CN106520121B - The preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor - Google Patents
The preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor Download PDFInfo
- Publication number
- CN106520121B CN106520121B CN201610953772.6A CN201610953772A CN106520121B CN 106520121 B CN106520121 B CN 106520121B CN 201610953772 A CN201610953772 A CN 201610953772A CN 106520121 B CN106520121 B CN 106520121B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- doped
- gadolinium
- oxysulfate
- calcining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- MCVAAHQLXUXWLC-UHFFFAOYSA-N [O-2].[O-2].[S-2].[Gd+3].[Gd+3] Chemical compound [O-2].[O-2].[S-2].[Gd+3].[Gd+3] MCVAAHQLXUXWLC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract 2
- 239000001301 oxygen Substances 0.000 title abstract 2
- 239000000843 powder Substances 0.000 claims abstract description 83
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 68
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 27
- -1 rare earth ion Chemical class 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910005563 Gd2O2SO4 Inorganic materials 0.000 claims abstract description 11
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 55
- 150000002910 rare earth metals Chemical class 0.000 claims description 48
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 40
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 claims description 22
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 21
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 229910002617 Gd(NO3)3·6H2O Inorganic materials 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910009500 Y2O2SO4 Inorganic materials 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7781—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
- C09K11/7789—Oxysulfides
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
A kind of preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor, belongs to materials science field.Method includes the following steps: (1) is by Gd (NO3)3·6H2O、Yb(NO3)3·6H2O and Ln (NO3)3·6H2O mixing, adds deionized water, obtains RE (NO3)3Solution；(2) ammonium sulfate is dissolved in RE (NO3)3Solution stirring, continues to stir, and ammonium hydroxide is added, and adjusts pH value, obtains suspension；(3) by suspension, at 100~150 DEG C, 1~72h of hydro-thermal reaction, cooled to room temperature obtains reaction product；(4) by reaction product centrifuge separation, cleaning, drying, white powder presoma is obtained；(5) by white powder presoma, rare earth ion doped Gd is made in calcining2O2S or Gd2O2SO4Up-conversion phosphor.This method efficiently solves the use in conventional method containing sulfur feedstock and the discharge of harmful side product, is a kind of environmentally protective technology of preparing.
Description
Technical Field
The invention belongs to the field of material science, and particularly relates to a preparation method of rare earth doped gadolinium oxysulfide and gadolinium oxysulfate upconversion fluorescent powder.
Background
The up-conversion luminescent material has unique capability of converting long-wave radiation into short-wave radiation, and is widely applied to the fields of up-conversion lasers, dye-sensitized solar cells, drug transportation, biological fluorescent marking, infrared anti-counterfeiting and the like. The current upconversion system with higher efficiency is fluoride (e.g., NaYF)4: Yb/Er), fluoride has the advantages of low phonon energy, high up-conversion efficiency and the like. However, the fluoride raw material is relatively toxic, and the mass production and practical application of the fluoride up-conversion luminescent material are greatly limited due to the defect. Although the rare earth oxide up-conversion system is non-toxic, the phonon energy is high, and the up-conversion efficiency is low. Therefore, the method has higher practical application value in exploring other types of up-conversion systems which are non-toxic and have lower phonon energy.
Gadolinium oxysulfide (Gd)2O2S) the phonon energy is lower and the chemical stability is good. Thus, there have been studies on the Yb/Ho and Yb/Er doping pairs in Gd2O2The upconversion luminescence property in S is found to be good. However, the problems existing at present are as follows: (1) other doping pairs of Yb/Tm and the like are in Gd2O2The up-conversion luminescence in S is reported; (2) the preparation of the compounds inevitably uses sulfur-containing raw materials with harmful environment or relates to sulfur-containing byproducts with harmful environment.
Gadolinium oxysulfate (Gd)2O2SO4) Have received much attention from researchers, primarily as down-converting luminescent matrices. Recent researchers have found that the Yb/Er doping pair is in Y2O2SO4Can show good up-conversion luminescence performance. Thus, Gd is also a compound of this class2O2SO4Is expected to exhibit good up-conversion luminescence property, and is associated with Y2O2SO4In contrast, Gd2O2SO4Is more covalent than Y2O2SO4While Gd2O2SO4Gd in (2)3+The fluorescent material has a half-full 4f shell layer, and the two characteristics enable the system to be expected to show better luminescence performance. The traditional preparation method of the compound is the same as Gd2O2Similar to the preparation method of S, the problems of using sulfur-containing raw materials harmful to the environment or involving the discharge of sulfur-containing byproducts harmful to the environment exist, and researchers find a novel sulfate type rare earth layered hydroxide Gd2(OH)4SO4·nH2O, and calcining the compound in air to prepare Gd in a green way2O2SO4But Gd2(OH)4SO4·nH2The preparation method of O is mainly limited to the precipitation method. The product obtained by the precipitation method is irregular aggregate. Calcined product Gd2O2SO4Morphology of (1) and its precursor Gd2(OH)4SO4·nH2The morphology of O is closely related. Therefore, the green preparation of Gd cannot be realized at present2O2SO4And meanwhile, the shape of the material is effectively regulated and controlled. And precipitating agents such as hexamethylenetetramine (HMT, (CH)2)6N4) Has the defects of slow hydrolysis at room temperature, low yield of the bottom precipitation reaction due to formaldehyde and derivatives thereof generated in the air at high temperature and the like. Due to Gd2(OH)4SO4·nH2The crystal water in the O is directly coordinated with the rare earth ions, so whether the crystal water in the structure directly influences the crystal structure characteristics of the product and the coordination mode of a coordination polyhedron taking the rare earth ions as the center.
