CN103131412B - Visible-ultraviolet up-conversion luminescent material BaGd2ZnO5: Er3+, preparation method thereof and application thereof - Google Patents

Visible-ultraviolet up-conversion luminescent material BaGd2ZnO5: Er3+, preparation method thereof and application thereof Download PDF

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CN103131412B
CN103131412B CN201310051102.1A CN201310051102A CN103131412B CN 103131412 B CN103131412 B CN 103131412B CN 201310051102 A CN201310051102 A CN 201310051102A CN 103131412 B CN103131412 B CN 103131412B
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luminescent material
ultraviolet
conversion luminescent
water
visible
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CN103131412A (en
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杨艳民
张伟
焦福运
李志强
杨志平
武永刚
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Hebei University
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    • 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
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    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

The invention discloses a visible-ultraviolet up-conversion luminescent material BaGd2ZnO5: Er3+. Rare earth element erbium is added to oxidizing materials of barium, gadolinium and zinc to prepare the body components of the visible-ultraviolet up-conversion luminescent material BaGd2ZnO5: Er3+. The molar ratio among all the elements, namely, the barium: the gadolinium: the zinc: erbium: oxygen is equal to 1: 1.98: 1: 0.02: 5. The visible-ultraviolet up-conversion luminescent material can be prepared by adoption of a liquid phase sol-gel method, and nanoscale powder products are obtained. Or a solid phase method is adopted, and micron-size powder products are obtained. Nanoscale materials are prepared to be water-soluble particles and the water-soluble particles are used for processing water bacteria. The materials prepared by the solid phase method or the sol-gel method are coated on the inner surface of a transparent object and the materials are used for sterilization on the inner portion of the object. The up-conversion luminescent material which aims at the defects that a 254-nm mercury lamp is poor in penetrating capacity and only can process superficial bacteria is provided, wherein the up-conversion luminescent material can generate UVC light under stimulation of a blue-light light-emitting diode (LED) is used for sterilization on the inner portion of a transparent container or disinfection of a water body.

