CN107008464A - A kind of visible light-responded NaYF4:The preparation method and application of La, Ce@TiO2 composites - Google Patents
A kind of visible light-responded NaYF4:The preparation method and application of La, Ce@TiO2 composites Download PDFInfo
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- CN107008464A CN107008464A CN201710236067.9A CN201710236067A CN107008464A CN 107008464 A CN107008464 A CN 107008464A CN 201710236067 A CN201710236067 A CN 201710236067A CN 107008464 A CN107008464 A CN 107008464A
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- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims description 8
- 239000011775 sodium fluoride Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000002114 nanocomposite Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229940053652 fluorinse Drugs 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 239000011941 photocatalyst Substances 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010298 TiOSO4 Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000120 microwave digestion Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910002339 La(NO3)3 Inorganic materials 0.000 description 1
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 1
- YUVLVONHNMXKBW-UHFFFAOYSA-L [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O YUVLVONHNMXKBW-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000006872 improvement Effects 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
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- VZOPRCCTKLAGPN-UHFFFAOYSA-L potassium;sodium;2,3-dihydroxybutanedioate;tetrahydrate Chemical class O.O.O.O.[Na+].[K+].[O-]C(=O)C(O)C(O)C([O-])=O VZOPRCCTKLAGPN-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/002—Grey water, e.g. from clothes washers, showers or dishwashers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of visible light-responded NaYF4:La,Ce@TiO2The preparation method of composite, belongs to technical field of semiconductor, in order to widen TiO2Light abstraction width, the visible ray in sunshine is made full use of, by TiO2With up-conversion luminescent material NaYF4:La, Ce formation compound, in NaYF4:La,Ce@TiO2In composite, up-conversion luminescent material can be effectively it will be seen that light be converted to ultraviolet light by TiO2Absorb；The invention also discloses a kind of visible light-responded NaYF4:La,Ce@TiO2Composite is used for the application of photocatalytic degradation laundrywastes under visible ray as catalysis material.A kind of visible light-responded NaYF of the present invention4:La,Ce@TiO2The preparation method of composite, the NaYF prepared using hydro-thermal method4:La,Ce@TiO2Composite, laundrywastes of degrading under visible light shows excellent photocatalytic activity；Present invention process is very simple, cheap and easy to get, with low cost, and the reaction time is shorter, so that energy consumption and reaction cost are reduced, it is nontoxic, meet environment-friendly requirement.
Description
Technical field
The invention belongs to technical field of semiconductor, and in particular to a kind of visible light-responded NaYF4:La,Ce@TiO2It is multiple
The preparation method and application of condensation material.
Background technology
At present, along with China's rapid economic development, human living standard is also improved constantly simultaneously, and now the mankind are faced
Environmental pollution and energy crisis also become increasingly serious, especially laundrywastes turn into sanitary sewage most, although
Contain a certain amount of nitrogen and phosphorus in laundrywastes, be the main nutrient elements of plant, but river course, meeting are directly discharged into without processing
Water, phosphorus content are sharply increased, and also contains exhibiting high surface activating agent in laundrywastes, more pollutions can be caused
Thing dissolves in water, ultimately forms body eutrophication, is destroyed water quality, finally causes the death such as fish.Therefore, it should
This waste water is renovated concentratedly.There are a variety of methods, such as chemical method, biological contact oxidation at present to the improvement of liquid detergent waste water
Change method, physics are with method for being combined of chemistry etc., but in recent years, photocatalysis degradation organic contaminant because have energy-conservation, it is efficient,
The advantages of contaminant degradation is thorough, has been generally considered the desirable route for solving the problems, such as current water body orgnic compound pollution.
But in solar spectrum, ultraviolet light only accounts for 5%, and the ratio of visible ray is up to 43%, and therefore, developing can practical application
Visible light-responded semiconductor light-catalyst be current photocatalysis research field hot issue.
More semi-conducting material TiO is studied at present2, although it is good, nontoxic, anti-light with dielectric constant height, heat endurance
The advantages of burn into is cheap, but be only capable of by λ<387.5nm (3.2eV) ultraviolet excitation (account for sunshine 5%) is produced
e-And h+, light-catalyzed reaction is completed, this largely hinders TiO2The practical application of photocatalysis technology.
The content of the invention
Goal of the invention：It is an object of the invention to provide a kind of visible light-responded NaYF4:La,Ce@TiO2Composite
Preparation method and application, using the purpose of Visible Light Induced Photocatalytic laundrywastes, improve TiO2To the utilization rate of visible ray, and then overcome
TiO2The defect of ultraviolet light can only be responded.
