CN104371715A - Water-soluble molybdenum trioxide up-conversion nanometer material and preparation method thereof - Google Patents
Water-soluble molybdenum trioxide up-conversion nanometer material and preparation method thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 34
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002086 nanomaterial Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 6
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- WCZAXBXVDLKQGV-UHFFFAOYSA-N n,n-dimethyl-2-(7-oxobenzo[c]fluoren-5-yl)oxyethanamine oxide Chemical compound C12=CC=CC=C2C(OCC[N+](C)([O-])C)=CC2=C1C1=CC=CC=C1C2=O WCZAXBXVDLKQGV-UHFFFAOYSA-N 0.000 claims description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000009736 wetting Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 5
- -1 amino, carboxyl Chemical group 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 abstract description 2
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000003937 drug carrier Substances 0.000 abstract description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract 1
- 229910004064 NOBF4 Inorganic materials 0.000 abstract 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000005642 Oleic acid Substances 0.000 abstract 1
- 239000007850 fluorescent dye Substances 0.000 abstract 1
- 238000001215 fluorescent labelling Methods 0.000 abstract 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000000975 co-precipitation Methods 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
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- 239000002127 nanobelt Substances 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
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Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a water-soluble molybdenum trioxide up-conversion nanometer material and a preparation method thereof. The preparation method includes steps of firstly adopting the high-temperature thermal decomposition method to synthesize up-conversion nanoparticles (UCNPs) based on molybdenum trioxide, adopting NOBF4 to treat the UCNPs for replacing oleic acid molecules on the surface of the UCNPs, finally subjecting the UCNPs to reaction with hydrophilic hyperbranched polymers to obtain the water-soluble molybdenum trioxide up-conversion nanometer material. By the water-soluble MoO3:Yb, Er/Tm nanometer material prepared, the optical performance of molybdenum trioxide is improved. The nanometer material can be used for solar cells, so that the spectral absorption range of the solar cells can be enlarged. Meanwhile, the water-soluble molybdenum trioxide up-conversion nanometer material has promising application prospect in bioimaging, fluorescent labelling, drug carriers and the like as being good in water solubility and high in light intensity and being provided with active groups such as amino, carboxyl and hydroxyl available for coupling biomacromolecules.
Description
Technical field
The present invention relates to a kind of water-soluble molybdic oxide up-conversion nano material and preparation method thereof, belong to field of nanometer material technology.
Background technology
Rare earth up-conversion luminescent material Up-conversion(UC) be a kind of luminescent material sending visible ray under near infrared light excites, namely by multi-photon mechanism, long-wave radiation is converted to short-wave radiation.This material emission runs counter to Stokes law, and be therefore otherwise known as anti-Stokes law luminescent material.UC luminescence is based on the interelectric transition of rare earth element 4f.Luminescence process can be divided into three steps: 1. parent lattice absorbs excitation energy; 2. parent lattice is by the spectroscope properties of absorption to excited ion, makes it excite; 3. the rare earth ion be excited sends fluorescence and returns matrix.Upper switching process mainly contains excited state absorption, transmission ofenergy, two-photon absorption and photon avalanches four kinds of forms.
Rare earth luminescent material mainly contains the compositions such as substrate material, activator (luminescence center), coactivator and sensitizing agent.The efficiency of up-conversion luminescence depends on the substrate material of conversion to a great extent.Substrate material itself is not luminous, but can provide suitable crystal field for active ions, makes it produce suitable transmitting.The selection general requirement of substrate material has the lattice, preferably chemical stability and the lower lattice vibration phonon energy etc. that match with dopant ion.According to the difference of matrix material component, the matrix of up-conversion luminescent material mainly can be divided into oxide compound, halogenide and sulfide etc.YF
3, LaF
3, NaYF
4and LiYF
4be all extraordinary matrix Deng material, under near infrared light excites, launch visible ray or even UV-light.Up to the present, the method for synthesizing UCNPs mainly contains precipitation/coprecipitation method, the hot method of hydrothermal/solvent, pyrolysis method, sol-gel method and self-propagating combustion etc.