Disclosure of Invention
Aiming at the existing preparation of rare earth doped Gd2O2The invention provides a preparation method of rare earth doped gadolinium oxysulfide upconversion fluorescent powder, which solves the problem of using sulfur-containing raw materials with harmful environment in the S technical routePreparing rare earth doped Gd by hydrothermal method2(OH)4SO4·nH2O and Gd2(OH)4SO4Two types of precursors, and the molar ratio of RE/S and RE in the two types of precursors2O2The two compounds are calcined in reducing atmosphere to prepare rare earth doped Gd in green2O2And S. In the preparation process of the precursor, mild ammonium sulfate is used as a sulfur source, and a byproduct in the calcination process is only water vapor. The method effectively solves the problems of the use of the sulfur-containing raw material which is harmful to the environment and the discharge of harmful byproducts in the conventional method, and is a green and environment-friendly preparation technology.
Aiming at the existing preparation of rare earth doped Gd2O2SO4The invention provides a preparation method of rare earth doped gadolinium oxysulfate upconversion fluorescent powder, which is used for preparing rare earth doped Gd by a hydrothermal method2(OH)4SO4·nH2O rare earth doped Gd of uniform agglomerated spheres by calcining the compound in air2O2SO4The preparation of the compound is also provided with a sulfate type rare earth layered hydroxide Gd doped with the rare earth of the quasi-hexagonal micron sheet2(OH)4SO4The compound is calcined in the air to prepare the rare earth doped Gd of the quasi-hexagonal micron sheet2O2SO4. The technical route realizes green preparation of rare earth doped Gd2O2SO4And meanwhile, the morphology of the material is effectively regulated and controlled.
The invention relates to a preparation method of rare earth doped gadolinium oxysulfide and gadolinium oxysulfate upconversion fluorescent powder, which comprises the following steps:
(1) gd (NO)3)3·6H2O、Yb(NO3)3·6H2O and Ln (NO)3)3·6H2O mixing, adding deionized water, and placing in a chamberStirring at warm temperature to obtain RE (NO)3)3A solution;
wherein, in terms of molar ratio, Gd3+∶Yb3+∶Ln3+＝(90～97)∶(5～2)∶(5～1)；
The Ln is one of Ho, Er or Tm;
said RE3+Is Gd3+、Yb3+And Ln3+Mixed ions of (2);
(2) dissolving ammonium sulfate in RE (NO)3)3Stirring the solution uniformly, then continuing stirring, adding ammonia water, and adjusting the pH value to 7.0-10.0 to obtain a suspension;
wherein, the molar ratio of sulfate radical to RE is3+＝(1～5)∶(2～1)；
(3) Transferring the suspension into a reaction kettle, carrying out hydrothermal reaction for 1-72 h at 100-150 ℃, taking out after the reaction is finished, and naturally cooling to room temperature to obtain a reaction product;
(4) centrifugally separating, cleaning and drying the reaction product to obtain a white powder precursor (Gd, Yb, Ln)2(OH)4SO4·nH2O, wherein n is 0 or 1.9-2.2;
(5) calcining the white powder precursor to obtain the rare earth ion doped Gd2O2S and Gd2O2SO4An up-conversion phosphor; wherein the calcination parameters are (a) or (b):
(a) calcining in air at 800-1000 deg.c for 0.5-4 hr to obtain RE ion doped Gd2O2SO4The up-conversion fluorescent powder is rare earth oxysulfate (Gd, Yb, Ln)2O2SO4；
(b) The calcining environment is a reducing atmosphere, the calcining temperature is 800-1200 ℃, the calcining time is 0.5-4 h, and the prepared rare earth ion doped Gd2O2The S up-conversion fluorescent powder is rare earth oxysulfide (Gd, Yb, Ln)2O2S。
Wherein,
said RE (NO)3)3RE of solution3+The concentration is 0.05-0.5 mol/L;
in the step (2), the stirring is carried out for 15-20 min.
In the step (2), ammonia water is added by adopting a dropwise adding method.
In the step (4), the centrifugal separation is to centrifuge the reaction product, remove the supernatant, and process the precipitate obtained by centrifugation;
in the step (4), the cleaning is carried out for three times by adding water, and is carried out for one time by adding absolute ethyl alcohol, so as to remove impurities in the white powder precursor;
in the step (4), the drying is carried out at a temperature of 50-80 ℃.
In the step (4), the white powder precursor is sulfate type rare earth layered hydroxide, the morphology of the white powder precursor is one of agglomerated spheres or quasi-hexagonal micron sheets, and the morphology of the white powder precursor can be regulated and controlled by adjusting process parameters such as pH, reaction temperature, reaction time, calcination temperature and the like, so that the morphology of the fluorescent powder can be controlled and designed.
In the step 5, the reducing atmosphere is H2And N2Mixing in proportion, wherein H25-100% of volume percentage and the balance of N2。
The invention relates to a preparation method of rare earth doped gadolinium oxysulfide and gadolinium oxysulfate upconversion fluorescent powder, which comprises the following chemical reaction formula:
RE2(OH)4SO4·nH2O→RE2(OH)4SO4+nH2O (3)
RE2(OH)4SO4→RE2O2SO4+2H2O (4)
RE2O2SO4+4H2→RE2O2S+4H2O (5)
the chemical reaction formula for preparing the rare earth oxysulfate is as follows:
RE2(OH)4SO4·nH2O→RE2(OH)4SO4+nH2O (3)
RE2(OH)4SO4→RE2O2SO4+2H2O (4)
the rare earth ion doped Gd of the invention2O2S and Gd2O2SO4Compared with the prior art, the preparation method of the up-conversion fluorescent powder has the characteristics and beneficial effects that:
gd doped with rare earth2(OH)4SO4And Gd2(OH)4SO4·nH2Molar ratio RE/S to RE in O2O2The S is completely consistent, the two compounds are calcined in a reducing atmosphere, and the rare earth doped Gd is prepared in an environment-friendly way2O2S, effectively solves the problem of rare earth doped Gd2O2S the problems related to the use of sulfur-containing raw materials harmful to the environment or the discharge of harmful products in the conventional preparation method are inevitable.