Technical scheme：To achieve the above object, the present invention provides following technical scheme：
A kind of visible light-responded NaYF4:La,Ce@TiO2The preparation method of composite, comprises the following steps：
1) NaYF is prepared4:La,Ce
Sodium fluoride is taken to be dissolved in deionized water, after ultrasonic disperse, by yttrium nitrate, lanthanum nitrate, the nitre that concentration is 0.2mol/L
After sour cerium solution is well mixed, it is added dropwise to the Fluorinse after above-mentioned ultrasound under being stirred continuously of magnetic stirring apparatus
In, reaction is stirred for after being added dropwise to complete, the solution after stirring is moved into polytetrafluoroethylliner liner reaction lining, hydro-thermal reaction is treated
Reactor is cooled to after room temperature, is dried to obtain required sample, i.e. NaYF with ethanol and deionized water cyclic washing for several times4:La,
Ce powder；
2) NaYF is prepared4:La,Ce@TiO2Composite
By NaYF4:La, Ce powder are by ultrasonic disperse in absolute ethyl alcohol；Then, by TiO2Evenly spread to anhydrous second
In alcoholic solution；Finally, above-mentioned two parts of solution is mixed into reaction at room temperature, reacts the anhydrous second of reaction product after terminating
White clear colloid is obtained after alcohol and water washing, centrifugation, white clear colloid is dispersed in absolute ethyl alcohol and is transferred to again
In the closed autoclave with polytetrafluoroethyllining lining, after hydro-thermal process, obtain with nuclear shell structure nano composite wood
Material, as visible light-responded NaYF4:La,Ce@TiO2Composite.
Wherein, titanyl sulfate TiOSO4Excessive precipitating reagent is added in solution, makes Ti4+Positive metatitanic acid Precipitation is formed completely,
It will be precipitated and dissolved with a certain amount of concentrated nitric acid after filtering, obtain clear TiO (NO3)2Solution, uses oxidimetry mark
Determine Ti4+Concentration, by the citric acid of various concentrations and the TiO (NO of certain volume3)2Solution is mixed, it is ensured that Ti4+Fully complexing,
The NH of different content is added into mixed solution4NO3, the mol ratio to change nitrate anion and citric acid, with ammoniacal liquor regulation pH
Value is to neutrality, and in 70~90 DEG C of temperature heating evaporations, with citric acid complex reaction occurs for metal ion, with the reduction of moisture,
Solution is gradually converted into pale yellow transparent gel, in the Muffle furnace that gel is placed in less than 200 DEG C, fully expanded charred rear heating
To 300 DEG C, gel be ignited occurring self-propagating combustion reaction it is burned after, obtain fluffy foam-like gray powder, ashes is 600
DEG C insulation 2h, obtain TiO2。
Step 1) in, described sodium fluoride, yttrium nitrate, lanthanum nitrate, the mol ratio of cerous nitrate are 300~600：15：1：4.
Step 1) in, the temperature of described hydro-thermal reaction is 160 °, and the time is 8h.
Step 2) in, described TiO2Mol ratio with yttrium nitrate is 500：3~35.
Step 2) in, the temperature of described hydro-thermal reaction is 160 °, and the time is 12h.
A kind of visible light-responded NaYF prepared using any one method4:La,Ce@TiO2Composite is used as photocatalysis
Material is used for the application of photocatalytic degradation laundrywastes under visible ray.
Inventive principle：In order to widen TiO2Light abstraction width, the visible ray in sunshine is made full use of, by TiO2With it is upper
Changing luminous material NaYF4:La, Ce formation compound, in NaYF4:La,Ce@TiO2In composite, up-conversion luminescent material
Can be effectively it will be seen that light be converted to ultraviolet light by TiO2Absorb, therefore, reached useless using Visible Light Induced Photocatalytic laundry
The purpose of water, improves TiO2To the utilization rate of visible ray, and then overcome TiO2The defect of ultraviolet light can only be responded.The present invention is adopted
NaYF is successfully prepared with two one-step hydrothermals4:La,Ce@TiO2Composite, is tied using X-ray diffraction (XRD) to product
Structure is analyzed, and photocatalytic degradation experiment is carried out by target contaminant of laundrywastes, is measured and inhaled by ultraviolet-visible spectrophotometer
Luminosity, to assess its photocatalytic activity.NaYF is assessed by COD and ammonia nitrogen determination4:La,Ce@TiO2Composite is most preferably put into
Amount.