Up-conversion luminescence nanomaterial (UCNPs) has high chemical stability, excellent light stability, narrow band gap transmitting, there is stronger tissue penetration under near-infrared laser excites, to biological tissue's not damaged, interference without background fluorescence, have a wide range of applications, as bio-imaging, biological detection, multi-modality imaging, cancer optical dynamic therapy, medicine carrying etc. in biomedicine etc.In addition, except the application at above-mentioned biological field is extensively concerned, abiotic field (as optical information store, 3D display, safety anti-fake and solar cell etc.) also have good application prospect.
MoO
3by MoO
6octahedron is basic structural unit, corner-sharing, forms chain and connects, and every two similar chains altogether limit are connected to form the MoO of stratiform
3stoichiometric structure, is connected by Van der Waals force between layers.Nano-sized molybdenum oxide receives increasing concern due to its special stuctures and properties, has potential and apply widely in battery electrode, catalyzer, resistance fumicants, sensor, optical material etc.Current nanometer MoO
3the preparation method of material is a lot, wherein mainly comprises the precipitator method, hydrothermal method, chemical Vapor deposition process, gel casting forming method, sol-gel method and sol-gel self-combustion synthesis etc.The MoO of different morphologies that utilized these methods to synthesize successively
3material, comprising threadiness, crystal whisker-shaped, flake, film like, bar-shaped, wire, nanotube, nano belt, spherical etc.
At present, the research of nano-sized molybdenum oxide mainly concentrates on the aspect such as preparation method and morphology controllable, and relatively less for the research of nano-sized molybdenum oxide based compound.Because molybdic oxide has special laminate structure, can by some small molecules or ion, such as hydrogen ion, alkalimetal ion, alkaline-earth metal ions, organic molecule etc. are inserted into space that octahedron is connected to form or interlayer forms MoO
3based compound.These lewis' acids inserted not only can rock steady structure, the most important thing is to improve MoO
3catalysis and optics and electric property etc.
Hai-Qiao Wang has prepared a kind of MoO
3: Yb/Er nano-complex (Solar Energy Materials & Solar Cells, 105 (2012), 196-201), and it is used for the buffer layer of organic photovoltaic battery, play the effect of two aspects, one is hole injection layer, and two is the sunlights that can absorb infrared band, expands the spectral absorption scope of organic photovoltaic battery.But MoO prepared by the document
3: Yb/Er nano-complex is not water miscible, and can only be used for photovoltaic cell field.
Summary of the invention
The present invention is directed to above-mentioned deficiency, prepare a kind of water-soluble molybdic oxide up-conversion nano material and preparation method thereof.
The present invention is achieved by following technical proposals:
(1) by Mo:Yb:Er/Tm mol ratio be the Ammonium Heptamolybdate (NH of 69%-78%:20%-30%:1%-2%
4)
6mo
7o
24, Yb (CF
3cOO)
3with Er (CF
3cOO)
3or Tm (CF
3cOO)
3dissolve in deionized water; bath raio 1:10; ultrasonic 1-24h; add trifluoroacetic acid adjust ph 2-5, after heating 1-5h, naturally cools to room temperature; add dehydrated alcohol in 100-120 DEG C of oil bath; to be centrifugally precipitated, repeatedly use water and washing with alcohol, finally anneal the centrifugal throw out obtained at 800 DEG C 4-10 h.
(2) by the 5mL Tetrafluoroboric acid nitrous NOBF of conversion nano particle hexane dispersion soln and 0.1-0.6g/L on the 5mL molybdic oxide of 1-5g/L
4dichloromethane solution at room temperature mixes, and is shaken gently by mixture, until UCNPs precipitation, and then centrifugation, removing supernatant liquor.
