CN106905959A - Preparation method of manganese-containing fluoride nanocrystal - Google Patents
Preparation method of manganese-containing fluoride nanocrystal Download PDFInfo
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- CN106905959A CN106905959A CN201710046027.8A CN201710046027A CN106905959A CN 106905959 A CN106905959 A CN 106905959A CN 201710046027 A CN201710046027 A CN 201710046027A CN 106905959 A CN106905959 A CN 106905959A
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- alcohol
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- nanocrystal
- rare earth
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- 239000002159 nanocrystal Substances 0.000 title claims abstract description 84
- 239000011572 manganese Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 41
- -1 rare earth ions Chemical class 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 7
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 229910021569 Manganese fluoride Inorganic materials 0.000 claims description 8
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 40
- 238000000034 method Methods 0.000 abstract description 19
- 230000033228 biological regulation Effects 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 5
- 230000005291 magnetic effect Effects 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 description 16
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 14
- 229910052769 Ytterbium Inorganic materials 0.000 description 11
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 11
- 150000002910 rare earth metals Chemical class 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 9
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- 229910052691 Erbium Inorganic materials 0.000 description 8
- 229910019324 NaMnF3 Inorganic materials 0.000 description 8
- 229910052779 Neodymium Inorganic materials 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 229910021644 lanthanide ion Inorganic materials 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000011565 manganese chloride Substances 0.000 description 5
- 235000002867 manganese chloride Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000000703 high-speed centrifugation Methods 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 229940099607 manganese chloride Drugs 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003937 drug carrier Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000799 fluorescence microscopy Methods 0.000 description 2
- 238000001748 luminescence spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910017544 NdCl3 Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940060038 chlorine Drugs 0.000 description 1
- 235000017168 chlorine Nutrition 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 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
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C09K11/7756—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing neodynium
- C09K11/7757—Halogenides
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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
- C09K11/779—Halogenides
- C09K11/7791—Halogenides with alkali or alkaline earth metals
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides a preparation method of a manganese-containing fluoride nanocrystal, which comprises the following steps: (1) dissolving alkali in alcohol-water solution, and adding organic compound CH3(CH2)nCOOH and/or CH3(CnH2n‑2) COOH is evenly mixed to obtain an alcohol-water-oil reaction system, wherein n is more than or equal to 6 and less than or equal to 18; (2) adding Mn into alcohol-water-oil reaction system2+And F of‑Water solution, and then reacting at 25-200 ℃ to obtain the manganese-containing fluoride nanocrystal; and (3) adding rare earth ions in the step (2) to obtain the rare earth ion doped manganese-containing fluoride nanocrystal. The method realizes the direct preparation of solid or hollow nanocrystals with small size, uniform particle size and high crystallinity by one-pot method, and regulates the alcohol-water-oil ratio and Mn2+And F‑The solid and hollow structures of the nano-crystal are regulated and controlled by distribution in alcohol-water-oil, and the regulation and control of doping rare earth ions not only realize the up-conversion and down-conversion regulation and control of single-color emitted light of the nano-crystal, but also realize the regulation and control of the magnetic property of the nano-crystal.
Description
Technical field
The present invention relates to a kind of synthetic method containing manganese fluoride nano crystal.
Background technology
Hollow nano-material than comparable size solid nanocrystal have bigger specific surface area, smaller density, and
Load capacity higher, has at aspects such as catalysis, energy storage, biomedicine, sensor and environment remediations and widely should
Use prospect.For example in biomedical sector, the inner chamber carrying medicament of hollow nano-material on the one hand can be utilized, on the other hand profit
With hollow nano-material magnetics and optical property in itself, thus they have in terms of the multi-modality imaging of tumour and treatment it is aobvious
Work advantage.Hollow nano-material generally uses template (such as hard template method, soft template method, self-template method) and template-free method system
It is standby.Template is usually directed to multistep synthetic procedure and has requirement higher to temperature control, and hollow obtained by template-free method
The size of inorganic nanocrystal is larger.How one-step method is directly synthesized that uniform particle diameter, size be smaller and that crystallinity is higher is hollow
Nanocrystal has important Research Significance.
Up-conversion luminescence nanomaterial is widely used in every field (such as optical dynamic therapy, the bio-imaging of biomedicine
With spike, novel multifunctional nano pharmaceutical carrier), present important scientific research value and application value.Up-conversion luminescence refers to
Up-conversion, by continuous Multiphoton Absorbtion and energy transfer, launches the process of high-energy light in the case where low energy light is excited.
Rare earth up-conversion luminescence nanomaterial has without autofluorescence, emission band narrow, long lifespan, and good light stability and flicker free etc. are excellent
Point, their more traditional fluorescent dyes in terms of fluorescence imaging and quantum dot have a clear superiority.Additionally, utilizing rare earth nano material
When material carries out bio-imaging and detection, the more heterogeneous light signal to noise ratio of monochromatic emission light of long wavelength is high.It is porous or hollow upper turn
Change the advantage that nano material then presents uniqueness in terms of drug loading and optical dynamic therapy.But it is equal to synthesize particle diameter at present
First, size is smaller, crystallinity is higher, the monochromatic emission light with long wavelength, and can realize solid and hollow upper conversion nano
The regulation and control method of crystal there is no report.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of preparation side containing manganese fluoride nano crystal
Method, the method achieve one kettle way and directly prepares smaller size, uniform particle diameter and crystallinity solid or hollow Nano crystal high.
One kind fluoride containing manganese (MMnF of the invention3(M=Na, K)) nanocrystal preparation method, including following step
Suddenly：
(1) by alkali soluble in alcohol-water solution after, add organic compound CH3(CH2)nCOOH and/or CH3(CnH2n-2)
COOH, stirs and evenly mixs, and lower reaction 5-60min, obtains alcohol-water-oil reaction system at room temperature；Wherein 6≤n≤18；Alcohol conduct
The conditioning agent of water and oil, the ratio with water can expand on demand；The ratio of alcohol-water-oil is adjustable, and preferably 1:1:2-4.
(2) added containing Mn in the alcohol-water-oil reaction system for obtaining to step (1)2+The aqueous solution and containing F-The aqueous solution, mixes
The presoma of fluoride nano crystal containing manganese is obtained, is then reacted at 25-200 DEG C, preferably 120-200 DEG C, still more preferably
120-160 DEG C, most preferably 160 DEG C, reaction solution is obtained after reaction completely.
(3) purification process that the reaction solution of gained in step (2) is used into centrifugation-precipitation-centrifugation-washing is purified, tool
Body be by reaction solution high speed centrifugation after, by supernatant liquor with precipitating reagent precipitate, centrifugation, then washed with water and absolute ethyl alcohol
Wash repeatedly, the solid or hollow fluoride nano crystal containing manganese of gained is dried to obtain solid powder, or be scattered in organic
The solid or hollow colloidal solution containing manganese fluoride nano crystal is obtained in solvent.
Further, in step (1), the alkali is NaOH, KOH, Na2CO3、NaHCO3、K2CO3、KHCO3In one kind or
It is several.
Further, in step (1), the alkali and CH3(CH2)nCOOH or CH3(CnH2n-2) COOH mol ratio be 1:1-
4。
Further, the alcohol is the one kind or several in methyl alcohol, ethanol, propyl alcohol, butanol, isopropanol, isobutanol, the tert-butyl alcohol
Kind.
Further, it is described containing Mn in step (2)2+The aqueous solution is the manganous salt containing the crystallization water and/or without the crystallization water
The aqueous solution, wherein the manganous salt is MnCl2、MnSO4、Mn(NO3)2、Mn(ClO4)2(Mn (CH3COO)2In one kind or
It is several.
Further, it is described containing F in step (2)-The aqueous solution is the NaF aqueous solution, the KF aqueous solution, NH4The F aqueous solution and HF water
One or more in solution.
Further, in step (2), the Mn2+With F-Mol ratio be 1:3-8.
Further, in step (2), rare earth ion, preferably lanthanide ion are additionally added in the alcohol-water-oil reaction system
Ln3+, obtain the MMnF of doping with rare-earth ions3Nanocrystal, i.e. MMnF3:Ln3+(M=Na, K) nanocrystal, the gold of rare earth element
Category salt and fluoride be dissolved in water respectively, if using rare earth ion oxide, it is necessary in advance with nitric acid or hydrochloric acid reaction
The slaine of corresponding rare earth element is generated, then sequentially continuous or certain interval of time adds alcohol-water-oil systems to be formed
Settled solution.
Further, the rare earth ion Ln3+It is Yb3+、Er3+、Tm3+、Ho3+And Nd3+In one or more, doping
Hydrochloride (YbCl of the rare earth ion from them3·6H2O、ErCl3·6H2O、TmCl3·6H2O、HoCl3·6H2O and
NdCl3·6H2O), nitrate Yb (NO3)3·5H2O、Er(NO3)3·5H2O、Tm(NO3)3·6H2O、Ho(NO3)3·5H2O and Nd
(NO3)3·6H2) and oxide (Yb O2O3、Er2O3、Tm2O3、Ho2O3And Nd2O3) in one or more.
Further, the Mn2+With Ln3+Mol ratio be 1-49:1.
Further, in step (2), the reaction time is 1-24h.
The invention discloses a kind of solid/hollow preparation method containing manganese fluoride nano crystal, in alcohol-one pot of water-oil
In reaction system, by the ratio, the adjustment manganese ion (Mn that regulate and control alcohol-water-oil2+) predecessor and fluorine ion (F-) predecessor exists
Distribution in alcohol-water-oil regulates and controls MMnF3The solid and hollow-core construction of (M=Na, K) nanocrystal, and by introduce rare earth from
Son (Ln3+) predecessor, realize solid and hollow nanostructured rare earth ion doped；Realized by the rare earth ion for adulterating different
The regulation and control of solid/hollow magnetics and optical property containing manganese fluoride nano crystal, realize the upper of nanocrystal monochromatic emission light
Conversion and lower conversion regulation and control；The solid and hollow fluoride nano crystal containing manganese of gained can be used as fluorescence imaging and Magnetic resonance imaging
Probe and pharmaceutical carrier.
By such scheme, the present invention at least has advantages below：
Compared with traditional preparation method, the present invention has advantages below：
1st, one kettle way directly prepares smaller size, uniform particle diameter and crystallinity solid or hollow fluoride nano containing manganese high
Crystal；
2nd, by regulate and control oil-phase component in alcohol-water-oil systems be capable of achieving it is solid or hollow containing manganese fluoride nano crystal
Synthesis；
3rd, can obtain solid or hollow, single rare earth by introducing one or more rare earth ion predecessor in water phase
Ion or various rare earth ion doped MMnF3(M=Na, K) nanocrystal；
4th, by regulating and controlling the phase co-conversion that different affecting factors can be realized between hollow-core construction and solid construction, and to receiving
The regulation and control of rice crystallomagnetism and optical property；
5th, the inventive method is easy to operate, and the hollow or solid nanocrystal of gained has the monochromatic emission light of long wavelength,
It is with a wide range of applications in terms of multi-modality imaging with treatment.
Described above is only the general introduction of technical solution of the present invention, in order to better understand technological means of the invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the hollow NaMnF of the gained of embodiment 1 in the present invention3The transmission electron microscope photo figure of nanocrystal.
Fig. 2 is the hollow NaMnF of the gained of embodiment 1 in the present invention3The powder x-ray diffraction spectrogram of nanocrystal.
Fig. 3 is the solid KMnF of the gained of embodiment 2 in the present invention3The transmission electron microscope photo figure of nanocrystal.
Fig. 4 is the solid KMnF of the gained of embodiment 2 in the present invention3The powder x-ray diffraction spectrogram of nanocrystal.
Fig. 5 is the solid KMnF of the doping neodymium of the gained of embodiment 3 in the present invention3The transmission electron microscope photo figure of nanocrystal.
Fig. 6 is the solid KMnF of the doping neodymium of the gained of embodiment 3 in the present invention3The powder x-ray diffraction spectrum of nanocrystal
Figure.
Fig. 7 is the solid KMnF of the doping neodymium of the gained of embodiment 3 in the present invention3The lower switching emission spectrum of nanocrystal
Figure.
Fig. 8 is the hollow NaMnF of the double rare earth ions of doping of the gained of embodiment 4 in the present invention3The transmission electricity of nanocrystal
Mirror photo figure.
Fig. 9 is the hollow NaMnF of the double rare earth ions of doping of the gained of embodiment 4 in the present invention3The powder X-ray of nanocrystal is penetrated
Line diffraction spectrogram.
Figure 10 is the hollow NaMnF of the double rare earth ions of doping of the gained of embodiment 4 in the present invention3The upper conversion of nanocrystal
Launching light spectrogram.
Figure 11 is the solid NaMnF of the double rare earth ions of doping of the gained of embodiment 5 in the present invention3The transmission electricity of nanocrystal
Mirror photo figure.
Figure 12 is the solid NaMnF of the double rare earth ions of doping of the gained of embodiment 5 in the present invention3The upper conversion of nanocrystal
Luminescent spectrum figure.
Figure 13 is the hollow NaMnF of the double rare earth ions of doping of the gained of embodiment 6 in the present invention3The transmission electricity of nanocrystal
Mirror photo figure.
Figure 14 is the hollow NaMnF of the double rare earth ions of doping of the gained of embodiment 6 in the present invention3The upper conversion of nanocrystal
Luminescent spectrum figure.
Figure 15 is the hollow NaMnF of the double rare earth ions of doping of the gained of embodiment 7 in the present invention3The transmission electricity of nanocrystal
Mirror photo figure.
Figure 16 is the hollow NaMnF of the double rare earth ions of doping of the gained of embodiment 7 in the present invention3The upper conversion of nanocrystal
Luminescent spectrum figure.
Figure 17 is 25 DEG C of solid KMnF of synthesis of the gained of embodiment 8 in the present invention3The transmission electron microscope photo of nanocrystal
Figure.
Figure 18 is 25 DEG C of solid KMnF of synthesis of the gained of embodiment 8 in the present invention3The powder x-ray diffraction of nanocrystal
Spectrogram.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiment of the invention is described in further detail.Hereinafter implement
Example is not limited to the scope of the present invention for illustrating the present invention.
Embodiment 1：Prepare the NaMnF of hollow-core construction3Nanocrystal
0.03mol NaOH is completely dissolved in 4mL water and 9mL absolute ethyl alcohols, 20mL oleic acid is added, 10min is stirred；
Then the manganese chloride aqueous solution of 1mL0.5mmol/mL and the potassium fluoride aqueous solution of 4mL0.375mmol/mL are sequentially added, is stirred
1h, obtains NaMnF3Nanocrystal presoma, is then transferred in 50mL reactors, and 24h is reacted at 160 DEG C.Reaction terminates
Afterwards, room temperature is cooled to, absolute ethyl alcohol precipitated product is added, 15min is centrifuged in the case where rotating speed is 8000rpm, centrifugation gained precipitation is used
Water and absolute ethyl alcohol are repeatedly washed, and obtain hollow NaMnF3Nanocrystal.Fig. 1 is hollow NaMnF manufactured in the present embodiment3Receive
The transmission electron microscope photo of meter Jing Ti, Fig. 2 is hollow NaMnF manufactured in the present embodiment3The powder x-ray diffraction spectrum of nanocrystal
Figure, its diffraction maximum and NaMnF3Standard diffraction peak it is consistent, it was demonstrated that products therefrom is pure NaMnF3。
Embodiment 2：Prepare the KMnF of solid construction3Nanocrystal
The step of the present embodiment, is substantially the same manner as Example 1, and difference is：Replace 0.03mol with 0.03mol potassium hydroxide
NaOH.Fig. 3 is solid KMnF manufactured in the present embodiment3The transmission electron microscope photo of nanocrystal, Fig. 4 is prepared for the present embodiment
Solid KMnF3The powder x-ray diffraction spectrogram of nanocrystal, its diffraction maximum is consistent with the standard diffraction peak of KMnF3, it was demonstrated that institute
It is pure KMnF to obtain product3。
Embodiment 3：Prepare the solid KMnF of doping single rare earth ion3Nanocrystal
0.03mol potassium hydroxide is completely dissolved in 4mL water and 9mL absolute ethyl alcohols, 20mL oleic acid, stirring are added afterwards
10min, then sequentially adds 1mL 0.5mmol/mL manganese chlorides and neodymium chloride (mol ratio Mn:Nd=49:1) mixed aqueous solution
And the potassium fluoride aqueous solution of 4mL 0.5mmol/mL, 1h is stirred, obtain the KMnF of doping with rare-earth ions neodymium3Nanocrystal forerunner
Body, is then transferred in 50mL reactors, and 24h is reacted at 160 DEG C.Reaction terminate after, be cooled to room temperature, by reaction system in
15min is centrifuged under rotating speed 11000rpm, products therefrom hexamethylene and absolute ethyl alcohol are repeatedly washed after high speed centrifugation.Fig. 5 is this
The solid KMnF of doping with rare-earth ions neodymium prepared by embodiment3The transmission electron microscope photo of nanocrystal, Fig. 6 is prepared for the present embodiment
Doping with rare-earth ions neodymium solid KMnF3The standard of the powder x-ray diffraction spectrogram of nanocrystal, its diffraction maximum and KMnF3
Diffraction maximum is consistent, it was demonstrated that the matrix of product is KMnF3.Fig. 7 is the solid KMnF of doping with rare-earth ions neodymium manufactured in the present embodiment3
The down-conversion fluorescent spectrum of nanocrystal, display neodymium 1064nm have very strong characteristic emission spectrum (4F3/2→4I11/2).Cause
This, neodymium is successfully entrained among KMnF3 matrixes.
Embodiment 4：Prepare the hollow NaMnF of the double rare earth ions of doping3Nanocrystal
0.03mol NaOH is completely dissolved in 4mL water and 9mL absolute ethyl alcohols, 20mL oleic acid, stirring are added afterwards
10min, then sequentially adds manganese chloride, ytterbium chloride, erbium chloride (the mol ratio Mn of 1mL0.5mmol/mL:Yb:Er=0.405：
0.09：0.005) mixed aqueous solution and the potassium fluoride aqueous solution of 4mL0.75mmol/mL, stir 1h, obtain doping with rare-earth ions
The NaMnF of ytterbium and erbium3Nanocrystal presoma, is then transferred in 50mL reactors, and 24h is reacted at 160 DEG C.Reaction terminates
Afterwards, be cooled to room temperature, by reaction system rotating speed be 10000rpm under high speed centrifugation 15min, then with absolute ethyl alcohol precipitate on
Layer clear liquid, high speed centrifugation gained precipitation, is repeatedly washed with water and absolute ethyl alcohol.Fig. 8 is doping ytterbium and erbium manufactured in the present embodiment
Hollow NaMnF3The transmission electron microscope photo of nanocrystal, Fig. 9 is the hollow NaMnF of doping ytterbium manufactured in the present embodiment and erbium3Receive
The powder x-ray diffraction spectrogram of meter Jing Ti, Figure 10 is the hollow NaMnF of doping ytterbium manufactured in the present embodiment and erbium3Nanocrystal
Up-conversion emission spectrum, display erbium 650-660nm characteristic emission (4F9/2→4I15/2), illustrate that the inventive method can be real
The regulation and control of existing rare earth ion monochromatic emission light.
Embodiment 5：Prepare the solid NaMnF of the double rare earth ions of doping3Nanocrystal
The step of the present embodiment, is substantially the same manner as Example 4, and its difference is：Reduce the ratio of manganese chloride, manganese chloride, chlorine
Change mol ratio Mn in ytterbium, the mixed aqueous solution of erbium chloride:Yb:Er=0.256：0.231：0.013.Figure 11 is prepared for the present embodiment
Doping ytterbium and erbium solid NaMnF3The transmission electron microscope photo of nanocrystal, Figure 12 is doping ytterbium and erbium manufactured in the present embodiment
Solid NaMnF3The up-conversion luminescence collection of illustrative plates of nanocrystal, display erbium 650-660nm characteristic emission (4F9/2→4I15/2)。
This explanation the inventive method can not only regulate and control the pattern of matrix material, can also realize the tune of rare earth ion monochromatic emission light
Control.
Embodiment 6：Oil is to MMnF in alcohol-water-oil synthetic system3The influence of nanocrystal
The step of the present embodiment, is substantially the same manner as Example 4, and difference is：With 20mL decanes acid substitution oleic acid.Figure 13
It is doping ytterbium manufactured in the present embodiment and the hollow NaMnF of erbium3The transmission electron microscope photo of nanocrystal, Figure 14 is the present embodiment system
Standby doping ytterbium and the hollow NaMnF of erbium3The up-conversion luminescence spectrum of nanocrystal, display erbium is sent out in the feature of 650-660nm
Penetrate (4F9/2→4I15/2), illustrate that the inventive method can realize the regulation and control of rare earth ion monochromatic emission light, change oil species and
Ratio does not influence the pattern and property of nanocrystal.
Embodiment 7：Influence of the alcohol to nanocrystal in alcohol-water-oil synthetic system
The step of the present embodiment, is substantially the same manner as Example 4, and difference is：Replace 9mL ethanol with the 14mL tert-butyl alcohols.Figure 15
It is smaller, doping ytterbium manufactured in the present embodiment and the NaMnF of erbium3The transmission electron microscope photo of nanocrystal, illustrates to use
The suitable solvent of the inventive method selection can regulate and control the size of nanocrystal.Figure 16 is doping ytterbium and erbium manufactured in the present embodiment
NaMnF3The up-conversion luminescence spectrum of nanocrystal, display erbium 650-660nm characteristic emission (4F9/2→4I15/2), explanation
The species and ratio for changing solvent do not influence regulation and control of the inventive method to nanocrystal optical property.
Embodiment 8：Prepare the KMnF of solid construction3The step of nanocrystal (25 DEG C of room temperature) the present embodiment and embodiment 2
Essentially identical, difference is：At ambient temperature after (about 25 DEG C) stirring reaction 1h, directly institute is processed with identical purification process
Obtain nanocrystal.Figure 17 is solid KMnF manufactured in the present embodiment3The transmission electron microscope photo of nanocrystal, Figure 18 is the present embodiment
The solid KMnF for preparing3The powder x-ray diffraction spectrogram of nanocrystal, its diffraction maximum is consistent with the standard diffraction peak of KMnF3, card
Bright products therefrom is pure KMnF3.Illustrating room temperature reaction can also obtain the nanocrystal of high-crystallinity, but its crystallinity relative to
The nanocrystal of pyroreaction decreases.
The above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, on the premise of the technology of the present invention principle is not departed from, can also make it is some improvement and
Modification, these are improved and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method containing manganese fluoride nano crystal, it is characterised in that comprise the following steps：
(1) by alkali soluble in alcohol-water solution after, add organic compound CH3(CH2)nCOOH and/or CH3(CnH2n-2) COOH,
Alcohol-water-oil reaction system is uniformly mixed so as to obtain, wherein 6≤n≤18；
(2) added containing Mn in the alcohol-water-oil reaction system for obtaining to step (1)2+The aqueous solution and containing F-The aqueous solution, is uniformly mixed so as to obtain
The presoma of fluoride nano crystal containing manganese, then reacts at 25-200 DEG C, obtains the fluoride nano crystal containing manganese.
2. preparation method according to claim 1, it is characterised in that：In step (1), the alkali be NaOH, KOH,
Na2CO3、NaHCO3、K2CO3、KHCO3In one or more.
3. preparation method according to claim 1, it is characterised in that：In step (1), the alkali and CH3(CH2)nCOOH or
CH3(CnH2n-2) COOH mol ratio be 1:1-4.
4. preparation method according to claim 1, it is characterised in that：In step (1), the alcohol is methyl alcohol, ethanol, third
One or more in alcohol, isopropanol, butanol, isobutanol, the tert-butyl alcohol.
5. preparation method according to claim 1, it is characterised in that：It is described containing Mn in step (2)2+The aqueous solution is containing knot
Brilliant water and/or the manganous salt aqueous solution without the crystallization water.
6. preparation method according to claim 1, it is characterised in that：It is described containing F in step (2)-The aqueous solution is that NaF is water-soluble
Liquid, the KF aqueous solution, NH4One or more in the F aqueous solution and the HF aqueous solution.
7. preparation method according to claim 1, it is characterised in that：In step (2), the Mn2+With F-Mol ratio be
1:3-8。
8. preparation method according to claim 1, it is characterised in that：In step (2), in the alcohol-water-oil reaction system
It is additionally added rare earth ion.
9. preparation method according to claim 8, it is characterised in that：The rare earth ion is Yb3+、Er3+、Tm3+、Ho3+With
Nd3+In one or more.
10. preparation method according to claim 8, it is characterised in that：The Mn2+It is 1- with the mol ratio of rare earth ion
49:1。
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