CN104861978B - The nanocrystalline method of the five fluorine yttrium potassium that are co-doped with using waste phosphor powder synthesizing rare-earth metal - Google Patents

The nanocrystalline method of the five fluorine yttrium potassium that are co-doped with using waste phosphor powder synthesizing rare-earth metal Download PDF

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CN104861978B
CN104861978B CN201510306659.4A CN201510306659A CN104861978B CN 104861978 B CN104861978 B CN 104861978B CN 201510306659 A CN201510306659 A CN 201510306659A CN 104861978 B CN104861978 B CN 104861978B
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chloride
potassium
filter residue
yttrium
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CN104861978A (en
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王友法
熊真敏
丁奕丹
梅光军
李正
赵书文
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Wuhan University of Technology WUT
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Abstract

The invention discloses a kind of nanocrystalline method of the five fluorine yttrium potassium that are co-doped with of utilization waste phosphor powder synthesizing rare-earth metal, rare earth ion, potassium bifluoride, potassium hydroxide heating are dispersed in oleic acid, form homogeneous solution, after mixing under hot conditions, react, the five fluorine yttrium potassium that generation ytterbium, europium, erbium are co-doped with are nanocrystalline, by controlling factor grain-size size and the visual intensities such as the ratios of additive such as rear-earth-doped ionic species concentration, potassium resource, Fluorine source and oleic acid, it is achieved that ultraviolet light and near infrared light are to the conversion of multi-wavelength's visible ray.The pattern of products therefrom of the present invention is homogeneous, size is controlled, and luminous intensity is high, can be applicable to the fields such as opto-electronic device, electric source lighting, solar cell and biological fluorescent labelling.Its preparation technology is simple to operate, without the need for special installation, low cost and environmental protection, it is adaptable to the preparation of multiple rare earth up-conversion luminescence nanometer crystals and large-scale industrial production.

Description

The nanocrystalline method of the five fluorine yttrium potassium that are co-doped with using waste phosphor powder synthesizing rare-earth metal
Technical field
The present invention relates to a kind of solid waste resource recovery utilizes new technology, it is particularly suitable for rare-earth trichromatic fluorescent powder and gives up The green high level recycling of material, relates particularly to a kind of rare earth secondary resource and prepares the five fluorine yttrium potassium that rare earth metal is co-doped with The method of nano material.
Background technology
When rare-earth fluorescent upconverting fluorescent material refers to that material is excited by light, two-photon or multi-photon mechanism can be based on, The long-wave radiation of low photon energy is absorbed, launches the shortwave radiation of high photon energy, its essence is that a kind of anti-Stokes is sent out Light.In recent years, up-conversion luminescent material is in Solid State Laser, Three-dimensional Display, infrared imaging, solar cell, especially as one Plant novel fluorescence label to have broad application prospects in large biological molecule analysis, biomedical clinical field, receive wide General concern.Compared with conventional fluorescent label, up-conversion luminescence nanomaterial has that toxicity is low, luminous intensity is high, anti-light drift The advantages of white and light degradation, it is possible to achieve overdelicate biological detection.Simultaneously because the exciting light of up-conversion luminescence nanomaterial For infrared light, interference and the scattering optical phenomenon of biological sample AF can be avoided, so as to reduce detection background, improves noise Than, and infringement of the infrared light to biological tissue in detection process is also less.
Although upper conversion rare earth nano fluorescent material has unique optical property, but this nano material is in biological neck The application study development in domain is scarcely out of swaddling-clothes.Compared with other biological fluorescence probe material, however it remains particle size Larger, the problems such as dispersed heterogeneity.These problems directly affect conversion rare earth nano fluorescent material in biomedical sector Practical application.Preferably the size of upper converting biological marker material should be less than 50nm, smoothly enter in cell to carry out Mark.Efficiently apply in the extensive of biomedical sector to realize which, it is desirable to prepare smaller, dispersiveness more Good upper conversion rare earth nano fluorescent material.
With progressively accreditation of the market to rare-earth fluorescent up-conversion, relevant industries are increasing to its demand.Mesh Front the most frequently used rare-earth fluorescent up-conversion be with the fluoride of yttrium as host material, in view of preparation method technology limitation Property is so need the purity of raw material to reach more than 99.9% yittrium oxide or the crystalline hydrate of yttrium chloride in preparation process Or yttrium nitrate crystalline hydrate is ensureing fluorescent effect, and above-mentioned purity reaches more than 99.9% raw material basic source in dilute Tu Kuang, exploitation Rare Earth Mine expend mass energy and resource and bring series of environmental problems, and the rare earth strategy storage of China Amount is increasingly reduced, and government starts progressively to limit the exploitation of rare earth, and therefore above-mentioned raw materials price is increasingly expensive, ultimately results in and prepares The rare-earth fluorescent up-conversion cost for coming remains high, and this is for industrialization and the marketing of rare-earth fluorescent up-conversion It is a critical defect.
Rare earth is non-renewable grand strategy resource, because of the many-side characteristic such as its excellent light, electricity, magnetic, extensively should For multiple fields such as electronic information, metallurgical machinery, petrochemical industry, energy environment, defence and militaries.China is that rare earth resources are most rich Rich country, but with factors such as the rare earth consumption demand increase of the country of China, a large amount of cheap outlets and long-term gophers Impact, China's rare earth reserves fall sharply.And the learies of China's rare-earth products and material are increasingly increasing in recent years, such as only 2014 Year China rare-earth trichromatic fluorescent powder waste material yield just reaches 8000 tons, but does not obtain and rationally recycle.Therefore, for The environmentally friendly resource of rare-earth trichromatic fluorescent powder waste material is recycled, and with environmental protection and can increase substantially rare earth money Source utilization benefit.The electronic product display screens such as waste and old CRT TV, waste and old PDP TV, three-color fluorescent lamp, mobile phone all contain greatly Amount rare earth element, averagely per platform waste and old CRT TV containing about 8 grams of fluorescent material, per platform waste and old PDP TV containing about 30 grams of fluorescent material, per Three-color fluorescent lamp is containing about 3 grams of fluorescent material.Rare earth element yttrium and europium is mainly contained in Waste fluorescent powder, is in addition also contained The rare earth elements such as cerium, terbium, dysprosium.From protection rare earth resources, rare earth resources, environmental angle is recycled, reclaim in fluorescent material Rare earth resources are imperative.
