CN104927864B - Rare earth ions doped fluoride matrix visible-ultraviolet upconversion luminescence material, preparation method therefor and application thereof - Google Patents
Rare earth ions doped fluoride matrix visible-ultraviolet upconversion luminescence material, preparation method therefor and application thereof Download PDFInfo
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- CN104927864B CN104927864B CN201510390146.6A CN201510390146A CN104927864B CN 104927864 B CN104927864 B CN 104927864B CN 201510390146 A CN201510390146 A CN 201510390146A CN 104927864 B CN104927864 B CN 104927864B
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Abstract
The invention discloses a rare earth ions doped fluoride matrix visible-ultraviolet upconversion luminescence material. In the material, fluoride acts as a matrix, Pr3+ is doped in the matrix material, and the molar ratio of elements is: fluoride:Pr3+ = 0.7-0.99:0.01-0.1. In addition, the invention further provides a preparation process of the material. The preparation process comprises: (a), according to the chemical formula, precisely weighing out a carbonate material or an oxide material of the corresponding element and ammonium biphosphate in accordance with the stoichiometric ratio; and (b) grinding the material into powder, burning the material at the temperature of 700-1,000 DEG C for 1.5-4 h, cooling the material to the room temperature, and grinding the material to obtain a powdery upconversion luminescence material. It is experimentally proved that the material, when excited by a common light source (such as an incandescent lamp, an xenon lamp, a fluorescent lamp, or an LED lamp) or especially sunlight, can emit UVC ultraviolet light capable of effectively killing bacteria. The material has better application prospects concerning food safety and environmental protection.
Description
Technical field
The present invention relates to luminescent material and its production and use, specifically a kind of fluoride-based rare earth ion is mixed
Miscellaneous visible-ultraviolet conversion luminous material and its preparation method and application.
Background technology
Ultraviolet-sterilization technology starts progressively to be applied to sewage, industrial disinfection field from 20 century 70s.The nineties with
The breakthrough of key technology, more because of its distinctive environment protection clean characteristic, and is used widely in American-European countries.Ultraviolet is a kind of
Invisible light wave, is present in the outside at spectrum violet ray end, and its DNA that can destroy in microflora organisms cell is (de-
Oxygen ribonucleic acid) or RNA (ribonucleic acid) molecular structure, cause growth cell death and（Or）Regenerative cell is dead,
Reach the effect of sterilizing.Through test, the effective wavelength range of ultraviolet sterilization can be divided into four different wave bands：UVA
（400～315nm）、UVB（315～280nm）、UVC（280～200nm）And vacuum ultraviolet（200～100nm）.Compared with UVA and
UVB section is compared, and UVC section ultraviolet can kill virus and antibacterial by destroying the DNA structure of microorganism at short notice, because
This, typically described ultraviolet disinfection actually refers to that UVC sterilizes.But ultraviolet light particularly UVC, because wavelength is short, is passing through
During object most of by object scatter and absorption, penetration depth very shallow it is seen then that being usually used in the device 254nm mercury lamp sterilizing at present
Also the shallower antibacterial of depth being exposed to outside can only be killed, and the antibacterial in deeper container is unable to reach at all and really kills
The purpose of bacterium.
Up-conversion luminescent material generally by inorganic material as substrate, rare earth ion as the centre of luminescence, by rare earth from
After son absorbs two or more lower energy photons, launch a high-energy photon and realize luminous purpose, it is widely used in
Illumination and field of display systems.With deepening continuously and laser technology to the aspect research such as upper switching mechanism and materials synthesis
Fast development, the application of up-conversion extends continuous.As Publication No. CN1977999A provides one kind ultraviolet
The method that up-conversion luminescence nanoparticulate selective kills cell, the method adopts the laser of 798nm as excitaton source, laser energy
Metric density is high, is conducive to Up-conversion emission；But the problem that it brings be laser excite area less it is impossible to kill large area
Antibacterial, and the laser of higher-wattage also can be to operation with using bringing potential safety hazard.And for example Publication No.
CN101976795A also reports a kind of ultraviolet up-conversion mixing Gd, and this material can produce 200-280nm（UVC）Purple
Outer light, but excitaton source is also the laser instrument equally employing 980nm.Therefore, research and develop one kind in ordinary light source（Non-laser）Excite
Under, the up-conversion luminescent material that particularly just can produce UVC ultraviolet light under sunlight undoubtedly there is higher application valency
Value.