(3) conversion nano particle on the molybdic oxide obtained in (2) is scattered in water again, 1:1-1:10 by volume, adds the wetting ability hyperbranched polymer aqueous solution of 0.01g/L-100g/L, ultrasonic reaction 10-120min, centrifugation, repeatedly washs with distilled water and ethanol, dry.
Preferably, the end group of the wetting ability hyperbranched polymer in step (3) is the one in hydroxyl, amido or carboxyl.
The synthesis of Hyperbranched Polymer with Terminal Amido can with reference to following open source literature: Zhang Feng, Chen Yuyue, Zhang Desuo, Hua Yanrong, Zhao Bing. the fabrication & properties [J] of Hyperbranched Polymer with Terminal Amido and quaternary ammonium salt thereof. polymer material science and engineering, 2009,25 (8): 141-144; CN200710020794.8 super-branching reactive dye salt-free dyeing auxiliary; Coloration technology, 2007,123 (6): 351-357; AATCC REVIEW, 2010,10 (6): 56-60; BIOMACROMOLECULES, 2010,11 (1): 245-251; CHEMICAL RESEARCH IN CHINESE UNIVERSITIES, 2005,21 (3): 345-354.
The synthesis of end carboxyl super branched polymer can with reference to following open source literature: torrential by force, Chen little Ke, Wang Xuechuan etc. the preparations and applicatio [J] of end carboxyl super branched polymer-aluminium chrome-free tanning agent. fine chemistry industry, 2012,29 (11): 1098-1102,1120; Torrential by force, Zhang Guoguo, Luo Min etc. the UV absorber [J] of generation end carboxyl super branched polymer. fine chemistry industry, 2012,29 (7): 692-696; Torrential by force. the synthesis of end carboxyl super branched polymer and help the research [D] of effect of tanning. Shaanxi Tech Univ, 2007.
The synthesis of Hyperbranched Polymer with Terminal Hydroxyl can with reference to following open source literature: Yang Baoping, Zhang Pengfei, Cui Jinfeng etc. the study on the modification of Hyperbranched Polymer with Terminal Hydroxyl and the application [J] in coating thereof. and Chinese coating, 2011,26 (3): 53-57; Wang Xuechuan, Hu Yanxin, Zheng Shujie etc. Hyperbranched Polymer with Terminal Hydroxyl is to Fe
3+absorption behavior research [J]. New Chemical Materials, 2011,39 (9): 26-29,47; Torrential by force, Zhang Guoguo, Wang Xuechuan etc. the synthesis of Hyperbranched Polymer with Terminal Hydroxyl and modification [J]. daily chemical industry, 2012,42 (6): 413-417.
Compared with prior art, the invention has the advantages that: water-soluble MoO prepared by the present invention
3: Yb, Er/Tm nano material, improve the optical property of molybdic oxide, can be used for solar cell, can improve the spectral absorption scope of solar cell, simultaneously due to good water solubility, luminous intensity is high, and surface is with for amino, carboxyl, the hydroxyl isoreactivity group of coupling biomacromolecule, can having a good application prospect in bio-imaging, fluorescent mark, pharmaceutical carrier etc.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.
Embodiment 1:
By 0.78mmol Ammonium Heptamolybdate (NH
4)
6mo
7o
24, 0.2mmol Yb (CF
3cOO)
3with the Er (CF of 0.02mmol
3cOO)
3dissolve in deionized water, bath raio 1:10, ultrasonic 1h, add trifluoroacetic acid adjust ph 2, heat 1h in 100 DEG C of oil baths after, naturally cool to room temperature, add dehydrated alcohol, centrifugally be precipitated, repeatedly use water and washing with alcohol, finally anneal the centrifugal throw out obtained at 800 DEG C 4 h.
By the 5mL Tetrafluoroboric acid nitrous NOBF of conversion nano particle hexane dispersion soln and 0.1g/L on the 5mL molybdic oxide of 1g/L
4dichloromethane solution at room temperature mixes, mixture is shaken gently, until UCNPs precipitation, then centrifugation, removing supernatant liquor, again be scattered in again in water, 1:10 by volume, add the Hyperbranched Polymer with Terminal Amido aqueous solution of 5g/L, ultrasonic reaction 20min, centrifugation, repeatedly washs with distilled water and ethanol, dry.
Embodiment 2:
By 0.69mmol Ammonium Heptamolybdate (NH
4)
6mo
7o
24, 0.3mmol Yb (CF
3cOO)
3with the Er (CF of 0.01mmol
3cOO)
3dissolve in deionized water, bath raio 1:10, ultrasonic 5h, add trifluoroacetic acid adjust ph 3, heat 2h in 110 DEG C of oil baths after, naturally cool to room temperature, add dehydrated alcohol, centrifugally be precipitated, repeatedly use water and washing with alcohol, finally anneal the centrifugal throw out obtained at 800 DEG C 6 h.
By the 5mL Tetrafluoroboric acid nitrous NOBF of conversion nano particle hexane dispersion soln and 0.3g/L on the 5mL molybdic oxide of 2g/L
4dichloromethane solution at room temperature mixes, mixture is shaken gently, until UCNPs precipitation, then centrifugation, removing supernatant liquor, again be scattered in again in water, 1:5 by volume, add the end carboxyl super branched polymer aqueous solution of 10g/L, ultrasonic reaction 60min, centrifugation, repeatedly washs with distilled water and ethanol, dry.
Embodiment 3:
By the Ammonium Heptamolybdate (NH of 0.78mmol
4)
6mo
7o
24, 0.2mmol Yb (CF
3cOO)
3with the Tm (CF of 0.02mmol
3cOO)
3dissolve in deionized water, bath raio 1:10, ultrasonic 10h, add trifluoroacetic acid adjust ph 4, heat 3h in 120 DEG C of oil baths after, naturally cool to room temperature, add dehydrated alcohol, centrifugally be precipitated, repeatedly use water and washing with alcohol, finally anneal the centrifugal throw out obtained at 800 DEG C 8 h.
By the 5mL Tetrafluoroboric acid nitrous NOBF of conversion nano particle hexane dispersion soln and 0.3g/L on the 5mL molybdic oxide of 3g/L
4dichloromethane solution at room temperature mixes, mixture is shaken gently, until UCNPs precipitation, then centrifugation, removing supernatant liquor, again be scattered in again in water, 1:1 by volume, add the Hyperbranched Polymer with Terminal Hydroxyl aqueous solution of 20g/L, ultrasonic reaction 90min, centrifugation, repeatedly washs with distilled water and ethanol, dry.
Embodiment 4:
By the Ammonium Heptamolybdate (NH of 0.69mmol
4)
6mo
7o
24, 0.3mmol Yb (CF
3cOO)
3with the Tm (CF of 0.01mmol
3cOO)
3dissolve in deionized water, bath raio 1:10, ultrasonic 12h, add trifluoroacetic acid adjust ph 5, heat 5h in 120 DEG C of oil baths after, naturally cool to room temperature, add dehydrated alcohol, centrifugally be precipitated, repeatedly use water and washing with alcohol, finally anneal the centrifugal throw out obtained at 800 DEG C 10 h.
By the 5mL Tetrafluoroboric acid nitrous NOBF of conversion nano particle hexane dispersion soln and 6g/L on the 5mL molybdic oxide of 5g/L
4dichloromethane solution at room temperature mixes, mixture is shaken gently, until UCNPs precipitation, then centrifugation, removing supernatant liquor, again be scattered in again in water, 1:1 by volume, add the Hyperbranched Polymer with Terminal Amido aqueous solution of 50g/L, ultrasonic reaction 120min, centrifugation, repeatedly washs with distilled water and ethanol, dry.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of amplifying out or variation be still in the row of protection scope of the present invention.
Claims (5)
1. water-soluble molybdic oxide up-conversion nano material and preparation method thereof, is characterized in that:
Step one, by a certain amount of Ammonium Heptamolybdate (NH
4)
6mo
7o
24, Yb (CF
3cOO)
3with Er (CF
3cOO)
3or Tm (CF
3cOO)
3dissolve in deionized water, bath raio 1:10, ultrasonic 1-24h, adjust ph 2-5, heat 1-5h in 100-120 DEG C of oil bath after, naturally cool to room temperature, add dehydrated alcohol, centrifugally to be precipitated, repeatedly to use water and washing with alcohol, finally by the centrifugal throw out anneal obtained;
Step 2, by the 5mL Tetrafluoroboric acid nitrous NOBF of conversion nano particle hexane dispersion soln and 0.1-0.6g/L on the 5mL molybdic oxide of 1-5g/L
4dichloromethane solution at room temperature mixes, and is shaken gently by mixture, until UCNPs precipitation, and then centrifugation, removing supernatant liquor;
Step 3, is scattered in water again by conversion nano particle on the molybdic oxide obtained in step 2,1:1-1:10 by volume, add the wetting ability hyperbranched polymer aqueous solution of 0.01g/L-100g/L, ultrasonic reaction 10-120min, centrifugation, repeatedly wash with distilled water and ethanol, dry.
2. water-soluble molybdic oxide up-conversion nano material of one according to claim 1 and preparation method thereof, is characterized in that, the Mo:Yb:Er/Tm mol ratio in step one is 69%-78%:20%-30%:1%-2%.
3. water-soluble molybdic oxide up-conversion nano material of one according to claim 1 and preparation method thereof, is characterized in that, the acid that in step one, adjust ph is used is trifluoroacetic acid CF
3cOOH.
4. water-soluble molybdic oxide up-conversion nano material of one according to claim 1 and preparation method thereof, is characterized in that, the anneal described in step one is the 4-10 h that anneals at 800 DEG C.
5. water-soluble molybdic oxide up-conversion nano material of one according to claim 1 and preparation method thereof, is characterized in that, the end group of the wetting ability hyperbranched polymer described in step 3 is the one in hydroxyl, amido or carboxyl.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762084A (en) * | 2015-04-10 | 2015-07-08 | 大连民族学院 | Preparation method of jellyfish-like rare-earth-doped MoO3 green upconversion luminescent material |
| CN107385882A (en) * | 2017-09-17 | 2017-11-24 | 赵兵 | Fluorescent fiber based on molybdenum trioxide up-conversion nano material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762084A (en) * | 2015-04-10 | 2015-07-08 | 大连民族学院 | Preparation method of jellyfish-like rare-earth-doped MoO3 green upconversion luminescent material |
| CN107385882A (en) * | 2017-09-17 | 2017-11-24 | 赵兵 | Fluorescent fiber based on molybdenum trioxide up-conversion nano material |
| CN107446581A (en) * | 2017-09-17 | 2017-12-08 | 赵兵 | A kind of fluorescent natural silk of the rear-earth-doped up-conversion nano material of LBL self-assembly |
| CN107557013A (en) * | 2017-09-17 | 2018-01-09 | 赵兵 | Three-dimensional porous sponge composite based on rare earth up-conversion luminescence nanomaterial |
| CN107385882B (en) * | 2017-09-17 | 2019-08-16 | 福建同利祥纺织实业有限公司 | Fluorescent fiber based on molybdenum trioxide up-conversion nano material |
| CN111094185A (en) * | 2017-11-24 | 2020-05-01 | 株式会社Lg化学 | Preparation method of hexagonal molybdenum trioxide nanorod |
| US11530136B2 (en) | 2017-11-24 | 2022-12-20 | Lg Energy Solution, Ltd. | Preparation method of hexagonal molybdenum oxide nanorod |
| CN110079315A (en) * | 2019-04-08 | 2019-08-02 | 昆明理工大学 | A kind of thermochromism MoO3: Yb, Er up-conversion phosphor, preparation method and its reversible regulation method of up-conversion luminescence |
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