Beneficial effect：Compared with prior art, a kind of visible light-responded NaYF of the invention4:La,Ce@TiO2Composite
Preparation method, the NaYF prepared using hydro-thermal method4:La,Ce@TiO2Composite, laundrywastes of degrading under visible light is shown
Go out excellent photocatalytic activity；Present invention process is very simple, cheap and easy to get, with low cost, and the reaction time is shorter, so as to reduce
Energy consumption and reaction cost, it is nontoxic, meet environment-friendly requirement.
Brief description of the drawings
NaYF prepared by Fig. 14:La,Ce@TiO2Composite XRD diffraction spectrograms；
Fig. 2 is different loads amount composite photo-catalyst to laundrywastes degradation property；
Fig. 3 is influence of the different catalysts dosage to COD clearances；
Fig. 4 is influence of the different catalysts dosage to ammonia nitrogen removal frank.
Embodiment
The present invention is further described with specific embodiment below in conjunction with the accompanying drawings.
A kind of visible light-responded NaYF4:La,Ce@TiO2The preparation method of composite, comprises the following steps：
1) NaYF is prepared4:La,Ce
Sodium fluoride is taken to be dissolved in deionized water, after ultrasonic disperse, by yttrium nitrate, lanthanum nitrate, the nitre that concentration is 0.2mol/L
After sour cerium solution is well mixed, it is added dropwise to the Fluorinse after above-mentioned ultrasound under being stirred continuously of magnetic stirring apparatus
In, reaction is stirred for after being added dropwise to complete, the solution after stirring is moved into polytetrafluoroethylliner liner reaction lining, hydro-thermal reaction is treated
Reactor is cooled to after room temperature, is dried to obtain required sample, i.e. NaYF with ethanol and deionized water cyclic washing for several times4:La,
Ce powder；
2) NaYF is prepared4:La,Ce@TiO2Composite
By NaYF4:La, Ce powder are by ultrasonic disperse in absolute ethyl alcohol；Then, by TiO2Evenly spread to anhydrous second
In alcoholic solution；Finally, above-mentioned two parts of solution is mixed into reaction at room temperature, reacts the anhydrous second of reaction product after terminating
White clear colloid is obtained after alcohol and water washing, centrifugation, white clear colloid is dispersed in absolute ethyl alcohol and is transferred to again
In the closed autoclave with polytetrafluoroethyllining lining, after hydro-thermal process, obtain with nuclear shell structure nano composite wood
Material, as visible light-responded NaYF4:La,Ce@TiO2Composite.
Wherein, titanyl sulfate TiOSO4Excessive precipitating reagent is added in solution, makes Ti4+Positive metatitanic acid Precipitation is formed completely,
It will be precipitated and dissolved with a certain amount of concentrated nitric acid after filtering, obtain clear TiO (NO3)2Solution, uses oxidimetry mark
Determine Ti4+Concentration, by the citric acid of various concentrations and the TiO (NO of certain volume3)2Solution is mixed, it is ensured that Ti4+Fully complexing,
The NH of different content is added into mixed solution4NO3, the mol ratio to change nitrate anion and citric acid, with ammoniacal liquor regulation pH
Value is to neutrality, and in 70~90 DEG C of temperature heating evaporations, with citric acid complex reaction occurs for metal ion, with the reduction of moisture,
Solution is gradually converted into pale yellow transparent gel, in the Muffle furnace that gel is placed in less than 200 DEG C, fully expanded charred rear heating
To 300 DEG C, gel be ignited occurring self-propagating combustion reaction it is burned after, obtain fluffy foam-like gray powder, ashes is 600
DEG C insulation 2h, obtain TiO2。
Step 1) in, sodium fluoride, yttrium nitrate, lanthanum nitrate, the mol ratio of cerous nitrate are 300~600：15：1：4.Step 1)
In, the temperature of hydro-thermal reaction is 160 °, and the time is 8h.
Step 2) in, TiO2Mol ratio with yttrium nitrate is 500：3~35.Step 2) in, the temperature of hydro-thermal reaction is
160 °, the time is 12h.
A kind of visible light-responded NaYF prepared using any one method4:La,Ce@TiO2Composite is used as photocatalysis
Material is used for the application of photocatalytic degradation laundrywastes under visible ray.
NaYF as shown in Figure 14:La, Ce are in TiO2Content be respectively 1%, 3%, 5% and 10% (mass ratio),
NaYF4:La,Ce@TiO2The characteristic peak of composite photo-catalyst is not because TiO2Addition and change, illustrate NaYF4:La,
Ce@TiO2The crystallinity of composite photo-catalyst is very high.As shown in Fig. 2 as the TiO of load 5%2When, NaYF4:La,Ce@TiO2It is multiple
Closing light catalyst can reach in 2h under visible ray to the degradation rate of laundrywastes to the photocatalytic activity highest of laundrywastes
75%.As shown in figure 3, when optimal addition is 2g/L, COD removal effects are best.As shown in figure 4, when addition is 2g/L,
Ammonia nitrogen removal effect is best.