Description

A kind of visible-ultraviolet conversion luminous material B aGd 2znO 5: Er 3+, Its Preparation Method And Use
Technical field
The invention belongs to up-conversion luminescent material technical field, relate to ultraviolet conversion luminous material and liquid phase thereof, solid phase preparation, can be applicable to biological and environmental improvement field.
Background technology
The DNA (thymus nucleic acid) of ultraviolet ray in can destroy microorganisms body cell or the molecular structure of RNA (Yeast Nucleic Acid), cause growth cell death and (or) reproducibility necrocytosis, reaches the effect of sterilization and disinfection.Through test, the effective wavelength range of ultra-violet sterilization can be divided into four different wave bands: UVA(400～315nm), UVB(315～280nm), UVC(280～200nm) and vacuum ultraviolet ray (200～100nm).With regard to sterilization speed, UVC, within microorganism absorption peak scope, can within 1s, kill virus and bacterium by the DNA structure by destroy microorganisms, and UVA and UVB is due to outside microorganism absorption peak scope, sterilization speed is very slow, often needs a few hours just can play germicidal action.Vacuum-ultraviolet light penetrativity extremely a little less than, fluorescent tube and sleeve pipe need to adopt the quartz of high transmittance, generally use the TOC in semicon industry degradation water, are not used in sterilization and disinfection.Therefore, in water supply and sewage work, said ultraviolet disinfection in fact just refers to UVC sterilization.Ultraviolet disinfection technology is on the basis based on anti-epidemiology of modern times, medical science and photodynamics, utilize high-level efficiency, high strength and long-life UVC wave band ultraviolet lighting water jets of particular design, various bacteriums, virus, parasite, algae and other pathogenic agent in water are directly killed, reach the object of sterilization.
The device that is usually used at present sterilization is 254nm mercury lamp, because the large sterilization effect of power is good, is widely used.But UV-light is UVC particularly, because wavelength is short, when by object, major part is by object scattering and absorption, and penetration depth is very shallow, therefore mercury lamp can only kill the more shallow bacterium of the degree of depth that is exposed to outside, and cannot reach sterilization effect for the bacterium in darker or Glass Containers.
Publication number is that CN1977999A has proposed the method with ultraviolet conversion luminous nano particles selectively killing cells.But patent applicant adopts the laser of 798nm as excitaton source, and laser energy density is high, is conducive to switching emission, however the problem of bringing be, laser excite area less, cannot process large-area bacterium, and laser also can bring danger to operation too by force.Publication number is that CN101976795A also reports the ultraviolet up-conversion of mixing Gd, can produce the UV-light of 200-280nm (UVC), but excitaton source is also to have adopted 980nm laser apparatus.Near infrared light particularly 980nm light people's eyes almost be can't see, and easily people is damaged.The ultraviolet up-conversion of inventing a kind of excited by visible light is more meaningful undoubtedly, ideal situation is just can produce the material of changing light in ultraviolet under solar light irradiation, this has important application prospect undoubtedly, and (this can process for water surrounding and grain, kill the germ in water, organize the grain mouldy).Yet the density of up-conversion luminous efficiency and exciting light is relevant, excitation density surpasses threshold value and could produce and change light.
In sum, find an area source at lower excitation density excite under, just can produce the material of changing light in ultraviolet, be the forward position of this area research, be also the difficult problem that ultra-violet light-emitting industry is needed solution badly.
Summary of the invention
The technical problem to be solved in the present invention is poor for 254nm mercury lamp penetrativity, can only process the shortcoming of shallow table bacterium, provide a kind of and excite the lower up-conversion luminescent material that can produce ultraviolet (UVC) light at blue-ray LED, for the sterilization of Glass Containers inside or the sterilization of water body.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows.
A kind of visible-ultraviolet conversion luminous material B aGd 2znO 5: Er 3+, its main body composition is that admixture rare earth element er makes in the oxide compound of barium, gadolinium, zinc, the mol ratio of each element is: barium: gadolinium: zinc: erbium: oxygen=1:1.98:1:0.02:5.
Above-mentioned visible-ultraviolet conversion luminous material B aGd 2znO 5: Er 3+sol-gel process for preparing, its step comprises:
A, in the mixture of gadolinium sesquioxide and Erbium trioxide, add dense HNO 3, adding distil water dilution simultaneously, fully, after reaction, obtains clear solution, and heating evaporation is removed unnecessary HNO 3, crystallization, makes corresponding nitrate solid; This nitrate solid and five water zinc nitrates, nitrate of baryta are mixed, be dissolved in deionized water, heated and stirred forms clear solution A;
