CN116179192B - Magneto-optical three-function composite microsphere and preparation method thereof - Google Patents
Magneto-optical three-function composite microsphere and preparation method thereof Download PDFInfo
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- CN116179192B CN116179192B CN202211727728.5A CN202211727728A CN116179192B CN 116179192 B CN116179192 B CN 116179192B CN 202211727728 A CN202211727728 A CN 202211727728A CN 116179192 B CN116179192 B CN 116179192B
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- 239000004005 microsphere Substances 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 35
- 239000011787 zinc oxide Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 17
- -1 rare earth salt Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 150000003746 yttrium Chemical class 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 150000002505 iron Chemical class 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011746 zinc citrate Substances 0.000 claims description 2
- 235000006076 zinc citrate Nutrition 0.000 claims description 2
- 229940068475 zinc citrate Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 238000001514 detection method Methods 0.000 abstract description 11
- 230000003287 optical effect Effects 0.000 abstract description 4
- 238000007885 magnetic separation Methods 0.000 abstract description 3
- 238000001917 fluorescence detection Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 15
- 239000000696 magnetic material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical group CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 1
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 1
- ILOTUXNTERMOJL-UHFFFAOYSA-K thulium(iii) chloride Chemical compound Cl[Tm](Cl)Cl ILOTUXNTERMOJL-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 1
- GONBZNBMLOZYAM-UHFFFAOYSA-K yttrium(3+);triformate Chemical compound [Y+3].[O-]C=O.[O-]C=O.[O-]C=O GONBZNBMLOZYAM-UHFFFAOYSA-K 0.000 description 1
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 1
Classifications
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- 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
- C09K11/7785—Chalcogenides with zinc or cadmium
-
- 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
- C09K11/7767—Chalcogenides
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Manufacturing & Machinery (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to a magneto-optical three-function composite microsphere and a preparation method thereof, belonging to the technical field of composite microspheres. The preparation method of the magneto-optical three-functional composite microsphere comprises the following steps of (1) dissolving zinc salt, yttrium salt and rare earth salt in water, regulating pH to 5-8, reacting for 2-8 hours at 120-180 ℃, centrifuging, washing with water, and drying to obtain a rare earth doped porous zinc oxide flower ball; (2) Dispersing rare earth doped porous zinc oxide flower balls, ferric salt and ferrous salt in water, regulating the pH value to 7-10, centrifuging, washing with water and drying to obtain the magneto-optical and optical three-function composite microsphere. The magneto-optical three-functional composite microsphere has magnetic property, fluorescence property and up-conversion fluorescence property, and can realize rapid magnetic separation of materials; the method can perform relevant detection by utilizing the fluorescence performance of the material, and can perform up-conversion fluorescence detection with larger depth by utilizing near infrared light with stronger penetrability.
Description
Technical Field
The invention belongs to the technical field of composite microspheres, and particularly relates to a magneto-optical three-function composite microsphere and a preparation method thereof.
Background
In recent years, fluorescent materials are widely used in the fields of clinical medicine detection, ion detection, environmental monitoring and the like, and therefore, fluorescent materials, particularly a fluorescent material with large stokes shift and slightly high fluorescence, are receiving a great deal of attention in the related fields.
Because of the specificity of part of the detected objects, such as detection depth problems caused by the problems of incapability of ultraviolet irradiation, small ultraviolet irradiation depth and the like, and the light absorption property of colored substances, a fluorescent material with up-conversion fluorescent property is explored, and has important application value.
Meanwhile, in order to realize the rapid separation of the fluorescent material, the detection efficiency and the recycling of the fluorescent material are quickened, the fluorescent property of the magnetic material is endowed, and the fluorescent material has important application value.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems that the detection signal is influenced by the detected substrate in the prior art, for example, the detection depth problem caused by the problems that part of samples cannot be irradiated by ultraviolet light, the ultraviolet irradiation depth is small and the like, the absorbance of colored substances and the separation of fluorescent microspheres is difficult and the like.
In order to solve the technical problems, the invention provides a magneto-optical and optical three-function composite microsphere and a preparation method thereof. The magneto-optical three-functional composite microsphere has magnetic property, fluorescence property and up-conversion fluorescence property, and has good application prospect in the fields of biological medicine, clinical medicine detection, environment monitoring, anti-counterfeiting and the like.
The first object of the invention is to provide a preparation method of magneto-optical three-function composite microsphere, comprising the following steps,
(1) Dissolving zinc salt, yttrium salt and rare earth salt in water, regulating the pH value to 5-8, reacting for 2-8 hours at 120-180 ℃, centrifuging, washing with water, and drying to obtain rare earth doped porous zinc oxide flower spheres;
(2) Dispersing the rare earth doped porous zinc oxide flower ball, ferric salt and ferrous salt in water, regulating the pH value to 7-10, centrifuging, washing with water and drying to obtain the magneto-optical three-function composite microsphere.