NaYF in the present invention4:La,Ce@TiO2The structure of composite photo-catalyst, can from Fig. 1 by X-ray diffraction (XRD) determination
To find out, the XRD crystallinity of different doping ratio samples is preferable.TiO2As main component, we are able to observe that anatase
The θ of characteristic diffraction peak 2 (25.245 °, 37.772 °, 48.036 °, 75.030 °) of crystalline phase, corresponding NaYF4:La, Ce diffraction maximum is
2θ(27.791°、30.781°、32.236°、46.258°).Simultaneously in NaYF4:La,Ce@TiO2The characteristic peak of composite photo-catalyst
Not because TiO2Addition and change, illustrate NaYF4:La,Ce@TiO2The crystallinity of composite photo-catalyst is very high.
Embodiment 1：NaYF4:La,Ce@TiO2The preparation of composite
(1)NaYF4:It is prepared by La, Ce：Take sodium fluoride to be dissolved in 50mL deionized waters, be by concentration after ultrasonic disperse 30min
0.2mol/L yttrium nitrate (Y (NO3)·6H2O), lanthanum nitrate (La (NO3)·6H2O), cerous nitrate (Ce (NO3)·6H2O) respectively
Add, wherein each material adds ratio such as following table：
| Ratio | TiO2(g) | Y(NO3)3(ml) | La(NO3)3(ml) | Ce(NO3)3(ml) | NaF(g) |
| 1% | 2 | 0.9 | 0.06 | 0.24 | 1 |
| 3% | 2 | 2.7 | 0.18 | 0.72 | 1 |
| 5% | 2 | 4.5 | 0.3 | 1.2 | 1 |
| 10% | 2 | 9 | 0.6 | 2.4 | 1.5 |
After solution is well mixed, it is slowly dropped into the fluorination liquid after above-mentioned ultrasound under being stirred continuously of magnetic stirring apparatus
In.It is stirred for reacting 1h after being added dropwise to complete.Solution after stirring is moved into polytetrafluoroethylliner liner reaction lining, at 180 DEG C
Hydro-thermal 12h.Question response kettle is cooled to after room temperature, obtained sample with ethanol and deionized water cyclic washing for several times, then 80
Required sample is dried to obtain in DEG C drying box.
(2)NaYF4:The preparation of La, Ce@TiO2 composites：First, by the NaYF of above-mentioned preparation4:La, Ce powder are distinguished
By ultrasonic disperse in 10mL absolute ethyl alcohols；Then, by four parts of 2g TiO2Evenly spread in ethanol solution；Most
Afterwards, by TiO2Solution is separately added into above-mentioned NaYF4:La, Ce solution mix reaction 20h at room temperature.After reaction terminates, instead
Answer product absolute ethyl alcohol and water washing, centrifugation repeatedly.White clear colloid is obtained, is dispersed in absolute ethyl alcohol and shifts again
Into the autoclave with polytetrafluoroethyllining lining closed 40mL, after 160 DEG C of hydro-thermal process 6h, obtain with core
The nano composite material of shell structure different proportion.
Embodiment 2：NaYF4:La,Ce@TiO2The sign of composite
NaYF in the present invention4:La,Ce@TiO2The structure of composite photo-catalyst, can from Fig. 1 by X-ray diffraction (XRD) determination
To find out, the XRD crystallinity of different doping ratio samples is preferable.TiO2As main component, we are able to observe that anatase
The θ of characteristic diffraction peak 2 (25.245 °, 37.772 °, 48.036 °, 75.030 °) of crystalline phase, corresponding NaYF4:La, Ce diffraction maximum is
2θ(27.791°、30.781°、32.236°、46.258°).Simultaneously in NaYF4:La,Ce@TiO2The characteristic peak of composite photo-catalyst
Not because TiO2Addition and change, illustrate NaYF4:La,Ce@TiO2The crystallinity of composite photo-catalyst is very high.
Embodiment 3：NaYF4:La,Ce@TiO2The COD and Two N-ammoniacal Measurements of composite
COD assay methods：6 samples can be cleared up every time using micro-wave digestion, No. six counteracting tank is used to determine blank value,
During determination sample, 1.5mL sample (No. six tanks are distilled water) is added in 6 counteracting tanks, 0.2mL sulfuric acid is then sequentially added
Mercury, 3mL sulfuric acid-silver sulfate, 0.5mL 0.5mol/L potassium bichromate, plus it is good after cover the lid of counteracting tank, be put into stove, if
Micro-wave digestion is put for single step run, parameter is then changed, it is 165 DEG C to set temperature, pressure is 20.0KPa, the time is one point five
Ten seconds, power was 1000W, when clearing up after end, treated that temperature is cooled to 60 DEG C of right and lefts and can take out counteracting tank, taking-up is cleared up
Then liquid capacity-fixed afterwards is centrifuged to 10mL, and the liquid after centrifugation is put into preheating 15min spectrophotometer,
Absorbance is determined under 600nm wavelength with spectrophotometer and then is substituted into and carries out calculating in formula and obtains x values, formula is y=
0.00003x+0.0418, its R2=0.994 formula is drawn by the standard curve of drafting solution.It is optimal as seen from Figure 3 plus
When entering amount for 2g/L, COD removal effects are best.
Two N-ammoniacal Measurements：By the solution after filtering taken respectively with pipette 0min, 30min, 60min, 90min,
Each 1mL of 120min samples is fitted into 5 colorimetric cylinders, and numbering 1,2,3,4, No. 5,5 colorimetric cylinders are settled to distilled water
50mL, then take colorimetric cylinder numbering to be No. 6, only add distilled water and be settled to 50mL, for measuring blank value.Then first add
1mL nessler reagent, then adds 1mL sodium potassium tartrate tetrahydrates, plus it is good after shake up, then stand 10 minutes, then use spectrophotometric
Meter measures absorbance at 420nm wavelength, then substitutes into progress calculating in formula and obtains x values, formula is y=0.1872x+
0.049, its R2=0.996 formula is drawn by drafting solution standard curve.Optimal addition is 2g/L as seen from Figure 4
When, ammonia nitrogen removal effect is preferably, consistent with the optimal injected volume of COD clearances.
Claims (6)
1. a kind of visible light-responded NaYF4:La,Ce@TiO2The preparation method of composite, it is characterised in that：Including following step
Suddenly：
1) NaYF is prepared4:La,Ce
Sodium fluoride is taken to be dissolved in deionized water, after ultrasonic disperse, by yttrium nitrate, lanthanum nitrate, the cerous nitrate that concentration is 0.2mol/L
After solution is well mixed, it is added dropwise in the Fluorinse after above-mentioned ultrasound under being stirred continuously of magnetic stirring apparatus, drop
Plus after the completion of be stirred for reaction, by after stirring solution move into polytetrafluoroethylliner liner reaction lining in, hydro-thermal reaction, question response kettle
It is cooled to after room temperature, is dried to obtain required sample, i.e. NaYF with ethanol and deionized water cyclic washing for several times4:La, Ce powder；
2) NaYF is prepared4:La,Ce@TiO2Composite
By NaYF4:La, Ce powder are by ultrasonic disperse in absolute ethyl alcohol；Then, by TiO2Evenly spread to absolute ethyl alcohol molten
In liquid；Finally, above-mentioned two parts of solution is mixed into reaction at room temperature, reaction terminate after reaction product absolute ethyl alcohol and
White clear colloid is obtained after water washing, centrifugation, white clear colloid is dispersed in absolute ethyl alcohol and is transferred to closed again
The autoclave with polytetrafluoroethyllining lining in, after hydro-thermal process, obtain with nuclear-shell structured nano-composite material, i.e.,
For visible light-responded NaYF4:La,Ce@TiO2Composite.
2. a kind of visible light-responded NaYF according to claim 14:La,Ce@TiO2The preparation method of composite, it is special
Levy and be：Step 1) in, described sodium fluoride, yttrium nitrate, lanthanum nitrate, the mol ratio of cerous nitrate are 300~600：15：1：4.
3. a kind of visible light-responded NaYF according to claim 14:La,Ce@TiO2The preparation method of composite, it is special
Levy and be：Step 1) in, the temperature of described hydro-thermal reaction is 160 °, and the time is 8h.
4. a kind of visible light-responded NaYF according to claim 14:La,Ce@TiO2The preparation method of composite, it is special
Levy and be：Step 2) in, described TiO2Mol ratio with yttrium nitrate is 500: 3~35.
5. a kind of visible light-responded NaYF according to claim 14:La,Ce@TiO2The preparation method of composite, it is special
Levy and be：Step 2) in, the temperature of described hydro-thermal reaction is 160 °, and the time is 12h.
6. a kind of visible light-responded NaYF that in claim 1-5 prepared by any one method4:La,Ce@TiO2Composite is made
It is used for the application of photocatalytic degradation laundrywastes under visible ray for catalysis material.
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