Content of the invention
It is an object of the invention to provide a kind of fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material and
Its preparation method and application, to solve to be currently used for the commonly used laser of up-conversion luminescent material sterilizing as excitaton source, its
Not only bring potential safety hazard to operator, and the problem that cannot be applied in large-area sterilization.
The purpose of the present invention is achieved through the following technical solutions：
A kind of fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material, with fluoride as substrate, described
Doped with Pr in substrate3+；With molar ratio computing,
Fluoride:Pr3+=0.7-0.99:0.01-0.1；This material under visible light illumination, launches UVC ultraviolet light.
Heretofore described fluoride is the alkali metal fluoride containing metallic yttrium, the fluorination of the alkaline-earth metal containing metallic yttrium
Any one in thing, the magnesium-yttrium-transition metal fluoride containing metallic yttrium or the carbon family metal fluoride containing metallic yttrium.
The heretofore described alkali metal fluoride containing metallic yttrium is fluorine yttrium lithium, fluorine yttrium sodium, fluorine yttrium potassium, fluorine yttrium rubidium, fluorine
Any one in yttrium caesium；Alkali earth metal fluoride containing metallic yttrium is fluorine yttrium calcium, any one in fluorine yttrium barium；Containing gold
The magnesium-yttrium-transition metal fluoride belonging to yttrium is fluorine yttrium molybdenum；The 3rd main group metal fluoride containing metallic yttrium is fluorine yttrium thallium；Containing gold
The carbon family metal fluoride belonging to yttrium is fluorine yttrium lead.
Preferably, the described alkali metal fluoride containing metallic yttrium be fluorine yttrium lithium, fluorine yttrium sodium, any one in fluorine yttrium potassium
Kind；Alkali earth metal fluoride containing metallic yttrium is fluorine yttrium calcium.
It is further preferable that the substrate of this material is fluorine yttrium lithium or fluorine yttrium sodium；Each unit in material is prepared for substrate with fluorine yttrium lithium
Element mol ratio be：Yttrium:Praseodymium:Lithium:Fluorine=0.98:0.02:1:4；Prepare the mol ratio of each element in material with fluorine yttrium sodium for substrate
For：Yttrium:Praseodymium:Sodium:Oxygen=0.97:0.03:1:4.
A kind of preparation method of fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material, walks including following
Suddenly：
（a）According to chemical composition as described above, stoichiometrically weigh carbonate or the oxide raw material of respective element
And ammonium dihydrogen phosphate；
（b）After alleged material is ground, calcination 1.5-4 h at 700-1200 DEG C, it is cooled to room temperature, grind, obtain
Powdered fluorinated thing base rare earth is visible-ultraviolet conversion luminous material.
It is preferable that step in preparation method of the present invention（a）According to yttrium：Praseodymium：Lithium：Fluorine=0.98:0.02:1:4 mole join
Ratio weighs lithium carbonate, yittrium oxide, praseodymium oxide, ammonium fluoride.
It is preferable that step in preparation method of the present invention（a）According to yttrium：Praseodymium：Sodium：Oxygen=0.97:0.03:1:4 mole join
Ratio weighs sodium fluoride, yittrium oxide, praseodymium oxide, ammonium fluoride.
It is preferable that step in preparation method of the present invention（b）In at 700-1000 DEG C calcination 2 h.
The present invention is prepared for by specific proportioning raw materials and process conditions can be in ordinary light source, particularly sunlight
Exciting under generation ultraviolet（UVC）Light；Its preparation process is simple, good operability, it is easy to large-scale production, can be used for medical treatment, ring
The sterilization field such as border.
Fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material of the present invention answering in sterilization
With wherein visible light source is any general visible source, preferably one of sunlight, electric filament lamp, LED or xenon lamp or two kinds
Above combination in any；Its more preferably sunlight.Because sunlight is the inexhaustible free energy, manageable
Scope is bigger, needs the field of large-area sterilization to have more actual application prospect for rivers and lakes pollution and grain security etc..
Described up-conversion luminescent material can be positioned in actual applications, be sprayed in implements or independent coating or and its
His material mixing is coated on the surface of implements, plays the purpose of sterilization under visible light source irradiates；It is specifically applied such as
For suppression silo surface from mildewing, can directly prepared sample be coated in inside silo, with sunlight, electric filament lamp, LED
Or xenon lamp irradiates the purpose reaching sterilization；And for example process culture dish within antibacterial when it is not necessary to open lid, can in advance by
It is coated in the inner surface of culture dish, with sunlight, electric filament lamp, and LED or xenon lamp are radiated on sample through culture dish, using sample
This sample can also be coated in body surface by the UVC uv disinfection that product send, and under the irradiation of sunlight, reach and prevent
The purpose of bacterial growth.