In one embodiment of the invention, in step (1), the zinc salt is zinc chloride, zinc sulfate, zinc nitrate, zinc acetate or zinc citrate.
In one embodiment of the invention, in step (1), the yttrium salt is yttrium chloride, yttrium acetate, yttrium formate, yttrium oxalate, yttrium nitrate or yttrium sulfate.
In one embodiment of the invention, in step (1), the rare earth elements gadolinium, thulium, terbium, dysprosium, europium, holmium and erbium are one or more of them.
In one embodiment of the present invention, in step (1), the rare earth salt is one or more of rare earth hydrochloride, rare earth acetate, rare earth formate, rare earth oxalate, rare earth nitrate, and rare earth sulfate;
in one embodiment of the present invention, in the step (1), the molar ratio of the zinc salt, yttrium salt and rare earth salt is 10 to 1000:0.1-10:1.
in one embodiment of the invention, in the step (1), the method further comprises adding an organic acid into the water, and grafting carboxyl groups on the surface of the rare earth doped porous zinc oxide flower sphere.
In one embodiment of the invention, the organic acid is one or more of oxalic acid, acetic acid, and propionic acid.
In one embodiment of the invention, in step (1), the pH adjusting agent is sodium citrate and/or urea.
In one embodiment of the invention, in step (2), the iron salt is ferric chloride, ferric sulfate, ferric acetate, ferric citrate, ferric oleate, ferric nitrate, or ferric oxalate.
In one embodiment of the present invention, in step (2), the ferrous salt is ferrous chloride, ferrous sulfate, or ferrous oxalate.
In one embodiment of the present invention, in step (2), the molar ratio of the iron salt to the ferrous salt is 1.5 to 4:1.
in one embodiment of the invention, in step (2), the pH adjuster is sodium hydroxide solution and/or aqueous ammonia.
In one embodiment of the invention, the concentration of sodium hydroxide solution is 0.1-1M.
In one embodiment of the invention, rare earth doped zinc oxide flower balls with fluorescence performance and up-conversion fluorescence performance are prepared by a hydrothermal method; and then the magnetic material is deposited in situ by utilizing the porous adsorption performance of the zinc oxide flower ball to prepare the magneto-optical three-function composite microsphere with magnetic property, fluorescence property and up-conversion fluorescence property.
The second object of the invention is to provide a magneto-optical three-function composite microsphere prepared by the method.
In one embodiment of the invention, the magneto-optical three-function composite microsphere emits red, green, yellow, orange or blue fluorescence when the irradiation wavelength is 365-410 nm; when the irradiation wavelength is 980nm near infrared light, the magneto-optical three-functional composite microsphere emits red, green, yellow, orange or blue up-conversion fluorescence.
In one embodiment of the invention, the fluorescence performance of the magneto-optical three-functional composite microsphere is affected by doped rare earth elements, and the fluorescence emission wavelength can be controlled by regulating the doped rare earth elements. By utilizing the specific absorption of yttrium element at 980nm, the magneto-optical three-function composite microsphere has 980nm excited up-conversion fluorescence performance by adding yttrium element. The characteristic wavelength of rare earth elements is utilized, and the fluorescence and up-conversion fluorescence color of the rare earth doped zinc oxide flower ball are controlled by controlling the doped system elements and the dosage thereof. Blue fluorescence is emitted by doping thulium; terbium or erbium doped emits green fluorescence; europium doped emits red fluorescence.
In one embodiment of the invention, the magneto-optical three-function composite microsphere has magnetic property, fluorescence property and up-conversion fluorescence property.
In one embodiment of the present invention, the emission wavelength of the upconversion fluorescence of the magneto-optical three-functional composite microsphere can be controlled by doped rare earth elements.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The magneto-optical three-functional composite microsphere has magnetic property, fluorescence property and up-conversion fluorescence property, and can realize rapid magnetic separation of materials; the method can perform relevant detection by utilizing the fluorescence performance of the material, and can perform up-conversion fluorescence detection with larger depth by utilizing near infrared light with stronger penetrability.
(2) The magneto-optical three-function composite microsphere can be obtained through simple steps of hydrothermal and adsorption deposition, and the method is simple and reliable, is easy to implement and is easy to realize industrial production.