B, the mixture of citric acid and ethylene glycol is dissolved in deionized water, be stirred to miscible evenly, form solution B;
C, above-mentioned A solution is slowly added dropwise in B solution, and at 60-80 ℃, is stirred to and forms homogeneous colloidal sol; 100-140 ℃ vacuum-drying 10-18 hour to forming gel, take out gel grind into powder; This powder is slowly warmed up to 280-320 ℃ and keep 1-3 hour, removes the organism in Gelatin powder; Naturally be cooled to room temperature, take out powder and grind; Gained powder is calcined 1-3 hour in 1000-1400 ℃, is down to room temperature, takes out, and again grinds, and obtains powder-product;
Wherein, the consumption of gadolinium sesquioxide, Erbium trioxide, five water zinc nitrates, nitrate of baryta makes the mol ratio of barium, gadolinium, zinc, four kinds of elements of erbium meet following relation: barium: gadolinium: zinc: erbium=1:1.98:1:0.02:5.
As a preferred technical solution of the present invention, the concrete operations parameter of step C is: above-mentioned A solution is slowly added dropwise in B solution, and at 70 ℃, is stirred to the homogeneous colloidal sol of formation; 120 ℃ of vacuum-drying is taken out gel grind into powder to forming gel in 14 hours; This powder is slowly warmed up to 300 ℃ and keep 2 hours, removes the organism in Gelatin powder; Naturally be cooled to room temperature, take out powder and grind; Gained powder is calcined 2 hours in 1200 ℃, is down to room temperature, takes out, and again grinds, and obtains nanoscale powder product.
Above-mentioned visible-ultraviolet conversion luminous material B aGd 2znO 5: Er 3+method for preparing solid phase, its step comprises: according to barium: a mole proportioning of gadolinium: zinc: erbium=1:1.98:1:0.02:5 takes barium carbonate, gadolinium sesquioxide, zinc oxide, Erbium trioxide; After above-mentioned material is ground at 1200-1600 ℃ calcination 2-4 hour, drop to room temperature, take out, again grind, obtain micron powder product.
Above-mentioned visible-ultraviolet conversion luminous material B aGd 2znO 5: Er 3+for ultraviolet-sterilization; Nanometer materials are prepared into water miscible particle for the treatment of water or biological Endophytic bacteria, irradiate the object that reaches sterilization with blue-ray LED; Powder body material is coated in transparent implements internal surface, with blue-ray LED, irradiates and reaches the internally sterilised object of implements.
As a preferred technical solution of the present invention, up-conversion luminescent material powder and silica gel or mixed with resin is even, be coated in above LED chip, heating, drying, obtains in the ultraviolet that blue-ray LED excites and changes diode chip for backlight unit.
The beneficial effect that adopts technique scheme to produce is: the device that is usually used at present sterilization is 254nm mercury lamp, UV-light is UVC particularly, because wavelength is short, when by object, major part is by object scattering and absorption, penetration depth is very shallow, therefore mercury lamp can only kill the more shallow bacterium of the degree of depth that is exposed to outside, and cannot reach sterilization effect for the bacterium in darker or Glass Containers or the bacterium of water body inside.Product of the present invention excites lower generation ultraviolet (UVC) light at blue light or the blue-ray LED of lower excitation density, due to the marketization of blue-ray LED, price is comparatively cheap, and volume is little, can form area source, blue light can see through glassware in addition, therefore this up-conversion is placed in vessel and can kills or suppress the bacterium in vessel, also can be used on water treatment simultaneously.In addition, utilize product of the present invention also can directly be made into the upper conversion of ultraviolet (UVC) diode that blue-ray LED excites (way: up-conversion luminescence powder and silica gel or mixed with resin is even, be coated in above LED chip, heating, drying, the blue-light excited upper conversion powder of LED transmitting sends UVC UV-light), because chip is little, can arbitrarily be combined into different shape, the place that can cannot use for 254nm mercury lamp.
The preparation method of up-conversion luminescent material of the present invention has sol-gel method and solid phase method.Sol-gel method can be prepared the material of nano-scale, and material prepared by solid phase method is micron order.The material of Nano grade can be prepared into the bacterium of water miscible particle in being used for disposing of sewage by the method such as coated.Material prepared by solid phase method and sol-gel method can be coated in glass or above transparent implements, can process the bacterium of its internal surface.
Referring to accompanying drawing 1, with blue light (300mW), LED excites sample of the present invention, has obtained the emmission spectrum of 200-450nm.Referring to accompanying drawing 2, sample of the present invention is encapsulated on blue-light LED chip, be made into the LED that sends out UV-light (UVC), and record its emmission spectrum, in figure, show, at UVC(200-300) locate 3 stronger emission peaks, this wave band is the useful range of sterilization.