The innovation of the present invention is with fluoride as substrate, the Pr of proper proportion of adulterating in this host material3+, lead to
Cross Solid phase synthesis a kind of in the up-conversion luminescent material that can produce efficient sterilizing UVC ultraviolet, this material is in general visible
Light source, particularly sunlight realize UVC ultraviolet light emission under exciting, realize sterilization or the purpose of bacteria growing inhibiting.This is not only
With regard to solve the problems, such as current material using laser excitation exist potential safety hazard and excite area less, cannot large-area sterilization,
And because visible ray is cheap, sunlight is inexhaustible, it is possible to while reducing sterilization cost, realize large area
Excite a large amount of ultraviolet lights of generation（UVC）For sterilizing.Therefore, use it for sky gas and water, food, medical treatment and people to rely life
In each living environment deposited, the killing of pathogenic bacterium has immeasurable economic benefit and social value.
Brief description
Fig. 1 is excitation spectrum under xenon lamp excites for the material and the emission spectra of embodiment 1 preparation.
Fig. 2 is ultraviolet image under sunlight excites for the blank sample.
Fig. 3 is the ultraviolet image under sunlight excites for the material of embodiment 1 preparation.
Fig. 4 is the ultraviolet image under sunlight excites for the material of embodiment 2 preparation.
Fig. 5 is the ultraviolet image under sunlight excites for the material of embodiment 4 preparation.
Fig. 6 is the ultraviolet image under sunlight excites for the material of embodiment 5 preparation.
Specific embodiment
Example below is used for further describing the present invention, but the invention is not limited in any way.
Embodiment 1
According to yttrium：Praseodymium：Lithium：Fluorine=0.98:0.02:1:4 mol ratio weighs lithium carbonate, yittrium oxide, praseodymium oxide, fluorination
Ammonium.After raw mill, in 900 DEG C of calcinations 2 hours, drop to room temperature.Take out, regrinding, obtain sample powder fluoride-based
Rare earth is visible-ultraviolet conversion luminous material.
Embodiment 2
According to yttrium：Praseodymium：Lithium：Fluorine=0.98:0.02:1:4 mol ratio weighs lithium carbonate, yittrium oxide, praseodymium oxide, fluorination
Ammonium.After raw mill, in 700 DEG C of calcinations 4 hours, drop to room temperature.Take out, regrinding, obtain sample powder fluoride-based
Rare earth is visible-ultraviolet conversion luminous material.
Embodiment 3
According to yttrium：Praseodymium：Lithium：Fluorine=0.98:0.02:1:4 mol ratio weighs lithium carbonate, yittrium oxide, praseodymium oxide, fluorination
Ammonium.After raw mill, in 1000 DEG C of calcinations 1.5 hours, drop to room temperature.Take out, regrinding, obtain sample powder fluoride
Base rare earth is visible-ultraviolet conversion luminous material.
Embodiment 4
According to yttrium：Praseodymium：Sodium：Fluorine=0.97:0.03:1:4 mol ratio weighs sodium fluoride, yittrium oxide, praseodymium oxide, fluorination
Ammonium.After raw mill, in 900 DEG C of calcinations 2 hours, drop to room temperature.Take out, regrinding, obtain sample powder fluoride-based
Rare earth is visible-ultraviolet conversion luminous material.
Embodiment 5
According to yttrium：Praseodymium：Calcium：Fluorine=3.92:0.02:0.98:13.72 mol ratio weighs calcium fluoride, yittrium oxide, oxidation
Praseodymium, ammonium fluoride.After raw mill, in 900 DEG C of calcinations 2 hours, drop to room temperature.Take out, regrinding, obtain sample powder fluorine
Compound base rare earth is visible-ultraviolet conversion luminous material.
The performance detection of the up-conversion luminescent material prepared by embodiment 6 present invention
Experimental technique：
1st, embodiment 1 prepares the excitation spectrum of material and the experiment testing conditions of emission spectrum：Test instrunment is Hitachi F-
4600, test temperature is room temperature.