CN104388087A discloses a kind of method that waste phosphor powder prepares rare-earth fluorescent up-conversion, the method Using ammonia precipitation process, together one oxalic acid secondary precipitation technique of liquid separation carries out rare earth leaching, but for denier in waste phosphor powder Lead, the element such as zinc fail effectively removing；Meanwhile, CN104388087A is adopted the mixing of anhydrous yttrium chloride and anhydrous Europium chloride Thing, MOH solid and MHF2 fine powder and the whole solid phase mixing of RmF3 or RmCl3 solid, are reacted, the nanocrystal for obtaining Spend greatly, more than 100nm, dispersion is not uniform enough for particle diameter, and rare earth ion fails all doping entrance host material lattices, causes Not excellent enough to rare-earth fluorescent up-conversion luminescent properties, limit its answering in fields such as biological medicine, solar cells With.
Meanwhile, K2YF5There is a stable physical and chemical performance, relatively low phonon energy, is that a kind of good up-conversion fluorescence is sent out Light matrix.While K2YF5Fluoride is a kind of up-and-coming newTL (thermoluminescence performance) material.For synthesis Eu3+、Yb3+、 Er3+Singly mix or be co-doped with K respectively2YF5Nanocrystalline technique and its corresponding luminosity research and report are seldom.Use waste phosphor powder Prepare Eu3+、Yb3+、Er3+Singly mix or be co-doped with K respectively2YF5Nanocrystalline technique there is no corresponding report.
Content of the invention
It is an object of the invention to provide a kind of rare earth metal three for preparing below particle diameter 20nm with waste phosphor powder as raw material The nanocrystalline method of the five fluorine yttrium potassium mixed.
The present invention solves the technical scheme that adopted of above-mentioned technical problem：Rare earth metal is prepared altogether using waste phosphor powder The nanocrystalline method of the five fluorine yttrium potassium mixed, it is characterised in that comprise the following steps：
1) weigh technique waste phosphor powder, fluorescent material leached by sulfuric acid and mixed in hydrochloric acid acid solution, using hydrogen peroxide as Cosolvent, obtains solution；
2) by step 1) in solution be put in centrifuge and carry out separation of solid and liquid, gained leachate ammoniacal liquor and extremely dilute sulphur Change potassium solution and extremely dilute potassium sulfate solution mixed solution adjusts pH 3.5-4, primary sedimentation is carried out, is filtered, obtains filtrate；
3) by step 2) in filtrate add ammoniacal liquor and extremely dilute potassium sulfide solution mixed solution, carry out secondary precipitation, tune PH 7-8, filters, obtains filter residue A and retain filtrate；
4) by step 3) in filtrate add ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution to mix Solution, carries out three precipitations, adjusts pH 8-9, filter, obtain filter residue B and retain filtrate；
5) by step 4) in filtrate add ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution to mix Solution, carries out four precipitations, adjusts pH 9-10, filter, obtain filter residue C；
6) by step 3) in filter residue A and step 4) in filter residue B and by step 5) in filter residue C's plus sulfuric acid and hydrochloric acid Mixed acid solution dissolving obtains pregnant solution, adds boiling water, stirs, is slowly added to oxalic acid solution, carries out five precipitations, ageing, mistake Filter, obtains filter residue D；
7) by step 6) in filter residue D high temperature sintering, after being cooled to room temperature, add KOH solution under the conditions of 100 DEG C of temperature 12h is kept, then carries out the mixture white powder that suction filtration obtains mainly containing yittrium oxide and europium oxide；It is subsequently adding hydrochloric acid solution It is completely dissolved, heating after the transparent clarification of solution is evaporated solution, obtains the mixture of anhydrous yttrium chloride and anhydrous Europium chloride；
8) weigh step 7) in the anhydrous yttrium chloride that obtains and anhydrous Europium chloride mixture solid, in atmosphere of inert gases Under protection, it is rapidly heated, maintains the temperature under conditions of 130 DEG C -200 DEG C, oleic acid is quickly dissolved in, until solution is transparent, cooling To room temperature, solution E is obtained；By a certain amount of KHF2Fine powder is rapidly heated, maintains the temperature under atmosphere of inert gases protection Under conditions of 120 DEG C -140 DEG C, oleic acid is quickly dissolved in, until solution is transparent, room temperature is cooled to, obtains solution F；Will be a certain amount of KOH solid is rapidly heated, maintains the temperature under conditions of 250 DEG C -300 DEG C under atmosphere of inert gases protection, anti-with oleic acid Should, until homogeneous liquid is formed, room temperature is cooled to, obtains liquid G；
9) by step 8) in the solution E that obtains and solution F and liquid G mix, under atmosphere of inert gases protection, It is rapidly heated, maintains the temperature under conditions of 330 DEG C -350 DEG C, certain time is reacted, the liquid for obtaining after completion of the reaction is carried out High speed centrifugation, the solidliquid mixture n-hexane for obtaining or acetone centrifugation supersound washing repeatedly, are placed in vacuum drying oven and dry, Then washed with boiling water repeatedly, dry, obtain final product the five fluorine yttrium potassium that rare earth metal is co-doped with nanocrystalline.
2nd, to prepare the five fluorine yttrium potassium that rare earth metal is co-doped with nanocrystalline for utilization waste phosphor powder according to claim 1 Method, it is characterised in that be also added with ytterbium chloride and chlorine in the mixture solid of described anhydrous yttrium chloride and anhydrous Europium chloride Change any one or the combinations thereof in erbium uniformly to be mixed.
By such scheme, step 2), step 4), step 5) in ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute sulfuric acid Potassium solution mixed solution be by by every 1000mL1:0.11g potassium sulfide solid is separately added in 1 ammoniacal liquor and 0.17g potassium sulfate is solid Body, appropriate stirring ageing, form uniform solution.
By such scheme, step 7) in anhydrous yttrium chloride and anhydrous Europium chloride mol ratio be 40:2.
By such scheme, KHF in yttrium chloride in solution E, the amount of total material of Europium chloride and solution F2Material The mol ratio of the amount of the material of the KOH solid added before amount and formation liquid G is 2:3:1.
By such scheme, step 8) in yttrium chloride, Europium chloride, ytterbium chloride, erbium chloride mol ratio be 76:3.8:16: 4.2；KHF in yttrium chloride, Europium chloride, ytterbium chloride, the amount of total material of erbium chloride and solution F in solution E2Material amount And the mol ratio of the amount of the material of the KOH solid added before forming liquid G is 2:3:1.
By such scheme, step 8) in yttrium chloride, Europium chloride, erbium chloride mol ratio be 40:2:2；Chlorination in solution E KHF in yttrium, Europium chloride, the amount of total material of erbium chloride and solution F2The amount of material and added before forming liquid G The mol ratio of the amount of the material of KOH solid is 2:3:1.
By such scheme, described mixture solid 1mol should be dissolved in 15mL oleic acid, and 1mmolKOH solid should be dissolved in 8mL oil Acid, 1mmolKHF2Powder should be dissolved in 7mL oleic acid.
Advantages of the present invention and feature:
1st, a part of raw material of the present invention is waste material, with low cost, simple easily obtain, this technological process is simple, Preparation condition is gentle, nothing secondary environmental pollution, compare conventional trifluoroacetic acid thermal decomposition method, this method need not discharge have poison gas Body, with low cost, the technology disclosed in CN104388087A is compared, impurity-eliminating effect more preferably, is conducive to synthesizing high-quality upper turn Change nanocrystalline, can realize rare-earth trichromatic fluorescent powder waste material rare earth elements green high level comprehensive utilization of resources and reduce dilute The preparation cost of native fluorescence up-conversion；
2nd, the present invention makees the wet chemistry method of solvent and surfactant using organic matters such as oleic acid, with KHF2Make Fluorine source, molten Liquid E and solution F and liquid G uniformly mix, and under the high temperature conditions, rear-earth-doped ion Effective Doping enters K2YF5Nanocrystalline Lattice, the five fluorine yttrium potassium that the rare earth metal three of formation below particle diameter 20nm is mixed are nanocrystalline, greatly improve materials synthesis efficiency, change It has been apt to the luminescent properties of material；
3rd, the nanocrystalline luminescent properties of the five fluorine yttrium potassium mixed of rare earth metal three that prepared by the present invention are good, and particle size meets life The application requirement in substance markers field, in addition to possessing good up-conversion luminescence performance, is also equipped with preferably lower conversion luminous Performance, effectively incorporates europium list and mixes the nanocrystalline function of five fluorine yttrium potassium that five fluorine yttrium potassium nano-probes and ytterbium, erbium be co-doped with, greatly Expanded the nanocrystalline application potential of five fluorine yttrium potassium that rare earth metal three mixes.
Description of the drawings
Fig. 1 is K prepared by embodiment 12Y0.76Eu0.038Er0.042Yb0.16F5Nanocrystalline XRD diffraction peak figure；
Fig. 2 is K prepared by embodiment 12Y0.76Eu0.038Er0.042Yb0.16F5Nanocrystalline Flied emission transmission electron microscope picture；
Fig. 3 is K prepared by embodiment 12Y0.76Eu0.038Er0.042Yb0.16F5Nanocrystalline in 980nm laser pumping 400nm The emissioning light spectrum of one 800nm wave band；
Fig. 4 is K prepared by embodiment 12Y0.76Eu0.038Er0.042Yb0.16F5Nanocrystalline under 375nm laser pumping The emissioning light spectrum of mono- 700nm wave band of 500nm.
Specific embodiment
With reference to the accompanying drawings and examples, further detailed description is carried out to the present invention, but this explanation will not be constituted Limitation of the present invention.
Embodiment 1
The nanocrystalline reality of five fluorine yttrium potassium that the rare earth metal three for below particle diameter 20nm being prepared as raw material with waste phosphor powder is mixed Apply mode as follows：
1) take 10g waste phosphor powder, plus sulfuric acid and mixed in hydrochloric acid acid solution (2mol/L sulfuric acid solution and 4mol/L hydrochloric acid molten Liquid by volume 1:1 is formulated) 100ml leaching fluorescent material, rotating speed is 1000rpm/min, plus the H of the 20% of 0.6ml2O2, temperature 70 DEG C 90 DEG C of degree, leaches 4h；
2) solution for leaching is put into separation of solid and liquid in centrifuge, obtains leachate, leachate ammoniacal liquor and extremely dilute sulfuration Potassium solution and extremely dilute potassium sulfate solution mixed solution adjust pH value in 3.5-4, and being then placed in centrifuge carries out separation of solid and liquid, Be removed most aluminium, iron, silicon, the filtrate of the impurity such as magnesium；Ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute sulfuric acid Potassium solution mixed solution be by by every 1000mL1:0.11g potassium sulfide solid is separately added in 1 ammoniacal liquor and 0.17g potassium sulfate is solid Body, appropriate stirring ageing, form uniform solution；
3) filtrate heating is boiled, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution mixed solution is added, it is secondary heavy to carry out Form sediment, pH 7-8 is adjusted, while hot suction filtration, obtain filter residue A and speckle with the quantitative filter paper of filter residue A and retain filtrate；
4) in filtrate, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution is added to mix molten Liquid, carries out three precipitations, adjusts pH 8-9, filter, obtain filter residue B and speckle with the quantitative filter paper of filter residue B and retain filtrate；
5) in filtrate, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution is added to mix molten Liquid, carries out four precipitations, adjusts pH 9-10, filter, obtain filter residue C and speckle with the quantitative filter paper of filter residue C；
6) by filter residue A, filter residue B, filter residue C together with speckle with respectively filter residue A, filter residue B, filter residue C quantitative filter paper add sulfuric acid and Mixed in hydrochloric acid acid solution (2mol/L sulfuric acid solution and 4mol/L hydrochloric acid solution by volume 1:1 is formulated) dissolving be enriched with Liquid, adds the boiling water of 120ml in rare-earth enrichment liquid, in 90 DEG C or so of temperature, under conditions of rotating speed is 1000rpm/min, The oxalic acid solution of 20g/L is slowly added to, after ageing 5-6h, five precipitations is carried out, oxalic rare earth precipitates is obtained, ageing, suction filtration, obtain To filter residue D and the quantitative filter paper for speckling with filter residue D；
7) filter residue D is put into crucible with the quantitative filter paper for speckling with filter residue D, calcination 2-4h, then washes at 950 DEG C, removes Decontamination calcium, finally calcination 1-2h at 850 DEG C again, obtains 1.9g containing 92.1% (mass ratio) Y2O3And 7.1%Eu2O3Mixing Rare earth, adds KOH solution to keep 12h under the conditions of 100 DEG C of temperature, then carries out suction filtration and obtains mainly containing yittrium oxide and europium oxide Mixture white powder；It is subsequently adding hydrochloric acid solution to be completely dissolved, heating after the transparent clarification of solution is evaporated solution, obtains To anhydrous yttrium chloride and anhydrous Europium chloride mixture (mol ratio of yttrium chloride and Europium chloride be 40:2)；
8) take 1mmol mol ratio and be about 76:3.8:16:4.2 yttrium chloride, Europium chloride, ytterbium chloride, erbium chloride hybrid solid It is added in 50mL three-neck flask, 15mL oleic acid is added, rotating speed is 4000rpm/min, by the solid mixture for obtaining lazy Property atmosphere protection under, be rapidly heated, maintain the temperature under conditions of 130 DEG C -200 DEG C, be quickly dissolved in oleic acid, until solution Transparent, room temperature is cooled to, obtains solution E；1.5mmolKHF2Powder is added in 50mL three-neck flask, adds 11mL oleic acid, Rotating speed is 4000rpm/min, under atmosphere of inert gases protection, is rapidly heated, maintains the temperature at 120 DEG C -140 DEG C of condition Under, oleic acid is quickly dissolved in, until solution is transparent, room temperature is cooled to, obtains solution F；0.5mmolKOH solid is added to 50mL In three-neck flask, 8mL oleic acid is added, under atmosphere of inert gases protection, be rapidly heated, maintain the temperature at 250 DEG C -300 DEG C Under conditions of, with elaidin reaction, until homogeneous liquid is formed, room temperature is cooled to, obtains liquid G；
9) solution E and solution F and liquid G are mixed, and under atmosphere of inert gases protection, are rapidly heated, are kept temperature Degree reacts certain time under conditions of 330 DEG C -350 DEG C, and the liquid for obtaining after completion of the reaction carries out high speed centrifugation, obtains Solidliquid mixture n-hexane or acetone centrifugation supersound washing repeatedly, are placed in vacuum drying oven and dry, it is therefore an objective to remove certain The oleic acid ligand of quantitative response its surface attachment, is then washed with boiling water repeatedly, is dried, it is therefore an objective to remove the pair inside reactant The accessory substances such as product chlorinated potassium, potassium fluoride, obtain final product that the five fluorine yttrium potassium that ytterbium, europium, erbium be co-doped with are nanocrystalline, and its molecular formula is K2Y0.76Eu0.038Er0.042Yb0.16F5.
Fig. 1 is K2YF5Eu3+、Yb3+、Er3+X-ray diffraction (XRD) figure.It can be seen that the x of synthetic sample is penetrated Line diffraction maximum position is substantially completely consistent with standard card. 16.39 °, 23.07 °, 28.01 °, 46.57 °, 47.05 °, Occur multiple KY at 55.15 ° respectively7F22Diffraction maximum, show to have crystalline phase KY in the middle of very small amount7F22Exist, forming K2YF5Brilliant After phase, very small amount K2YF5Crystalline phase is KY with KF reaction conversions7F22.Show that synthesized sample principal crystalline phase is K2YF5But have few Amount KY7F22Crystalline phase is present, using sample (310) face as the crystal face for calculating crystallite dimension, by the calculated sample of Scherrer formula The average diameter of product is 20nm.By TEM Fig. 2, it can be seen that the rear-earth-doped K for obtaining2YF5Nanocrystalline distribution is more uniform, is single Scattered nanocrystalline basic without agglomeration, statistical analysis understands that particle size is about 20nm.
K is excited with 980nm infrared excitation light2YF5Eu3+、Yb3+、Er3+Nanocrystalline, as can be seen from Figure 3, up-conversion fluorescence is launched Bands of a spectrum include tetra- bands of a spectrum of 378nm, 410nm, 544nm and 656nm, are respectively derived from Er3+Ion4G11/2→4I15/2、2H11/2→4I15/2、4S3/2→4I15/2With4F9/2→4I15/2Transition between energy level.As above-mentioned up-conversion fluorescence emission band mainly has Tetra- bands of a spectrum of 378nm, 410nm, 544nm and 656nm are from Er3+Transition between ion energy level, i.e. Eu3+Fail appearance 4fNConfiguration and 4fNdConfiguration transition between energy level.Due to Eu3+In K2YF5 lattice, content is less, if Eu3+With Er3+Between there is energy Transmission is measured, is then only possible to the presence of non-radiative energy transmission, it is possible to biography energy is penetrated by the non-good fortune that resonates or phonon aids in non-good fortune to penetrate Pass can or intersect the non-good fortune in her Henan penetrate biography can, finally non-good fortune penetrates loss.
K is excited with 375nm uv excitation light2YF5Eu3+、Yb3+、Er3+Nanocrystalline, as can be seen from Figure 4, down-conversion fluorescent is launched Bands of a spectrum include tri- bands of a spectrum of 540nm, 558nm and 709nm, and for the phenomenon of this ultraviolet down-conversion fluorescent, we can be from Er3+ And Yb3+Level structure analyze its reason, the ultraviolet light of 375nm can be by Er3+The electronics of ion from lowest energy level (4I15/2) excite To higher energy level (4G11/2), under the auxiliary of phonon and surface defect, relax towards through radiationless2H11/2With4S3/2Energy level, and By radiative relaxation generation green glow, and from4S3/2Energy level continues down that relaxation is extremely4F9/2Energy level, can then be produced by radiative relaxation red Light, due to2H11/2With4S3/2Under energy level and its4F9/2Level spacing larger (about 2900cm 1), radiationless relaxation rate Relatively low, in the case of Yb/Er is co-doped with, due to there is Yb3+And Er3+Between cross relaxation4F7/2→4F5/2(Yb3+) and2H11/2→2I11/2(Er3+) and weaken the transmitting of green glow, so red light emitting intensity is more obvious.
Embodiment 2
The nanocrystalline embodiment of five double-doped fluorine yttrium potassium of particle diameter europium, erbium is prepared as raw material with waste phosphor powder as follows：
1) take 10g waste phosphor powder, plus sulfuric acid and mixed in hydrochloric acid acid solution (2mol/L sulfuric acid solution and 4mol/L hydrochloric acid molten Liquid by volume 1:1 is formulated) 100ml leaching fluorescent material, rotating speed is 1000rpm/min, plus the H of the 20% of 0.6ml2O2, temperature 70 DEG C 90 DEG C of degree, leaches 4h；
2) solution for leaching is put into separation of solid and liquid in centrifuge, obtains leachate, leachate ammoniacal liquor and extremely dilute sulfuration Potassium solution and extremely dilute potassium sulfate solution mixed solution adjust pH value in 3.5-4, and being then placed in centrifuge carries out separation of solid and liquid, Be removed most aluminium, iron, silicon, the filtrate of the impurity such as magnesium；Ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute sulfuric acid Potassium solution mixed solution be by by every 1000mL1:0.11g potassium sulfide solid is separately added in 1 ammoniacal liquor and 0.17g potassium sulfate is solid Body, appropriate stirring ageing, form uniform solution；
3) filtrate heating is boiled, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution mixed solution is added, it is secondary heavy to carry out Form sediment, pH 7-8 is adjusted, while hot suction filtration, obtain filter residue A and speckle with the quantitative filter paper of filter residue A and retain filtrate；
4) in filtrate, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution is added to mix molten Liquid, carries out three precipitations, adjusts pH 8-9, filter, obtain filter residue B and speckle with the quantitative filter paper of filter residue B and retain filtrate；
5) in filtrate, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution is added to mix molten Liquid, carries out four precipitations, adjusts pH 9-10, filter, obtain filter residue C and speckle with the quantitative filter paper of filter residue C；
6) by filter residue A, filter residue B, filter residue C together with speckle with respectively filter residue A, filter residue B, filter residue C quantitative filter paper add sulfuric acid and Mixed in hydrochloric acid acid solution (2mol/L sulfuric acid solution and 4mol/L hydrochloric acid solution by volume 1:1 is formulated) dissolving be enriched with Liquid, adds the boiling water of 120ml in rare-earth enrichment liquid, in 90 DEG C or so of temperature, under conditions of rotating speed is 1000rpm/min, The oxalic acid solution of 20g/L is slowly added to, after ageing 5-6h, five precipitations is carried out, oxalic rare earth precipitates is obtained, ageing, suction filtration, obtain To filter residue D and the quantitative filter paper for speckling with filter residue D；
7) filter residue D is put into crucible with the quantitative filter paper for speckling with filter residue D, calcination 2-4h, then washes at 950 DEG C, removes Decontamination calcium, finally calcination 1-2h at 850 DEG C again, obtains 1.9g containing 92.1% (mass ratio) Y2O3And 7.1%Eu2O3Mixing Rare earth, adds KOH solution to keep 12h under the conditions of 100 DEG C of temperature, then carries out suction filtration and obtains mainly containing yittrium oxide and europium oxide Mixture white powder；It is subsequently adding hydrochloric acid solution to be completely dissolved, heating after the transparent clarification of solution is evaporated solution, obtains To anhydrous yttrium chloride and anhydrous Europium chloride mixture (mol ratio of yttrium chloride and Europium chloride be 40:2)；
8) take 1mmol mol ratio and be about 40:2:2 yttrium chloride, Europium chloride, erbium chloride hybrid solid are added to tri- neck of 50mL In flask, 15mL oleic acid is added, rotating speed is 4000rpm/min, and the solid mixture for obtaining is protected in atmosphere of inert gases Under, it is rapidly heated, maintains the temperature under conditions of 130 DEG C -200 DEG C, oleic acid is quickly dissolved in, until solution is transparent, is cooled to room Temperature, obtains solution E；1.5mmolKHF2Powder is added in 50mL three-neck flask, adds 11mL oleic acid, and rotating speed is 4000rpm/min, under atmosphere of inert gases protection, is rapidly heated, maintains the temperature under conditions of 120 DEG C -140 DEG C, quickly Oleic acid is dissolved in, until solution is transparent, room temperature is cooled to, obtains solution F；0.5mmolKOH solid is added to 50mL three-neck flask In, 8mL oleic acid is added, under atmosphere of inert gases protection, is rapidly heated, maintains the temperature under conditions of 250 DEG C -300 DEG C, With elaidin reaction, until homogeneous liquid is formed, room temperature is cooled to, obtains liquid G；
9) solution E and solution F and liquid G are mixed, and under atmosphere of inert gases protection, are rapidly heated, are kept temperature Degree reacts certain time under conditions of 330 DEG C -350 DEG C, and the liquid for obtaining after completion of the reaction carries out high speed centrifugation, obtains Solidliquid mixture n-hexane or acetone centrifugation supersound washing repeatedly, are placed in vacuum drying oven and dry, then washed with boiling water Repeatedly, dry, obtain final product five double-doped fluorine yttrium potassium of europium, erbium nanocrystalline.
Embodiment 3
The nanocrystalline embodiment of five fluorine yttrium potassium that europium list mixes is prepared as raw material with waste phosphor powder as follows：
1) take 10g waste phosphor powder, plus sulfuric acid and mixed in hydrochloric acid acid solution (2mol/L sulfuric acid solution and 4mol/L hydrochloric acid molten Liquid by volume 1:1 is formulated) 100ml leaching fluorescent material, rotating speed is 1000rpm/min, plus the H of the 20% of 0.6ml2O2, temperature 70 DEG C 90 DEG C of degree, leaches 4h；
2) solution for leaching is put into separation of solid and liquid in centrifuge, obtains leachate, leachate ammoniacal liquor and extremely dilute sulfuration Potassium solution and extremely dilute potassium sulfate solution mixed solution adjust pH value in 3.5-4, and being then placed in centrifuge carries out separation of solid and liquid, Be removed most aluminium, iron, silicon, the filtrate of the impurity such as magnesium；Ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute sulfuric acid Potassium solution mixed solution be by by every 1000mL1:0.11g potassium sulfide solid is separately added in 1 ammoniacal liquor and 0.17g potassium sulfate is solid Body, appropriate stirring ageing, form uniform solution；
3) filtrate heating is boiled, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution mixed solution is added, it is secondary heavy to carry out Form sediment, pH 7-8 is adjusted, while hot suction filtration, obtain filter residue A and speckle with the quantitative filter paper of filter residue A and retain filtrate；
4) in filtrate, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution is added to mix molten Liquid, carries out three precipitations, adjusts pH 8-9, filter, obtain filter residue B and speckle with the quantitative filter paper of filter residue B and retain filtrate；
5) in filtrate, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution is added to mix molten Liquid, carries out four precipitations, adjusts pH 9-10, filter, obtain filter residue C and speckle with the quantitative filter paper of filter residue C；
6) by filter residue A, filter residue B, filter residue C together with speckle with respectively filter residue A, filter residue B, filter residue C quantitative filter paper add sulfuric acid and Mixed in hydrochloric acid acid solution (2mol/L sulfuric acid solution and 4mol/L hydrochloric acid solution by volume 1:1 is formulated) dissolving be enriched with Liquid, adds the boiling water of 120ml in rare-earth enrichment liquid, in 90 DEG C or so of temperature, under conditions of rotating speed is 1000rpm/min, The oxalic acid solution of 20g/L is slowly added to, after ageing 5-6h, five precipitations is carried out, oxalic rare earth precipitates is obtained, ageing, suction filtration, obtain To filter residue D and the quantitative filter paper for speckling with filter residue D；
7) filter residue D is put into crucible with the quantitative filter paper for speckling with filter residue D, calcination 2-4h, then washes at 950 DEG C, removes Decontamination calcium, finally calcination 1-2h at 850 DEG C again, obtains 1.9g containing 92.1% (mass ratio) Y2O3And 7.1%Eu2O3Mixing Rare earth, adds KOH solution to keep 12h under the conditions of 100 DEG C of temperature, then carries out suction filtration and obtains mainly containing yittrium oxide and europium oxide Mixture white powder；It is subsequently adding hydrochloric acid solution to be completely dissolved, heating after the transparent clarification of solution is evaporated solution, obtains To anhydrous yttrium chloride and anhydrous Europium chloride mixture (mol ratio of yttrium chloride and Europium chloride be 40:2)；
8) take 1mmol mol ratio and be about 40:2 yttrium chloride, Europium chloride hybrid solid are added in 50mL three-neck flask, then 15mL oleic acid is added, rotating speed is 4000rpm/min, by the solid mixture for obtaining under atmosphere of inert gases protection, quick liter Temperature, maintains the temperature under conditions of 130 DEG C -200 DEG C, is quickly dissolved in oleic acid, until solution is transparent, is cooled to room temperature, obtains molten Liquid E；1.5mmolKHF2Powder is added in 50mL three-neck flask, adds 11mL oleic acid, and rotating speed is 4000rpm/min, lazy Property atmosphere protection under, be rapidly heated, maintain the temperature under conditions of 120 DEG C -140 DEG C, be quickly dissolved in oleic acid, until solution Transparent, room temperature is cooled to, obtains solution F；0.5mmolKOH solid is added in 50mL three-neck flask, 8mL oleic acid is added, Under atmosphere of inert gases protection, it is rapidly heated, maintains the temperature under conditions of 250 DEG C -300 DEG C, and elaidin reaction, until shape Become homogeneous liquid, room temperature is cooled to, obtain liquid G；
9) solution E and solution F and liquid G are mixed, and under atmosphere of inert gases protection, are rapidly heated, are kept temperature Degree reacts certain time under conditions of 330 DEG C -350 DEG C, and the liquid for obtaining after completion of the reaction carries out high speed centrifugation, obtains Solidliquid mixture n-hexane or acetone centrifugation supersound washing repeatedly, are placed in vacuum drying oven and dry, then washed with boiling water Repeatedly, dry, obtain final product the five fluorine yttrium potassium that europium list mixes nanocrystalline.
Embodiment 4
The nanocrystalline embodiment of five double-doped fluorine yttrium potassium of europium, ytterbium is prepared as raw material with waste phosphor powder as follows：
1) take 10g waste phosphor powder, plus sulfuric acid and mixed in hydrochloric acid acid solution (2mol/L sulfuric acid solution and 4mol/L hydrochloric acid molten Liquid by volume 1:1 is formulated) 100ml leaching fluorescent material, rotating speed is 1000rpm/min, plus the H of the 20% of 0.6ml2O2, temperature 70 DEG C 90 DEG C of degree, leaches 4h；
2) solution for leaching is put into separation of solid and liquid in centrifuge, obtains leachate, leachate ammoniacal liquor and extremely dilute sulfuration Potassium solution and extremely dilute potassium sulfate solution mixed solution adjust pH value in 3.5-4, and being then placed in centrifuge carries out separation of solid and liquid, Be removed most aluminium, iron, silicon, the filtrate of the impurity such as magnesium；Ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute sulfuric acid Potassium solution mixed solution be by by every 1000mL1:0.11g potassium sulfide solid is separately added in 1 ammoniacal liquor and 0.17g potassium sulfate is solid Body, appropriate stirring ageing, form uniform solution；
3) filtrate heating is boiled, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution mixed solution is added, it is secondary heavy to carry out Form sediment, pH 7-8 is adjusted, while hot suction filtration, obtain filter residue A and speckle with the quantitative filter paper of filter residue A and retain filtrate；
4) in filtrate, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution is added to mix molten Liquid, carries out three precipitations, adjusts pH 8-9, filter, obtain filter residue B and speckle with the quantitative filter paper of filter residue B and retain filtrate；
5) in filtrate, above-mentioned ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution is added to mix molten Liquid, carries out four precipitations, adjusts pH 9-10, filter, obtain filter residue C and speckle with the quantitative filter paper of filter residue C；
6) by filter residue A, filter residue B, filter residue C together with speckle with respectively filter residue A, filter residue B, filter residue C quantitative filter paper add sulfuric acid and Mixed in hydrochloric acid acid solution (2mol/L sulfuric acid solution and 4mol/L hydrochloric acid solution by volume 1:1 is formulated) dissolving be enriched with Liquid, adds the boiling water of 120ml in rare-earth enrichment liquid, in 90 DEG C or so of temperature, under conditions of rotating speed is 1000rpm/min, The oxalic acid solution of 20g/L is slowly added to, after ageing 5-6h, five precipitations are carried out, oxalic rare earth precipitates are obtained, ageing, suction filtration, Obtain filter residue D and speckle with the quantitative filter paper of filter residue D；
7) filter residue D is put into crucible with the quantitative filter paper for speckling with filter residue D, calcination 2-4h, then washes at 950 DEG C, removes Decontamination calcium, finally calcination 1-2h at 850 DEG C again, obtains 1.9g containing 92.1% (mass ratio) Y2O3Mix with 7.1%Eu2O3 Rare earth, adds KOH solution to keep 12h under the conditions of 100 DEG C of temperature, then carries out suction filtration and obtains mainly containing yittrium oxide and europium oxide Mixture white powder；It is subsequently adding hydrochloric acid solution to be completely dissolved, heating after the transparent clarification of solution is evaporated solution, obtains To anhydrous yttrium chloride and anhydrous Europium chloride mixture (mol ratio of yttrium chloride and Europium chloride be 40:2)；
8) take 1mmol mol ratio and be about 76:3.8:16 yttrium chloride, Europium chloride, ytterbium chloride hybrid solid are added to 50mL In three-neck flask, 15mL oleic acid is added, rotating speed is 4000rpm/min, by the solid mixture for obtaining in atmosphere of inert gases Under protection, it is rapidly heated, maintains the temperature under conditions of 130 DEG C -200 DEG C, oleic acid is quickly dissolved in, until solution is transparent, cooling To room temperature, solution E is obtained；1.5mmolKHF2Powder is added in 50mL three-neck flask, adds 11mL oleic acid, and rotating speed is 4000rpm/min, under atmosphere of inert gases protection, is rapidly heated, maintains the temperature under conditions of 120 DEG C -140 DEG C, quickly Oleic acid is dissolved in, until solution is transparent, room temperature is cooled to, obtains solution F；0.5mmolKOH solid is added to 50mL three-neck flask In, 8mL oleic acid is added, under atmosphere of inert gases protection, is rapidly heated, maintains the temperature under conditions of 250 DEG C -300 DEG C, With elaidin reaction, until homogeneous liquid is formed, room temperature is cooled to, obtains liquid G；
9) solution E and solution F and liquid G are mixed, and under atmosphere of inert gases protection, are rapidly heated, are kept temperature Degree reacts certain time under conditions of 330 DEG C -350 DEG C, and the liquid for obtaining after completion of the reaction carries out high speed centrifugation, obtains Solidliquid mixture n-hexane or acetone centrifugation supersound washing repeatedly, are placed in vacuum drying oven and dry, then washed with boiling water Repeatedly, dry, obtain final product the five fluorine yttrium potassium that ytterbium, europium, erbium be co-doped with nanocrystalline.