By utilizing a hydrothermal synthesis route and by modulating reaction parameters such as pH value, temperature and reaction time, the rare earth doped Gd of the quasi-hexagonal micron sheet plate with uniform size or good dispersibility is prepared2O2SO4The green preparation is realized, and the appearance is effectively regulated and controlled.
Drawings
FIG. 1 is a process flow diagram of the present invention for preparing rare earth doped gadolinium oxysulfide and gadolinium oxysulfate upconversion phosphor;
FIG. 2 shows sulfate type rare earth layered hydroxides (Gd, Yb, Ln) prepared in examples 1 to 6 of the present invention2(OH)4SO4·nH2An XRD pattern of O, wherein (a) was obtained from example 1 and example 2, (b) was obtained from example 3 and example 4, and (c) was obtained from example 5 and example 6;
FIG. 3 shows sulfate type rare earth layered hydroxides (Gd, Yb, Ln) prepared in examples 1 to 6 of the present invention2(OH)4SO4·nH2SEM topography of O, wherein (a) was obtained from example 1 and example 2, (b) was obtained from example 3 and example 4, and (c) was obtained from example 5 and example 6;
FIG. 4 shows (Gd, Yb, Ln) prepared in example 1, example 3 and example 5 of the present invention2O2SO4An XRD pattern of the upconversion phosphor, wherein (a) was obtained from example 1, (b) was obtained from example 3, and (c) was obtained from example 5;
FIG. 5 shows (Gd, Yb, Ln) prepared in example 1, example 3 and example 5 of the present invention2O2SO4SEM topography for upconversion phosphors, wherein (a) was prepared from example 1, (b) was prepared from example 3, and (c) was prepared from example 5;
FIG. 6 shows (Gd, Yb, Ln) prepared in example 2, example 4 and example 6 of the present invention2O2An XRD pattern of the conversion phosphor on S, wherein (a) was obtained from example 2, (b) was obtained from example 4, and (c) was obtained from example 6;
FIG. 7 shows (Gd, Yb, Ln) prepared in example 2, example 4 and example 6 of the present invention2O2An SEM topography for the converted phosphor on S, wherein (a) was obtained from example 2, (b) was obtained from example 4, and (c) was obtained from example 6;
FIG. 8 shows (Gd, Yb, Ln) prepared in examples 7 to 12 of the present invention2(OH)4SO4Wherein (a) is obtained from example 7 and example 8, (b) is obtained from example 9 and example 10, and (c) is obtained from example 11 and example 12;
FIG. 9 shows (Gd, Yb, Ln) prepared in examples 7 to 12 of the present invention2(OH)4SO4Wherein (a) was obtained from example 7 and example 8, (b) was obtained from example 9 and example 10, and (c) was obtained from example 11 and example 12;
FIG. 10 shows (Gd, Yb, Ln) prepared in example 7, example 9 and example 11 of the present invention2O2SO4An XRD pattern of the upconversion phosphor, wherein (a) was obtained from example 7, (b) was obtained from example 9, and (c) was obtained from example 11;
FIG. 11 shows (Gd, Yb, Ln) prepared in example 7, example 9 and example 11 of the present invention2O2SO4SEM topography for upconversion phosphors, wherein (a) was prepared from example 7, (b) was prepared from example 9, and (c) was prepared from example 11;
FIG. 12 shows (Gd, Yb, Ln) prepared in example 7, example 9 and example 11 of the present invention2O2SO4An upconversion emission spectrum of the upconversion phosphor, wherein (a) is obtained from example 7, (b) is obtained from example 9, and (c) is obtained from example 11;
FIG. 13 shows (Gd, Yb, Ln) produced in example 8, example 10 and example 12 of the present invention2O2An XRD pattern of the conversion phosphor on S, wherein (a) was obtained from example 8, (b) was obtained from example 10, and (c) was obtained from example 12;
FIG. 14 shows (Gd, Yb, Ln) produced in example 8, example 10 and example 12 of the present invention2O2An SEM topography for the converted phosphor on S, wherein (a) was obtained from example 8, (b) was obtained from example 10, and (c) was obtained from example 12;
FIG. 15 shows (Gd, Yb, Ln) produced in example 8, example 10 and example 12 of the present invention2O2An up-conversion emission spectrum of an S up-conversion phosphor, wherein (a) was obtained from example 8, (b) was obtained from example 10, and (c) was obtained from example 12;
Detailed Description
The chemical reagents used in the following examples are analytical grade products;
the following examples were subjected to XRD analysis using a RINT2200V/PC type X-ray diffractometer manufactured by Rigaku corporation, Japan; observing the morphology (SEM) of the sample by using a S-5000 type field emission scanning electron microscope (FE-SEM) of Hitachi corporation of Japan;
the upconversion luminescence performance of the sample was measured using an FP-6500 type fluorescence spectrophotometer manufactured by JASCO of Japan, and a 978nm near infrared laser diode (KS3-12322-105, Kyoto Kaprilin optical technology Co., Ltd.) was used as an excitation light source.