(3) The modification method of the magneto-optical three-function composite microsphere can change the addition of raw materials in the preparation process, so as to change the fluorescence emission of the materials, and prepare the composite material with different fluorescence emission wavebands so as to adapt to the detection of different detection environments.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is an electron microscope image of a rare earth doped porous zinc oxide flower sphere and a magneto-optical three-function composite microsphere according to embodiment 2 of the present invention; wherein A is a rare earth doped porous zinc oxide flower ball; b is magneto-optical light three-function composite microsphere.
FIG. 2 is a magneto-optical performance test chart of the magneto-optical and optical three-functional composite microsphere according to embodiment 2 of the present invention; wherein A is the state before magnetic adsorption; b is a state after magnetic adsorption; c is the state under ultraviolet irradiation; d is a state under 980nm laser irradiation.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
In the present invention, unless otherwise indicated, the preparation of single fluorescent microspheres is substantially the same as the preparation of micron rare earth doped zinc oxide fluorescent flower spheres in the examples, except that yttrium salt is not added during the preparation process.
Example 1
A magneto-optical three-function composite microsphere (red fluorescence) and a preparation method thereof specifically comprise the following steps:
1. thermal method for preparing micron rare earth doped zinc oxide fluorescent flower ball (double fluorescent microsphere)
(1) 0.66g of zinc acetate, 0.006g of europium chloride and 0.005g of yttrium chloride are weighed and dissolved in 80mL of pure water;
(2) Adding 0.07g of sodium citrate and 0.36g of urea at a time, adjusting the pH to 7, and stirring for dissolution;
(3) The reaction solution was transferred to a 100mL hydrothermal reaction vessel and reacted at 150℃for 6h.
(4) After the reaction is finished, removing reactants, centrifuging to remove a reaction solution, and washing a precipitated product for a plurality of times by using ethanol and pure water;
(5) Drying for 24 hours at 60 ℃ in a blast drying oven to obtain the micron rare earth doped zinc oxide fluorescent flower ball.
2. Preparing magneto-optical and optical three-function composite microsphere
(1) Weighing 2g of micron rare earth doped zinc oxide fluorescent flower spheres, and dispersing the spheres in 50g of pure water;
(2) 1.35g of ferric chloride hexahydrate and 0.99g of ferrous chloride tetrahydrate are added, and the mixture is fully stirred and dissolved;
(3) Adding ammonia water to adjust the pH to 9, and stirring for reaction for 30min;
(4) After the reaction is finished, centrifuging at 4000rpm for 10min, removing supernatant, and removing unreacted substances and singly nucleated magnetic particles;
(5) And (3) performing magnetic separation, cleaning with pure water and ethanol for multiple times, and drying at 60 ℃ to obtain the magneto-optical three-function composite microsphere.
Example 2
A magneto-optical three-function composite microsphere (green fluorescence) and a preparation method thereof specifically comprise the following steps:
substantially the same as in example 1, except that 0.006g of europium chloride in the preparation of the micrometer rare earth doped zinc oxide fluorescent flower ball was replaced with 0.004g of terbium chloride and 0.002g of erbium chloride.
Example 3
A magneto-optical three-function composite microsphere (blue fluorescence) and a preparation method thereof specifically comprise the following steps:
substantially as in example 1, except that 0.006g of europium chloride in the preparation of the micrometer rare earth doped zinc oxide fluorescent flower ball was replaced with 0.007g of thulium chloride.
Test example 1
Based on examples 1-3, the fluorescence properties of single fluorescent microspheres, double fluorescent microspheres and magneto-optical light three-functional composite microspheres were tested. The emission wavelength and the emission intensity of the fluorescent microspheres are tested by adopting a Japanese Hitachi F-7000 fluorescence spectrophotometer and adopting a 360nm excitation light source for excitation under the conditions of 700V voltage, 2.5nm slit width and 1200nm/min scanning speed. The test results are shown in table 1:
TABLE 1
Test example 2
Based on examples 1-3, the up-conversion fluorescence performance of the double fluorescent microsphere and the magneto-optical three-function composite microsphere was tested. The fluorescent microsphere is excited by adopting a Japanese Hitachi F-7000 fluorescent spectrophotometer under the conditions of 700V voltage, 5nm slit width and 1200nm/min scanning speed by adopting an external light source 980nm laser, the power of the laser is set to be 2.5W, the irradiation distance is 10cm, and the emission wavelength and the emission intensity of the fluorescent microsphere are tested. The test results are shown in table 2:
TABLE 2
Test example 3
The magnetic properties of the magneto-optical three-function composite microspheres of examples 1 to 3 were tested. Taking 0.1g of magneto-optical three-functional microsphere, dispersing in 0.9mL of pure water by ultrasonic, preparing microsphere dispersion liquid with the solid content of 10%, and then placing the microsphere dispersion liquid on a magnetic frame to observe the magnetic adsorption time. The test results are shown in table 3:
TABLE 3 Table 3
| Sample preparation | Magnetic adsorption time |
| Example 1 | 20.1s |
| Example 2 | 19.2s |
| Example 3 | 21.4s |
From tables 1 to 3, the magneto-optical three-function composite microsphere of the embodiment of the invention has good magnetic adsorption performance, which indicates that the magneto-optical three-function composite microsphere has good magnetic property and can be separated by magnetic adsorption.
Test example 4
The dual fluorescent microsphere and magneto-optical three-functional composite microsphere of example 2 were subjected to scanning electron microscopy, and the results are shown in fig. 1. As can be seen from FIG. 1A, the zinc oxide fluorescent microsphere is a flower-shaped microsphere, and has a porous characteristic and a multi-stage structure. The zinc oxide flower-shaped microsphere with the multilevel structure has larger specific surface area and better adsorption characteristic, and plays an important role in the subsequent adsorption and in-situ deposition of the magnetic material. Compared with fig. 1A, fig. 1B has no multilevel structure, and the microspheres slightly grow up, which means that in the deposition process of the magnetic material, the zinc oxide microspheres adsorb the magnetic material into the sheets and holes of the magnetic material, and the magnetic material is formed in situ, so that the multilevel structure of the original fluorescent microspheres is filled up and then continues to grow, and the particle size is increased. The deposition amount of the magnetic material can be adjusted according to the magnetic property and the particle size requirement, so that partial multisection structure is reserved, and the particle size is adjusted.
Test example 5
Taking the magneto-optical three-functional composite microsphere of example 2 as an example, magneto-optical performance test was performed, and the magnetic adsorption performance, fluorescence performance and upconversion fluorescence performance of the composite microsphere were observed, and as a result, as shown in fig. 2, a was a microsphere dispersion state before magnetic adsorption, B was a state after magnetic adsorption, C was a state under ultraviolet irradiation, and D was a state under 980nm laser irradiation.
As can be seen from fig. 2A-2B, the magneto-optical three-functional microsphere has good magnetic adsorption performance and good adsorption effect; as can be seen from fig. 2C, the material can fluoresce bright green under uv light; as can be seen from fig. 2D, under the irradiation of 980nm near infrared light, the magneto-optical three-functional composite microsphere can emit bright green fluorescence, which indicates that the magneto-optical three-functional composite microsphere has better up-conversion fluorescence performance.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (7)
1. A preparation method of magneto-optical three-function composite microspheres is characterized by comprising the following steps,
(1) Dissolving zinc salt, yttrium salt and rare earth salt in water, regulating the pH value to 5-8, reacting for 2-8 hours at 120-180 ℃, centrifuging, washing with water, and drying to obtain rare earth doped porous zinc oxide flower spheres; the rare earth element is one or more of thulium, terbium, europium and erbium; the molar ratio of the zinc salt to the yttrium salt to the rare earth salt is 10-1000:0.1-10:1, a step of;
(2) Dispersing the rare earth doped porous zinc oxide flower ball, ferric salt and ferrous salt in water, regulating the pH value to 7-10, centrifuging, washing with water and drying to obtain the magneto-optical three-function composite microsphere.
2. The method of claim 1, wherein in step (1), the zinc salt is zinc chloride, zinc sulfate, zinc nitrate, zinc acetate or zinc citrate.
3. The method of claim 1, wherein in the step (2), the iron salt is ferric chloride, ferric sulfate, ferric acetate, ferric citrate, ferric oleate, ferric nitrate or ferric oxalate.
4. The method of claim 1, wherein in the step (2), the ferrous salt is ferrous chloride, ferrous sulfate or ferrous oxalate.
5. The method for preparing magneto-optical three-functional composite microspheres according to claim 1, wherein in the step (2), the molar ratio of the iron salt to the ferrous salt is 1.5-4:1.
6. a magneto-optical three-function composite microsphere prepared by the method of any one of claims 1 to 5.
7. The magneto-optical three-function composite microsphere according to claim 6, wherein the magneto-optical three-function composite microsphere emits red, green, yellow, orange or blue fluorescence when irradiated with light having a wavelength of 365-410 nm; when the irradiation wavelength is 980nm near infrared light, the magneto-optical three-functional composite microsphere emits red, green, yellow, orange or blue up-conversion fluorescence.
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| CN109607593A (en) * | 2019-01-10 | 2019-04-12 | 沈阳化工大学 | A kind of preparation and its application of NiO-ZnO flower-like structure composite material |
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