Accompanying drawing explanation
Fig. 1 is the emmission spectrum of the sample prepared of the present invention under 300mW blue-ray LED excites.
Fig. 2 is encapsulated in gained emmission spectrum on blue-light LED chip by sample of the present invention.
Embodiment
Following examples describe the present invention in detail.Various raw material used in the present invention and items of equipment are conventional commercially available prod, all can be bought directly and be obtained by market.
Embodiment 1, visible-ultraviolet conversion luminous material
The chemical formula of up-conversion luminescent material of the present invention is: BaGd 2znO 5: 1%Er 3+, the meaning that wherein colon representative is adulterated, " 1%Er in formula 3+" representative Er 2o 3to have replaced 1% Gd 2o 3.
The liquid phase preparation of embodiment 2, up-conversion luminescent material
First, by the gadolinium sesquioxide Gd of 1.795g 2o 3(0.00495mol) with 0.019g Erbium trioxide Er 2o 3(0.00005mol) in mixture, add the dense HNO of 3ml 3add distilled water diluting to 60ml, fully, after reaction, obtain clear solution, reheat evaporation and remove unnecessary HNO 3, crystallization, makes its corresponding nitrate solid, adds 1.485g five water zinc nitrates (0.005mol) and 1.305g nitrate of baryta (0.005mol), is dissolved in 100ml deionized water, and heating magnetic agitation are to forming clear solution A;
Then the mixture of 4.2g citric acid and 2.5ml ethylene glycol is dissolved in the deionized water of 40ml, magnetic stirrer 30 minutes, to guarantee that all reagent is uniformly dispersed, forms solution B;
Finally, A solution is slowly added dropwise in B solution, and at 70 ℃ in magnetic stirring apparatus heated and stirred one hour above to forming homogeneous colloidal sol; 120 ℃ vacuum-drying 12-16 hour to forming gel, take out gel grind into powder; This powder is put into alumina cup and be then placed in box-type high-temperature furnace and be slowly warmed up to 300 ℃ and keep 2 hours, remove the organism in Gelatin powder; Then power-off cools to room temperature naturally, takes out powder and grinds, and then powder being put into box-type high-temperature furnace and calcine, and keeps two hours at 1200 ℃, then cools to natural room temperature; Take out, again grind, obtain sample powder.
The solid phase preparation of embodiment 3, up-conversion luminescent material
Analytically pure raw material, 0.987g BaCO 3, 1.795g Gd 2o 3, 0.019g Er 2o 3, 0.407gZnO; Raw material is ground in ball mill after 4 hours, 1400 ℃ of calcinations 3 hours, drop to room temperature; .Take out, again grind, obtain sample powder.
The purposes of embodiment 4, up-conversion luminescent material
A lot of with up-conversion luminescent material method for disinfection, according to different situations, can use diverse ways.Purposes is exemplified below:
For the bacterium in sewage, above-mentioned nanometer up-conversion can be prepared to coated silica improves water-soluble, externally link can with the organism of pending bacteriological action, after sample after preparation is put into pending sewage and be combined with bacterium, with blue-ray LED irradiation sewage, reach the object of killing bacterium.
For suppressing silo surface from mildewing, can directly the sample of preparing with solid phase method be coated in to silo inner side, can use blue-ray LED, incandescent light even, white light or xenon lamp irradiation reach the object of sterilization.
The bacterium of processing culture dish inside, can be coated in sample the internal surface of culture dish, sees through culture dish and is radiated on sample, the UVC uv disinfection that utilizes sample to send with blue-ray LED.
Foregoing description only proposes as the enforceable technical scheme of the present invention, not as the Single restriction condition to its technical scheme itself.

Claims (3)

1. visible-ultraviolet conversion luminous material B aGd 2znO 5: Er 3+purposes, the main body composition of this up-conversion luminescent material is that admixture rare earth element er makes in the oxide compound of barium, gadolinium, zinc, the mol ratio of each element is: barium: gadolinium: zinc: erbium: oxygen=1:1.98:1:0.02:5, is characterized in that: for converting blue-ray LED light to UV-light UVC for sterilization.
2. purposes according to claim 1, is characterized in that: the luminescent material converted in nano level of preparing with sol-gel method is prepared into water miscible particle for the treatment of the bacterium in water or organism, irradiates the object that reaches sterilization with blue-ray LED.
3. purposes according to claim 1, is characterized in that: described up-conversion luminescent material is coated in to transparent implements internal surface, irradiates implements reach the object of killing the inner bacterium of implements with blue-ray LED.
CN201310051102.1A 2013-02-05 2013-02-05 Visible-ultraviolet up-conversion luminescent material BaGd2ZnO5: Er3+, preparation method thereof and application thereof Expired - Fee Related CN103131412B (en)

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