2nd, the experiment testing conditions that lower embodiment prepares the ultraviolet image of material are excited to be in sunlight：The ultraviolet being used
Imager model CoroCAM504, by South Africa science and industrial research meeting（CSIR）Researched and developed and produced, its basic performance
Parameter is as follows：Test wavelength scope is 240-280nm, minimum ultraviolet luminous sensitivity 8 × 10-18W/cm2, ultraviolet detector is variable
Gain 0%-100% continuous variable.Surveyed blank sample is ultraviolet image during not setting-out product under sunlight, as shown in Figure 2.
Its testing result is shown in Fig. 1-3, from figure 1 it appears that exciting the sample of the embodiment of the present invention 1 preparation with xenon lamp,
Corresponding excitation spectrum and emission spectrum are obtained, its launch wavelength belongs to the effective wavelength range of sterilization.We incite somebody to action this simultaneously
In invention, the sample of embodiment 1 preparation is placed under sunlight, obtains the ultraviolet image of sample, as shown in Figure 3, from image
It can be seen that sample can excite lower generation UVC section ultraviolet light in sunlight, this wave band is the effective range of sterilization.
In the same manner, as shown in Fig. 4 to Fig. 6, it all can be for the performance test results of the luminescent material of embodiment 2,4,5 preparation
Sunlight excites lower generation UVC section ultraviolet light.
Claims (8)
1. application in sterilization for a kind of fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material, its feature exists
In with fluoride as substrate, doped with Pr in described substrate3+；With molar ratio computing, fluoride:Pr3+=0.7-0.99:0.01-
0.1；This material under visible light illumination, launches UVC ultraviolet light, using the UVC uv disinfection sending；Described fluoride
It is the alkali metal fluoride containing metallic yttrium, the alkali earth metal fluoride containing metallic yttrium.
2. fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material according to claim 1 is in sterilization
Application it is characterised in that the described alkali metal fluoride containing metallic yttrium be fluorine yttrium lithium, fluorine yttrium sodium, fluorine yttrium potassium, fluorine yttrium rubidium,
Any one in fluorine yttrium caesium；Alkali earth metal fluoride containing metallic yttrium is fluorine yttrium calcium, any one in fluorine yttrium barium.
3. fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material according to claim 2 is in sterilization
Application it is characterised in that the described alkali metal fluoride containing metallic yttrium be fluorine yttrium lithium, fluorine yttrium sodium, any in fluorine yttrium potassium
A kind of.
4. fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material according to claim 2 is in sterilization
Application it is characterised in that the described alkali earth metal fluoride containing metallic yttrium be fluorine yttrium calcium.
5. fluoride-based ion doping rare earth according to claim 1 visible-ultraviolet conversion luminous material is in sterilization
Application it is characterised in that described up-conversion luminescent material is placed in, on the surface that is sprayed in implements or is coated in implements,
The purpose of sterilization is played under visible light source irradiates.
6. fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material according to claim 5 is in sterilization
Application it is characterised in that described visible light source is one of sunlight, electric filament lamp, LED or xenon lamp or two or more
Combination in any.
7. fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material according to claim 5 or 6 is in sterilization
In application it is characterised in that described visible light source is sunlight.
8. a kind of preparation method of fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material is it is characterised in that wrap
Include following steps：
（a）With fluoride as substrate, doped with Pr in described substrate3+；With molar ratio computing, fluoride:Pr3+=0.7-0.99:
0.01-0.1；According to the described chemical composition of material, stoichiometrically weigh carbonate or the oxide raw material of respective element
And ammonium dihydrogen phosphate；Described fluoride is the alkali metal fluoride containing metallic yttrium or the fluorination of the alkaline-earth metal containing metallic yttrium
Thing；
（b）After alleged material is ground, calcination 1.5-4 h at 700-1000 DEG C, it is cooled to room temperature, grind, obtain powder
Fluoride-based rare earth ion doped visible-ultraviolet conversion luminous material of shape.
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| CN111137945B (en) * | 2020-01-13 | 2022-07-05 | 中国科学院南京土壤研究所 | Method for removing antibiotics in sewage by utilizing microorganism-photocatalysis coupling and upconversion-titanium dioxide composite material thereof |
| CN111545224A (en) * | 2020-05-13 | 2020-08-18 | 重庆大学 | Up-conversion photocatalytic material and preparation method and application thereof |
| CN111672522A (en) * | 2020-05-13 | 2020-09-18 | 重庆大学 | NYF-Ti binary composite photocatalyst and preparation method thereof |
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| CN103059863A (en) * | 2011-10-19 | 2013-04-24 | 海洋王照明科技股份有限公司 | Fluoride phosphors for up-conversion luminescence, and preparation method and application thereof |
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