and nanostructured photocatalysts | |
| CN105457621B (en) | The preparation method of the rear-earth-doped vanadate composite nano fiber catalysis material of heterojunction type titanium dioxide | |
| CN106732504A (en) | The preparation method and application of Graphene optically catalytic TiO 2 composite | |
| Zhang et al. | Uniform hollow TiO2: Sm3+ spheres: Solvothermal synthesis and luminescence properties | |
| Komaraiah et al. | Influence of Fe3+ ion doping on the luminescence emission behavior and photocatalytic activity of Fe3+, Eu3+-codoped TiO2 thin films | |
| Wang et al. | Photoluminescence properties of the rare-earth ions in the TiO2 host nanofibers prepared via electrospinning | |
| CN105002599A (en) | Preparation method of high-purity N-doped TiO2 mesoporous nanofiber | |
| Xie et al. | Enhanced photocatalytic activity and dielectric property of c-axis oriented Bi2VO5. 5 thin film by Gd3+ doping | |
| Jadhav et al. | Effect of different additives on the size control and emission properties of Y2O3: Eu3+ nanoparticles prepared through the coprecipitation method | |
| Lin et al. | Luminescent properties and characterization of one dimensional Gd2O3: Eu3+ phosphor nano-wire for field emission application | |
| Navgire et al. | Effect of poly (ethylene glycol) surfactant on carbon-doped MoO 3 nanocomposite materials and its photocatalytic activity | |
| Huan et al. | Enhanced ferro-photocatalytic performance for ANbO 3 (A= Na, K) nanoparticles | |
| Zhang et al. | Tuning the defects and luminescence of ZnO:(Er, Sm) nanoflakes for application in organic wastewater treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171103 Termination date: 20191124 |