The inner container of the hydrothermal reaction kettle is made of polytetrafluoroethylene with the specification of 100ml, the steel sleeve is made of stainless steel, the oven is an electronic temperature control oven, and the temperature difference is less than 1 ℃; the high-temperature furnace is a tubular furnace, and the rated temperature is 1550 ℃;
the determination of the crystal water content of the sample in the invention is determined according to thermogravimetric analysis (TGA), and the type of the adopted thermogravimetric analysis instrument is as follows: model STA449F3 thermogravimetric analyzer of Netzsch, Germany.
The present invention will be described in further detail with reference to the following examples, which are preferred embodiments of the present invention.
Example 1
A preparation method of rare earth doped gadolinium oxysulfate upconversion fluorescent powder comprises the following steps:
(1) gd (NO)3)3·6H2O、Yb(NO3)3·6H2O and Ho (NO)3)3·6H2O, adding deionized water, stirring at room temperature to obtain RE3+The ion concentration was 0.05mol/L RE (NO)3)3A solution;
wherein, in terms of molar ratio, Gd3+∶Yb3+∶Ho3+＝90∶5∶5；
(2) 0.4g of ammonium sulfate was dissolved in 0.05mol/L RE (NO)3)3In solution, RE (NO)3)3Stirring the solution for 20min at room temperature with the volume of 60mL, then continuously stirring and dropwise adding ammonia water, and adjusting the pH value to 7.0 to obtain a suspension;
wherein, the molar ratio of sulfate radical to RE is3+＝1∶1；
(3) Transferring the suspension into a reaction kettle, carrying out hydrothermal reaction for 72 hours at 100 ℃, taking out after the reaction is finished, and naturally cooling to room temperature to obtain a reaction product;
(4) centrifuging reaction product, washing with water for three times, washing with anhydrous ethanol for one time, and oven drying at 70 deg.CTo obtain white powder precursor-sulfate type rare earth layered hydroxide (Gd)0.90Yb0.05Ho0.05)2(OH)4SO4·nH2O (n ═ 1.9) and having an XRD pattern as shown in fig. 2 (a); the morphology of the material is agglomerated balls, and the size of the agglomerated balls is 80-110 mu m, as shown in figure 3 (a);
(5) calcining the white powder precursor in air at 800 deg.C for 1h to obtain rare earth oxysulfate (Gd)0.90Yb0.05Ho0.05)2O2SO4The XRD of the up-conversion phosphor is shown in figure 4(a), and the product can be seen to be pure phase; the morphology of the precursor is similar to that of the precursor, the precursor is an agglomerated sphere, and the diameter of the agglomerated sphere is 80-110 mu m, as shown in figure 5 (a).
Example 2
A preparation method of rare earth doped gadolinium oxysulfide up-conversion fluorescent powder comprises the following steps:
the steps (1), (2), (3) and (4) are the same as those in example 1;
(5) placing the white powder precursor in H2And N2Mixed gas (volume ratio, H)2∶N2Calcining at 800 deg.C for 1h in 50: 50) atmosphere to obtain rare earth oxysulfide (Gd)0.90Yb0.05Ho0.05)2O2The XRD of the S fluorescent powder is shown in figure 6(a), and the product can be seen to be pure phase; the morphology of the precursor is similar to that of the precursor, the precursor is an agglomerated sphere, and the diameter of the agglomerated sphere is 80-110 mu m, as shown in FIG. 7 (a).
Example 3
A preparation method of rare earth doped gadolinium oxysulfate upconversion fluorescent powder comprises the following steps:
(1) gd (NO)3)3·6H2O、Yb(NO3)3·6H2O and Er (NO)3)3·6H2O, adding deionized water, stirring at room temperature to obtain RE3+The ion concentration was 0.5mol/L RE (NO)3)3A solution;
wherein, in terms of molar ratio, Gd3+∶Yb3+∶Er3+＝97∶2∶1；
(2) 4g of ammonium sulfate was dissolved in 0.5mol/L RE (NO)3)3In solution, RE (NO)3)3Stirring the solution for 20min at room temperature with the volume of 60mL, then continuously stirring and dropwise adding ammonia water, and adjusting the pH value to 7.0 to obtain a suspension;
wherein, the molar ratio of sulfate radical to RE is3+＝1∶1；
(3) Transferring the suspension into a reaction kettle, carrying out hydrothermal reaction for 1h at 100 ℃, taking out after the reaction is finished, and naturally cooling to room temperature to obtain a reaction product;
(4) centrifugally separating the reaction product, adding water to wash for three times, adding absolute ethyl alcohol to wash for one time, and drying at 70 ℃ to obtain a white powder precursor, namely sulfate type rare earth layered hydroxide (Gd)0.97Yb0.02Er0.01)2(OH)4SO4·nH2And O (n ═ 2.2), the XRD pattern of which is shown in figure 2(b), the morphology of which is agglomerated spheres with the diameter of 80-110 μm, and which is shown in figure 3 (b).
(5) Calcining the white powder precursor in air at 1000 deg.C for 1h to obtain rare earth oxysulfate (Gd)0.97Yb0.02Er0.01)2O2SO4The XRD of the up-conversion phosphor is shown in figure 4(b), and the product can be seen to be pure phase; the morphology of the precursor is similar to that of the precursor, the precursor is an agglomerated sphere, and the diameter of the agglomerated sphere is 80-110 mu m, as shown in FIG. 5 (b).