Claims (3)

1. prepare the nanocrystalline method of five fluorine yttrium potassium that rare earth metal is co-doped with using waste phosphor powder, it is characterised in that include with Lower step：
1) technique waste phosphor powder is weighed, fluorescent material is leached by sulfuric acid and mixed in hydrochloric acid acid solution, using hydrogen peroxide as hydrotropy Agent, obtains solution；
2) by step 1) in solution be put in centrifuge and carry out separation of solid and liquid, gained leachate ammoniacal liquor and extremely dilute potassium sulfide Solution and extremely dilute potassium sulfate solution mixed solution adjust pH 3.5-4, carry out primary sedimentation, filter, obtain filtrate；
3) by step 2) in filtrate add ammoniacal liquor and extremely dilute potassium sulfide solution mixed solution, carry out secondary precipitation, tune pH 7- 8, filter, obtain filter residue A and retain filtrate；
4) by step 3) in filtrate add ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution mixed solution, Three precipitations are carried out, pH 8-9 is adjusted, filter, obtain filter residue B and retain filtrate；
5) by step 4) in filtrate add ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate solution mixed solution, Four precipitations are carried out, pH 9-10 is adjusted, filter, obtain filter residue C；
6) by step 3) in filter residue A and step 4) in filter residue B and by step 5) in filter residue C's plus sulfuric acid and mixed in hydrochloric acid Acid solution dissolving obtains pregnant solution, adds boiling water, stirs, is slowly added to oxalic acid solution, carries out five precipitations, is aged, filters, obtain To filter residue D；
7) by step 6) in filter residue D high temperature sintering, after being cooled to room temperature, add KOH solution to keep under the conditions of 100 DEG C of temperature 12h, then carries out the mixture white powder that suction filtration obtains mainly containing yittrium oxide and europium oxide；Be subsequently adding hydrochloric acid solution by its It is completely dissolved, heating after the transparent clarification of solution is evaporated solution, obtains the mixture of anhydrous yttrium chloride and anhydrous Europium chloride；Anhydrous The mol ratio of yttrium chloride and anhydrous Europium chloride is 40:2；
8) weigh step 7) in the anhydrous yttrium chloride that obtains and anhydrous Europium chloride mixture solid, described anhydrous yttrium chloride and Any one or combinations thereof in ytterbium chloride and erbium chloride is also added with the mixture solid of anhydrous Europium chloride to carry out Uniform mixing, under atmosphere of inert gases protection, is rapidly heated, maintains the temperature under conditions of 130 DEG C -200 DEG C, be quickly dissolved in Oleic acid, until solution is transparent, is cooled to room temperature, obtains solution E；By a certain amount of KHF2Fine powder is protected in atmosphere of inert gases Under, it is rapidly heated, maintains the temperature under conditions of 120 DEG C -140 DEG C, oleic acid is quickly dissolved in, until solution is transparent, is cooled to room Temperature, obtains solution F；By a certain amount of KOH solid under atmosphere of inert gases protection, it is rapidly heated, maintains the temperature at 250 DEG C -300 Under conditions of DEG C, with elaidin reaction, until homogeneous liquid is formed, room temperature is cooled to, obtains liquid G；Described yttrium chloride, chlorination Europium, ytterbium chloride, the mol ratio of erbium chloride are 76:3.8:16:4.2；Yttrium chloride, Europium chloride in solution E, ytterbium chloride, erbium chloride The amount of total material and solution F in KHF2The amount of material and the material of KOH solid added before forming liquid G amount Mol ratio be 2:3:1 or described yttrium chloride, Europium chloride, erbium chloride mol ratio be 40:2:2；Chlorination in solution E KHF in yttrium, Europium chloride, the amount of total material of erbium chloride and solution F2The amount of material and added before forming liquid G The mol ratio of the amount of the material of KOH solid is 2:3:1；
9) by step 8) in the solution E that obtains and solution F and liquid G mix, under atmosphere of inert gases protection, quickly Heat up, maintain the temperature under conditions of 330 DEG C -350 DEG C, certain time is reacted, the liquid for obtaining after completion of the reaction is carried out at a high speed Centrifugation, the solidliquid mixture n-hexane for obtaining or acetone centrifugation supersound washing repeatedly, are placed in vacuum drying oven and dry, then Washed with boiling water repeatedly, dry, obtain final product the five fluorine yttrium potassium that rare earth metal is co-doped with nanocrystalline.
2. utilization waste phosphor powder according to claim 1 prepares the nanocrystalline side of five fluorine yttrium potassium that rare earth metal is co-doped with Method, it is characterised in that step 2), step 4), step 5) in ammoniacal liquor and extremely dilute potassium sulfide solution and extremely dilute potassium sulfate molten Liquid mixed solution be by by every 1000mL1:0.11g potassium sulfide solid and 0.17g potassium sulfate solid is separately added in 1 ammoniacal liquor, Appropriate stirring ageing, forms uniform solution.
3. utilization waste phosphor powder according to claim 1 prepares the nanocrystalline side of five fluorine yttrium potassium that rare earth metal is co-doped with Method, it is characterised in that described mixture solid 1mmol should be dissolved in 15mL oleic acid, 1mmolKOH solid should be dissolved in 8mL oleic acid, 1mmolKHF2Powder should be dissolved in 7mL oleic acid.
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CN104327855A (en) * 2014-11-21 2015-02-04 武汉理工大学 Method for preparing rare-earth doped potassium yttrium fluoride up-conversion luminescence nano material
CN104388087A (en) * 2014-11-21 2015-03-04 武汉理工大学 Method for preparing rare-earth fluorescent up-conversion material by use of waste fluorescent powder

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* Cited by examiner, † Cited by third party
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WO2007078262A1 (en) * 2006-01-06 2007-07-12 National University Of Singapore Method of preparing nano-structured material(s) and uses thereof
CN103087705A (en) * 2013-01-16 2013-05-08 大连理工大学 High-strength rare earth-doped up-conversion luminescence nanometer material and preparation method thereof
CN104327855A (en) * 2014-11-21 2015-02-04 武汉理工大学 Method for preparing rare-earth doped potassium yttrium fluoride up-conversion luminescence nano material
CN104388087A (en) * 2014-11-21 2015-03-04 武汉理工大学 Method for preparing rare-earth fluorescent up-conversion material by use of waste fluorescent powder

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