Example 4
A preparation method of rare earth doped gadolinium oxysulfide up-conversion fluorescent powder comprises the following steps:
the steps (1), (2), (3) and (4) are the same as those in example 3;
(5) placing the white powder precursor in H2And N2Mixed gas (volume ratio, H)2∶N2Calcining at 1200 deg.C for 1h in 60: 40) atmosphere to obtain rare earth oxysulfide (Gd)0.97Yb0.02Er0.01)2O2The XRD of the S fluorescent powder is shown in figure 6(b), and the product can be seen to be pure phase; the morphology of the precursor is similar to that of the precursor, the precursor is an agglomerated sphere, and the diameter of the agglomerated sphere is 80-110 mu m, as shown in FIG. 7 (b).
Example 5
A preparation method of rare earth doped gadolinium oxysulfate upconversion fluorescent powder comprises the following steps:
(1) gd (NO)3)3·6H2O、Yb(NO3)3·6H2O and Tm (NO)3)3·6H2O, adding deionized water, stirring at room temperature to obtain RE3+The ion concentration was 0.1mol/L RE (NO)3)3A solution;
wherein, in terms of molar ratio, Gd3+∶Yb3+∶Tm3+＝97∶2∶1；
(2) 0.8g of ammonium sulfate was dissolved in 0.1mol/L RE (NO)3)3In solution, RE (NO)3)3Stirring the solution for 15min at room temperature with the volume of 60mL, then continuously stirring and dropwise adding ammonia water, and adjusting the pH value to 7.0 to obtain a suspension;
wherein, the molar ratio of sulfate radical to RE is3+＝1∶1；
(3) Transferring the suspension into a reaction kettle, carrying out hydrothermal reaction for 24 hours at 100 ℃, taking out after the reaction is finished, and naturally cooling to room temperature to obtain a reaction product;
(4) centrifugally separating the reaction product, adding water to wash for three times, adding absolute ethyl alcohol to wash for one time, and drying at 70 ℃ to obtain a white powder precursor, namely, a sulfate type rare earth layered hydroxide (Gd)0.97Yb0.02Tm0.01)2(OH)4SO4·nH2O (n ═ 2.1), the XRD spectrum of which is shown in figure 2(c), the morphology of which is agglomerated spheres, and the size of which is 80-110 μm, as shown in figure 3 (c);
(5) calcining the white powder precursor in air at 1000 deg.C for 1h to obtain rare earth oxysulfate (Gd)0.97Yb0.02Tm0.01)2O2SO4The XRD of the up-conversion phosphor is shown in figure 4(c), and the product can be seen to be pure phase; the morphology of the precursor is similar to that of the precursor, the precursor is an agglomerated sphere, and the diameter of the agglomerated sphere is 80-110 mu m, as shown in FIG. 5 (c).
Example 6
A preparation method of rare earth doped gadolinium oxysulfide up-conversion fluorescent powder comprises the following steps:
the steps (1), (2), (3) and (4) are the same as those in example 5;
(5) placing the white powder precursor in H2And N2Mixed gas (volume ratio, H)2∶N2Calcining at 1200 deg.C for 1h in 5: 95) atmosphere to obtain rare earth oxysulfide (Gd)0.97Yb0.02Tm0.01)2O2The XRD of the S phosphor is shown in figure 6(c), and the product can be seen as a pure phase. The morphology of the precursor is similar to that of the precursor, the precursor is an agglomerated sphere, and the diameter of the agglomerated sphere is 80-110 mu m, as shown in FIG. 7 (c).
Example 7
A preparation method of rare earth doped gadolinium oxysulfate upconversion fluorescent powder comprises the following steps:
(1) gd (NO)3)3·6H2O、Yb(NO3)3·6H2O and Ho (NO)3)3·6H2O, adding deionized water, stirring at room temperature to obtain RE3+The ion concentration was 0.1mol/L RE (NO)3)3A solution;
wherein, in terms of molar ratio, Gd3+∶Yb3+∶Ho3+＝97∶1∶2；
(2) 4g of ammonium sulfate was dissolved in 0.1mol/L RE (NO)3)3In solution, RE (NO)3)3Stirring the solution for 20min at room temperature with the volume of 60mL, then continuously stirring and dropwise adding ammonia water, and adjusting the pH value to 10.0 to obtain a suspension;
wherein, the molar ratio of sulfate radical to RE is3+＝5∶1；
(3) Transferring the suspension into a reaction kettle, carrying out hydrothermal reaction for 24 hours at 150 ℃, taking out after the reaction is finished, and naturally cooling to room temperature to obtain a reaction product;
(4) centrifugally separating the reaction product, adding water to wash for three times, adding absolute ethyl alcohol to wash for one time, and drying at 70 ℃ to obtain a white powder precursor, namely sulfate type rare earth layered hydroxide (Gd)0.97Yb0.01Ho0.02)2(OH)4SO4The XRD spectrum is shown in figure 8(a), and XRD shows that the material is pure phase, the morphology of the material is a quasi-hexagonal micron sheet, the thickness of the material is 0.5-0.8 mu m, and the length of the material is 4-8 mu m, as shown in figure 9 (a);
(5) calcining the white powder precursor in air at 1000 deg.C for 1h to obtain rare earth oxysulfate (Gd)0.97Yb0.01Ho0.02)2O2SO4The XRD of the up-conversion phosphor is shown in figure 10(a), and the product can be seen to be pure phase; the shape of the plate is similar to that of the precursor, the plate is a quasi-hexagonal micron plate, the thickness of the plate is 0.5-0.8 mu m, the length of the plate is 4-8 mu m, and as shown in figure 11(a), the up-conversion emission spectrum of the plate is shown in figure 12 (a).
Example 8
A preparation method of rare earth doped gadolinium oxysulfide up-conversion fluorescent powder comprises the following steps:
the steps (1), (2), (3) and (4) are the same as those in example 7;
(5) placing the white powder precursor in H2And N2Mixed gas (volume ratio, H)2∶N270: 30) atmosphere, and calcining at 1200 ℃ for 1h to obtain rare earth oxysulfide (Gd)0.97Yb0.01Ho0.02)2O2The XRD of the S fluorescent powder is shown in figure 13(a), the XRD shows that the S fluorescent powder is pure phase, the morphology of the S fluorescent powder is similar to that of a precursor of the S fluorescent powder, the S fluorescent powder is a quasi-hexagonal micron plate, the thickness of the S fluorescent powder is 0.5-0.8 mu m, the length of the S fluorescent powder is 4-8 mu m, as shown in figure 14(a), and the up-conversion emission spectrum of the S fluorescent powder is shown in figure 15 (a.
Example 9
A preparation method of rare earth doped gadolinium oxysulfate upconversion fluorescent powder comprises the following steps:
(1) gd (NO)3)3·6H2O、Yb(NO3)3·6H2O and Er (NO)3)3·6H2O, adding deionized water, stirring at room temperature to obtain RE3+The ion concentration was 0.1mol/L RE (NO)3)3A solution;
wherein, in terms of molar ratio, Gd3+∶Yb3+∶Er3+＝97∶1∶2；
(2) 0.4g of ammonium sulfate was dissolved in 0.1mol/L RE (NO)3)3In solution, RE (NO)3)3Stirring the solution for 15min at room temperature with the volume of 60mL, then continuously stirring and dropwise adding ammonia water, and adjusting the pH value to 10.0 to obtain a suspension;
wherein, the molar ratio of sulfate radical to RE is3+＝1∶2；
(3) Transferring the suspension into a reaction kettle, carrying out hydrothermal reaction for 24 hours at 150 ℃, taking out after the reaction is finished, and naturally cooling to room temperature to obtain a reaction product;
(4) centrifugally separating the reaction product, adding water to wash for three times, adding absolute ethyl alcohol to wash for one time, and drying at 50 ℃ to obtain a white powder precursor, namely sulfate type rare earth layered hydroxide (Gd)0.97Yb0.01Er0.02)2(OH)4SO4The XRD spectrum is shown in figure 8(b), and XRD shows that the material is a pure phase, the appearance of the material is a quasi-hexagonal micron sheet, the thickness of the material is 0.5-0.8 mu m, and the length of the material is 4-8 mu m, as shown in figure 9 (b);
(5) calcining the white powder precursor in air at 1000 deg.C for 4 hr to obtain rare earth oxysulfate (Gd)0.97Yb0.01Er0.02)2O2SO4The XRD of the up-conversion phosphor is shown in figure 10(b), and the XRD shows that the up-conversion phosphor is pure phase; the shape of the plate is similar to that of the precursor, and the plate is a quasi-hexagonal micron plate, the thickness of the plate is 0.5-0.8 mu m, and the length of the plate is 4-8 mu m, as shown in fig. 11 (b); the up-converted emission spectrum is shown in fig. 12 (b).
Example 10
A preparation method of rare earth doped gadolinium oxysulfide up-conversion fluorescent powder comprises the following steps:
the steps (1), (2), (3) and (4) are the same as those in example 9;
(5) placing the white powder precursor in H2Calcining at 1200 ℃ for 4h in a reducing atmosphere to obtain rare earth oxysulfide (Gd)0.97Yb0.01Er0.02)2O2The XRD of the S fluorescent powder is shown in figure 13(b), the XRD shows that the S fluorescent powder is pure phase, the morphology of the S fluorescent powder is similar to that of a precursor of the S fluorescent powder, the S fluorescent powder is a quasi-hexagonal micron sheet, the thickness of the S fluorescent powder is 0.5-0.8 mu m, the length of the S fluorescent powder is 4-8 mu m, and as shown in figure 14(b), emitted light is converted on the S fluorescent powder and emittedThe spectrum is shown in FIG. 15 (b).
Example 11
A preparation method of rare earth doped gadolinium oxysulfate upconversion fluorescent powder comprises the following steps:
(1) gd (NO)3)3·6H2O、Yb(NO3)3·6H2O and Tm (NO)3)3·6H2O, adding deionized water, stirring at room temperature to obtain RE3+The ion concentration was 0.1mol/L RE (NO)3)3A solution;
wherein, in terms of molar ratio, Gd3+∶Yb3+∶Tm3+＝97∶1∶2；
(2) 0.8g of ammonium sulfate was dissolved in 0.1mol/L RE (NO)3)3In solution, RE (NO)3)3Stirring the solution for 20min at room temperature with the volume of 60mL, then continuously stirring and dropwise adding ammonia water, and adjusting the pH value to 10.0 to obtain a suspension;
wherein, in terms of molar ratio, sulfate radical: RE3+＝1∶1；
(3) Transferring the suspension into a reaction kettle, carrying out hydrothermal reaction for 24 hours at 150 ℃, taking out after the reaction is finished, and naturally cooling to room temperature to obtain a reaction product;
(4) centrifugally separating the reaction product, adding water to wash for three times, adding absolute ethyl alcohol to wash for one time, and drying at 80 ℃ to obtain a white powder precursor, namely sulfate type rare earth layered hydroxide (Gd)0.97Yb0.01Tm0.02)2(OH)4SO4The XRD pattern is shown in figure 8(c), and XRD shows that the crystal is pure phase; the shape of the plate is a quasi-hexagonal micron plate, the thickness of the plate is 0.5-0.8 mu m, and the length of the plate is 4-8 mu m, as shown in figure 9 (c).
(5) Putting the white powder precursor into air, calcining for 0.5h at 1000 ℃ to obtain the rare earth-containingOxysulfate (Gd)0.97Yb0.01Tm0.02)2O2SO4The XRD of the up-conversion fluorescent powder is shown in figure 10(c), the XRD shows that the up-conversion fluorescent powder is pure phase, has the similar appearance with the precursor, is a quasi-hexagonal micron sheet, has the thickness of 0.5-0.8 mu m and the length of 4-8 mu m, and is shown in figure 11(c), and the up-conversion emission spectrum thereof is shown in figure 12 (c).
Example 12
A preparation method of rare earth doped gadolinium oxysulfide up-conversion fluorescent powder comprises the following steps:
the steps (1), (2), (3) and (4) are the same as those in example 11;
(5) placing the white powder precursor in H2And N2Mixed gas (volume ratio, H)2∶N280: 20) atmosphere, and calcining at 1200 ℃ for 0.5h to obtain rare earth oxysulfide (Gd)0.97Yb0.01Tm0.02)2O2The XRD of the S fluorescent powder is shown in figure 13(c), the XRD shows that the S fluorescent powder is pure phase, the morphology of the S fluorescent powder is similar to that of a precursor of the S fluorescent powder, the S fluorescent powder is a quasi-hexagonal micron plate, the thickness of the S fluorescent powder is 0.5-0.8 mu m, the length of the S fluorescent powder is 4-8 mu m, as shown in figure 14(c), and the up-conversion emission spectrum of the S fluorescent powder is shown in figure 15 (c.
Claims (7)
1. A preparation method of rare earth doped gadolinium oxysulfide and gadolinium oxysulfate up-conversion fluorescent powder is characterized by comprising the following steps:
(1) gd (NO)3)3·6H2O、Yb(NO3)3·6H2O and Ln (NO)3)3·6H2Mixing O, adding deionized water, stirring at room temperature to obtain RE (NO)3)3A solution;
wherein, in terms of molar ratio, Gd3+:Yb3+:Ln3+=(90~97):(5~2):(5~1)；
Ln is Ho or Tm;
said RE3+Is Gd3+、Yb3+And Ln3+Mixed ions of (2);
(2) dissolving ammonium sulfate in RE (NO)3)3Stirring the solution uniformly, then continuing stirring, adding ammonia water, and adjusting the pH value to 7.0-10.0 to obtain a suspension;
wherein, according to the mol ratio, the sulfate radical is RE3+=(1~5):(2~1)；
(3) Transferring the suspension into a reaction kettle, carrying out hydrothermal reaction for 1-72 h at 100-150 ℃, taking out after the reaction is finished, and naturally cooling to room temperature to obtain a reaction product;
(4) centrifugally separating, cleaning and drying the reaction product to obtain a white powder precursor (Gd, Yb, Ln)2(OH)4SO4·nH2O, wherein,n=0 or 1.9-2.2;
the white powder precursor is sulfate type rare earth layered hydroxide, and the morphology of the white powder precursor is one of agglomerated balls or quasi-hexagonal micron sheets;
(5) calcining the white powder precursor to obtain the rare earth ion doped Gd2O2S and Gd2O2SO4An up-conversion phosphor; wherein the calcination parameters are (a) or (b):
(a) calcining in air at 800-1000 deg.c for 0.5-4 hr to obtain RE ion doped Gd2O2SO4The up-conversion fluorescent powder is rare earth oxysulfate (Gd, Yb, Ln)2O2SO4；
(b) The calcining environment is a reducing atmosphere, the calcining temperature is 800-1200 ℃, the calcining time is 0.5-4 h, and the prepared rare earth ion doped Gd2O2The S up-conversion fluorescent powder is rare earth oxysulfide (Gd, Yb, Ln)2O2S。
2. The method of claim 1, wherein the rare earth-doped gadolinium oxysulfide and gadolinium oxysulfate upconversion phosphor is prepared byCharacterized in that said RE (NO)3)3RE of solution3+The concentration is 0.05-0.5 mol/L.
3. The method for preparing the rare earth-doped gadolinium oxysulfide and gadolinium oxysulfate upconversion phosphor according to claim 1, wherein in the step (2), the stirring is performed for 15-20 min.
4. The method for preparing the rare earth-doped gadolinium oxysulfide and gadolinium oxysulfate upconversion phosphor according to claim 1, wherein in the step (2), ammonia water is added by a dropwise addition method.
5. The method for preparing the rare earth-doped gadolinium oxysulfide and gadolinium oxysulfate upconversion phosphor according to claim 1, wherein in the step (4), the washing is performed by adding water for three times and then adding absolute ethyl alcohol for one time.
6. The method for preparing the rare earth-doped gadolinium oxysulfide and gadolinium oxysulfate upconversion phosphor according to claim 1, wherein in the step (4), the drying temperature is 50-80 ℃.
7. The method for preparing the rare earth-doped gadolinium oxysulfide and gadolinium oxysulfate upconversion phosphor of claim 1, wherein in step 5, the reducing atmosphere is H2And N2Mixing in proportion, wherein H25-100% of volume percentage and the balance of N2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610953772.6A CN106520121B (en) | 2016-10-27 | 2016-10-27 | The preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610953772.6A CN106520121B (en) | 2016-10-27 | 2016-10-27 | The preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106520121A CN106520121A (en) | 2017-03-22 |
| CN106520121B true CN106520121B (en) | 2019-02-05 |
Family
ID=58325394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610953772.6A Expired - Fee Related CN106520121B (en) | 2016-10-27 | 2016-10-27 | The preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106520121B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107238592B (en) * | 2017-05-31 | 2019-12-06 | 青岛科技大学 | Ferric ion detection reagent and preparation method and application thereof |
| CN108300471A (en) * | 2018-03-01 | 2018-07-20 | 渤海大学 | A kind of oxygen-containing lanthanum sulfate fluorescent powder and preparation method thereof of transmitting near infrared light |
| CN111439775A (en) * | 2020-06-05 | 2020-07-24 | 眉山博雅新材料有限公司 | Method for preparing GOS-doped scintillation powder |
| CN114380319B (en) * | 2020-10-19 | 2024-02-13 | 厦门稀土材料研究所 | Novel rare earth oxysulfide with sheet stacking spherical structure and preparation method and application thereof |
| CN112322293B (en) * | 2020-11-09 | 2022-03-15 | 厦门大学 | Multiband oxysulfide elastic stress luminescent material and preparation method thereof |
| CN113667477A (en) * | 2021-08-04 | 2021-11-19 | 北京科技大学 | Preparation method of magneton-shaped high-fluorescence rare earth oxysulfide |
| CN113800550B (en) * | 2021-10-08 | 2023-06-23 | 江西理工大学 | Flaky Gd 2 O 2 SO 4 And a method for preparing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003027058A (en) * | 2001-07-18 | 2003-01-29 | Kinya Adachi | Manufacturing method for ultrafine particle of rare earth oxysulfide |
| CN100467382C (en) * | 2007-04-29 | 2009-03-11 | 东北大学 | Method for synthesizing rare-earth oxide sulfate nano-grain by high-molecular gel network template |
| KR101458026B1 (en) * | 2007-11-29 | 2014-11-06 | 삼성디스플레이 주식회사 | A rare earth nano phosphor and synthetic method thereof |
| CN105062484B (en) * | 2015-08-04 | 2017-12-22 | 温州医科大学 | Conversion nano pipe and preparation method thereof on a kind of rare-earth oxide sulfate |
-
2016
- 2016-10-27 CN CN201610953772.6A patent/CN106520121B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106520121A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106520121B (en) | The preparation method of rear-earth-doped gadolinium oxysulfide and oxygen-containing Digadolinium trisulfate up-conversion phosphor | |
| CN106544025B (en) | A kind of preparation method of rear-earth-doped gadolinium oxysulfide fluorescent powder | |
| DE112005000930B4 (en) | α-SiAlON powder and process for the preparation thereof | |
| Singh et al. | Synthesis and enhanced luminescent characterization of SrAl 4 O 7: Eu 2+, RE 3+(RE= Nd, Dy) nanophosphors for light emitting applications | |
| CN104403672B (en) | A kind of up-conversion luminescent material and its preparation method and application | |
| CN102775985A (en) | One method for synthesizing Sr2MgSi2O7nanowire with long afterglow luminescence (Eu2+, dy3+) | |
| CN104031647B (en) | A kind of preparation method of round pie europium doping vanadic acid lanthanum red fluorescence powder | |
| CN106542560B (en) | A kind of preparation method of rare earth oxysulfate | |
| CN105712299B (en) | Metal hydroxides not soluble in water and preparation method thereof | |
| CN101357775A (en) | Method for preparing fine monodisperse rare-earth sulfur oxide | |
| Jinglei et al. | Synthesis of LiEu1-xBix (MoO4) 2 red phosphors by sol-gel method and their luminescent properties | |
| Li et al. | Synthesis and characterizations of pompon-like Y2O2SO4: Eu3+ phosphors using a UBHP technique based on UAS system | |
| CN105752957B (en) | Using the method for preparing nano-scale rare earth phosphate phosphor from sacrifice template method | |
| CN108165269A (en) | A kind of fluorination lutetium potassium that phase change delay and Up-conversion Intensity greatly improve is nanocrystalline and preparation method thereof | |
| CN109796045B (en) | Method for preparing compound tungstate by adopting self-sacrificial template | |
| CN1621490A (en) | Process for preparing rare-earth red luminescent materials | |
| CN103666471A (en) | Novel method of synthesizing high-performance YAG: Ce fluorescent powder | |
| CN103087716A (en) | Synthesis method of rare earth doped hexagonal-phase cerium sodium fluoride nanocrystalline | |
| Ji et al. | Synthesis of high quality Ce: YAG nanopowders by graphene oxide nanosheet-assisted co-precipitation method | |
| CN105776331B (en) | A kind of sacrifice masterplate synthetic method certainly for preparing rare-earth vanadate as masterplate with LRH | |
| CN109810706B (en) | Preparation method of hydrangea-like europium-doped calcium molybdate powder | |
| Huang et al. | Molten salt synthesis of La2O2SO4 nanosheets and their luminescent properties with Eu3+ doping | |
| Liu et al. | Synthesis and characterization of Gd2O2S: Pr3+, Ce3+ (GOS) scintillation phosphors via a homogeneous precipitation followed by solid-state reaction method | |
| Han et al. | Upconversion White Light Output in (Y0. 9Gd0. 1) 2O2S Matrix Tri-Doped with Yb3+/Tm3+/Er3+ or Yb3+/Tm3+/Ho3+ | |
| Xu et al. | Electrospun LaOCl: Eu 3+, Ce 4+ nanofibers with color-tunable fluorescence between red and orange |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Xuejiao Inventor after: Zhu Qi Inventor after: Li Xiaodong Inventor after: Sun Xudong Inventor before: Li Jiguang Inventor before: Wang Xuejiao Inventor before: Zhu Qi Inventor before: Li Xiaodong Inventor before: Sun Xudong |
|
| CB03 | Change of inventor or designer information | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190205 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |