CN104371715B - A kind of water solublity molybdenum trioxide up-conversion nano material and preparation method thereof - Google Patents
A kind of water solublity molybdenum trioxide up-conversion nano material and preparation method thereof Download PDFInfo
- Publication number
- CN104371715B CN104371715B CN201410702157.9A CN201410702157A CN104371715B CN 104371715 B CN104371715 B CN 104371715B CN 201410702157 A CN201410702157 A CN 201410702157A CN 104371715 B CN104371715 B CN 104371715B
- Authority
- CN
- China
- Prior art keywords
- molybdenum trioxide
- conversion nano
- water
- coo
- nano material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 239000008187 granular material Substances 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 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 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 238000005119 centrifugation Methods 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
- 239000002244 precipitate Substances 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
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000003384 imaging method Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 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
- 239000007850 fluorescent dye Substances 0.000 abstract description 2
- 238000001215 fluorescent labelling Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 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
- 239000000463 material Substances 0.000 description 16
- 229920000587 hyperbranched polymer Polymers 0.000 description 9
- 238000004020 luminiscence type Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- -1 rare earth ion Chemical class 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229910002319 LaF3 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
- 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000003081 coactivator Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of water solublity molybdenum trioxide up-conversion nano material and preparation method thereof, the upper conversion nano granule being substrate with molybdenum trioxide initially with the synthesis of high temperature thermal decomposition method, then adopt Tetrafluoroboric acid nitrous NOBF4Process UCNPs, replace the oleic acid molecular on its surface, finally react with hydrophilic dissaving polymer, obtain a kind of water solublity molybdenum trioxide up-conversion nano material。Water solublity MoO prepared by the present invention3: Yb, Er/Tm nano material, improve the optical property of molybdenum trioxide, can be used for solaode, can improving the spectral absorption scope of solaode, simultaneously because good water solubility, luminous intensity is high, and surface is with being available for the amino of coupling biomacromolecule, carboxyl, hydroxyl isoreactivity group, has a good application prospect in bio-imaging, fluorescent labeling, pharmaceutical carrier etc.。
Description
Technical field
The present invention relates to a kind of water solublity molybdenum trioxide 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) it is a kind of luminescent material sending visible ray under near infrared light excites, by multi-photon mechanism, long-wave radiation can be converted to shortwave 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 by absorb spectroscope properties to excited ion so that it is excite；3. the rare earth ion being excited sends fluorescence and returns substrate。Upper transformation process mainly has the transmission of Excited-state Absorption, energy, two-photon absorption and four kinds of forms of photon avalanches。
Rare earth luminescent material mainly has the compositions such as host material, activator (centre of luminescence), coactivator and sensitizer。The efficiency of up-conversion luminescence depends greatly on the host material of conversion。Host material itself is not luminous, but can provide suitable crystalline field for active ions so that it is produce suitable transmitting。The general requirement that selects of host material has the lattice matched with dopant ion, good chemical stability and relatively low lattice vibration phonon energy etc.。Difference according to matrix material component, it is possible to the substrate of up-conversion luminescent material is broadly divided into oxide, halogenide and sulfide etc.。YF3、LaF3、NaYF4And LiYF4It is all extraordinary substrate Deng material, under near infrared light excites, launches visible ray or even ultraviolet light。Up to the present, the method synthesizing UCNPs mainly has precipitation/coprecipitation, hydrothermal/solvent full-boiled process, pyrolysis method, sol-gel process 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, without the interference of background fluorescence, have a wide range of applications in biomedical etc., such as bio-imaging, biological detection, multi-modality imaging, cancer optical dynamic therapy, medicine carrying etc.。Additionally, except the application at above-mentioned biological field is extensively concerned, abiotic field (as optical information store, 3D shows, safety anti-fake and solaode etc.) also have good application prospect。
MoO3It is by MoO6Octahedron is basic structural unit, and corner-sharing, formation chain connect, the MoO of the chain limit connection formation stratiform altogether that each two is similar3Stoichiometric structure, is connected by Van der Waals force between layers。Nano-sized molybdenum oxide receives more and more attention due to its special structure and performance, has potential and be widely applied in battery electrode, catalyst, resistance fumicants, sensor, optical material etc.。Current nanometer of MoO3The preparation method of material is a lot, wherein mainly includes the sedimentation method, hydro-thermal method, chemical vapour deposition technique, gel casting forming method, sol-gel process and sol-gel self-combustion synthesis etc.。These methods are utilized to synthesize the MoO of different morphologies successively3Material, including threadiness, crystal whisker-shaped, flake, film like, bar-shaped, wire, nanotube, nano belt, spherical etc.。
At present, the research of nano-sized molybdenum oxide is concentrated mainly on the aspect such as preparation method and morphology controllable, and the research for nano-sized molybdenum oxide based compound is relatively fewer。Owing to molybdenum trioxide has special layer structure, it is possible to by some little molecule or ion, for instance hydrion, alkali metal ion, alkaline-earth metal ions, organic molecule etc. are inserted into the octahedra space connecting formation or interlayer forms MoO3Based compound。The lewis' acid of these insertions is possible not only to rock-steady structure, it is most important that can improve MoO3Catalysis and optically and electrically performance etc.。
Hai-QiaoWang is prepared for a kind of MoO3: Yb/Er nano-complex (SolarEnergyMaterials&SolarCells, 105 (2012), 196-201), and it is used for the cushion of organic photovoltaic battery, play the effect of two aspects, one is hole injection layer, and two are able to absorb the sunlight of infrared band, expand the spectral absorption scope of organic photovoltaic battery。But MoO prepared by the document3: Yb/Er nano-complex is not water miscible, and is only used for photovoltaic cell field。
Summary of the invention
The present invention is directed to above-mentioned deficiency, be prepared for a kind of water solublity molybdenum trioxide up-conversion nano material and preparation method thereof。
The technical scheme is that:
(1) by ammonium heptamolybdate (NH that Mo:Yb:Er/Tm mol ratio is 69%-78%:20%-30%:1%-2%4)6Mo7O24、Yb(CF3COO)3With Er (CF3COO)3Or Tm (CF3COO)3Dissolving is in deionized water; bath raio 1:10; ultrasonic 1-24h; adds trifluoroacetic acid and regulates pH value 2-5, after heating 1-5h, naturally cool to room temperature in 100-120 DEG C of oil bath; add dehydrated alcohol; is centrifuged and is precipitated, and repeatedly by water and washing with alcohol, finally anneal 4-10h by the centrifugal precipitate obtained at 800 DEG C。
(2) by the 5mL Tetrafluoroboric acid nitrous NOBF of conversion nano granule hexane dispersion soln on the 5mL molybdenum trioxide of 1-5g/L Yu 0.1-0.6g/L4Dichloromethane solution at room temperature mixes, and is shaken gently for by mixture, until UCNPs precipitation, is then centrifuged for separating, removes supernatant。
(3) conversion nano granule on the molybdenum trioxide obtained in (2) is scattered in water again, 1:1-1:10 by volume, adds the hydrophilic dissaving 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 hydrophilic dissaving polymer in step (3) is the one in hydroxyl, amido or carboxyl。
The synthesis of Hyperbranched Polymer with Terminal Amido is referred to following open source literature: Zhang Feng, Chen Yuyue, Zhang Desuo, Hua Yanrong, Zhao Bing. the preparation of Hyperbranched Polymer with Terminal Amido and quaternary ammonium salt thereof and performance [J]. polymer material science and engineering, 2009,25 (8): 141-144；CN200710020794.8 super-branching reactive dye salt-free dyeing auxiliary；Colorationtechnology, 2007,123 (6): 351-357；AATCCREVIEW, 2010,10 (6): 56-60；BIOMACROMOLECULES, 2010,11 (1): 245-251；CHEMICALRESEARCHINCHINESEUNIVERSITIES, 2005,21 (3): 345-354。
The synthesis of end carboxyl super branched polymer is referred to following open source literature: torrential by force, Chen little Ke, Wang Xuechuan etc. the preparation of end carboxyl super branched polymer-aluminum chrome-free tanning agent and application [J]. fine chemistry industry, 2012,29 (11): 1098-1102,1120；Torrential by force, Zhang Guoguo, Luo Min etc. the preparation of generation end carboxyl super branched polymer and sign [J]. 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 tan effect. Shaanxi Tech Univ, 2007。
The synthesis of Hyperbranched Polymer with Terminal Hydroxyl is referred 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 China's coating, 2011,26 (3): 53-57；Wang Xuechuan, Hu Yanxin, Zheng Shujie etc. Hyperbranched Polymer with Terminal Hydroxyl is to Fe3+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 modified [J]. daily chemical industry, 2012,42 (6): 413-417。
Compared with prior art, it is an advantage of the current invention that: water solublity MoO prepared by the present invention3: Yb, Er/Tm nano material, improve the optical property of molybdenum trioxide, can be used for solaode, can improving the spectral absorption scope of solaode, simultaneously because good water solubility, luminous intensity is high, and surface is with being available for the amino of coupling biomacromolecule, carboxyl, hydroxyl isoreactivity group, has a good application prospect in bio-imaging, fluorescent labeling, pharmaceutical carrier etc.。
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further。
Embodiment 1:
By 0.78mmol ammonium heptamolybdate (NH4)6Mo7O24, 0.2mmol Yb (CF3COO)3Er (CF with 0.02mmol3COO)3Dissolve in deionized water, bath raio 1:10, ultrasonic 1h, add trifluoroacetic acid and regulate pH value 2, after 1h is heated in 100 DEG C of oil baths, naturally cool to room temperature, add dehydrated alcohol, being centrifuged and be precipitated, repeatedly by water and washing with alcohol, finally anneal 4h by the centrifugal precipitate obtained at 800 DEG C。
5mL Tetrafluoroboric acid nitrous NOBF by conversion nano granule hexane dispersion soln on the 5mL molybdenum trioxide of 1g/L Yu 0.1g/L4Dichloromethane solution at room temperature mixes, mixture is shaken gently for, until UCNPs precipitation, is then centrifuged for separating, remove supernatant, again it is scattered in again in water, 1:10 by volume, adds 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 (NH4)6Mo7O24, 0.3mmol Yb (CF3COO)3Er (CF with 0.01mmol3COO)3Dissolve in deionized water, bath raio 1:10, ultrasonic 5h, add trifluoroacetic acid and regulate pH value 3, after 2h is heated in 110 DEG C of oil baths, naturally cool to room temperature, add dehydrated alcohol, being centrifuged and be precipitated, repeatedly by water and washing with alcohol, finally anneal 6h by the centrifugal precipitate obtained at 800 DEG C。
5mL Tetrafluoroboric acid nitrous NOBF by conversion nano granule hexane dispersion soln on the 5mL molybdenum trioxide of 2g/L Yu 0.3g/L4Dichloromethane solution at room temperature mixes, mixture is shaken gently for, until UCNPs precipitation, is then centrifuged for separating, remove supernatant, again it is scattered in again in water, 1:5 by volume, adds 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 0.78mmol4)6Mo7O24, 0.2mmol Yb (CF3COO)3Tm (CF with 0.02mmol3COO)3Dissolve in deionized water, bath raio 1:10, ultrasonic 10h, add trifluoroacetic acid and regulate pH value 4, after 3h is heated in 120 DEG C of oil baths, naturally cool to room temperature, add dehydrated alcohol, being centrifuged and be precipitated, repeatedly by water and washing with alcohol, finally anneal 8h by the centrifugal precipitate obtained at 800 DEG C。
5mL Tetrafluoroboric acid nitrous NOBF by conversion nano granule hexane dispersion soln on the 5mL molybdenum trioxide of 3g/L Yu 0.3g/L4Dichloromethane solution at room temperature mixes, mixture is shaken gently for, until UCNPs precipitation, is then centrifuged for separating, remove supernatant, again it is scattered in again in water, 1:1 by volume, adds 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 0.69mmol4)6Mo7O24, 0.3mmol Yb (CF3COO)3Tm (CF with 0.01mmol3COO)3Dissolve in deionized water, bath raio 1:10, ultrasonic 12h, add trifluoroacetic acid and regulate pH value 5, after 5h is heated in 120 DEG C of oil baths, naturally cool to room temperature, add dehydrated alcohol, being centrifuged and be precipitated, repeatedly by water and washing with alcohol, finally anneal 10h by the centrifugal precipitate obtained at 800 DEG C。
5mL Tetrafluoroboric acid nitrous NOBF by conversion nano granule hexane dispersion soln on the 5mL molybdenum trioxide of 5g/L Yu 6g/L4Dichloromethane solution at room temperature mixes, mixture is shaken gently for, until UCNPs precipitation, is then centrifuged for separating, remove supernatant, again it is scattered in again in water, 1:1 by volume, adds 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 clearly demonstrating example of the present invention, 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 all of embodiment be given exhaustive。Every belong to apparent change that technical scheme amplified out or the variation row still in protection scope of the present invention。
Claims (1)
1. the preparation method of a water solublity molybdenum trioxide up-conversion nano material, it is characterised in that:
Step one, by the ammonium heptamolybdate (NH that Mo:Yb:Er or Mo:Yb:Tm mol ratio is 69%-78%:20%-30%:1%-2%4)6Mo7O24、Yb(CF3COO)3、Er(CF3COO)3Or (NH4)6Mo7O24、Yb(CF3COO)3、Tm(CF3COO)3Dissolve in deionized water, bath raio 1:10, ultrasonic 1-24h, use trifluoroacetic acid CF3COOH regulates pH value 2-5, after heating 1-5h, naturally cools to room temperature, adds dehydrated alcohol, be centrifuged and be precipitated in 100-120 DEG C of oil bath, repeatedly by water and washing with alcohol, and annealing 4-10h at the precipitate 800 DEG C that finally will centrifugal obtain；
Step 2, on molybdenum trioxide step one obtained, conversion nano granule is configured to the 5mL hexane dispersion soln of 1-5g/L, with the 5mL Tetrafluoroboric acid nitrous NOBF of 0.1-0.6g/L4Dichloromethane solution at room temperature mixes, and is shaken gently for by mixture, until conversion nano particle precipitation on molybdenum trioxide, is then centrifuged for separating, removes supernatant；
Step 3, conversion nano granule on the molybdenum trioxide obtained in step 2 is scattered in water again, 1:1-1:10 by volume, add the hydrophilic dissaving polymer aqueous solution of 0.01g/L-100g/L, the end group of wherein said hydrophilic dissaving polymer is the one in hydroxyl, amido or carboxyl, ultrasonic reaction 10-120min, centrifugation, repeatedly wash with distilled water and ethanol, dry。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410702157.9A CN104371715B (en) | 2014-11-28 | 2014-11-28 | A kind of water solublity molybdenum trioxide up-conversion nano material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410702157.9A CN104371715B (en) | 2014-11-28 | 2014-11-28 | A kind of water solublity molybdenum trioxide up-conversion nano material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104371715A CN104371715A (en) | 2015-02-25 |
| CN104371715B true CN104371715B (en) | 2016-06-22 |
Family
ID=52550917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410702157.9A Active CN104371715B (en) | 2014-11-28 | 2014-11-28 | A kind of water solublity molybdenum trioxide up-conversion nano material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104371715B (en) |
Families Citing this family (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 |
| 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 |
| 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 |
| KR102423807B1 (en) * | 2017-11-24 | 2022-07-20 | 주식회사 엘지에너지솔루션 | Process for preparing hexagonal molybdenum oxides nano rods |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254890A (en) * | 2013-05-20 | 2013-08-21 | 桂林理工大学 | Preparation method of hyperbranched poly-glycidyl ether grated rare earth up-conversion luminescence nanocrystal |
| CN103589432A (en) * | 2013-11-27 | 2014-02-19 | 中国科学院福建物质结构研究所 | Rare earth-doped lithium lutetium fluoride nano-material, and preparation method and application thereof |
| CN104043138A (en) * | 2014-05-29 | 2014-09-17 | 北京大学 | Rare earth-based nanoparticle magnetic resonance contrast agent and preparation method thereof |
-
2014
- 2014-11-28 CN CN201410702157.9A patent/CN104371715B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254890A (en) * | 2013-05-20 | 2013-08-21 | 桂林理工大学 | Preparation method of hyperbranched poly-glycidyl ether grated rare earth up-conversion luminescence nanocrystal |
| CN103589432A (en) * | 2013-11-27 | 2014-02-19 | 中国科学院福建物质结构研究所 | Rare earth-doped lithium lutetium fluoride nano-material, and preparation method and application thereof |
| CN104043138A (en) * | 2014-05-29 | 2014-09-17 | 北京大学 | Rare earth-based nanoparticle magnetic resonance contrast agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| A Generalized Ligand-Exchange Strategy Enabling Sequential Surface Functionalization of Colloidal Nanocrystals;Angang Dong等;《J. Am. Chem. Soc.》;20111231;第133卷;196–201 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104371715A (en) | 2015-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104371715B (en) | A kind of water solublity molybdenum trioxide up-conversion nano material and preparation method thereof | |
| CN104371714B (en) | A kind of molybdic oxide-graphene oxide composite material and preparation method thereof | |
| Zhao et al. | Spectroscopic studies of the optical properties of carbon dots: recent advances and future prospects | |
| CN104371727B (en) | Conversion nano granule and preparation method thereof on a kind of water solublity | |
| Ragazzon et al. | Optical processes in carbon nanocolloids | |
| Gavrilović et al. | Multifunctional Eu3+-and Er3+/Yb3+-doped GdVO4 nanoparticles synthesized by reverse micelle method | |
| CN104449714B (en) | Conversion nano granule-graphene oxide composite material and preparation method thereof in one | |
| Shen et al. | The production of pH-sensitive photoluminescent carbon nanoparticles by the carbonization of polyethylenimine and their use for bioimaging | |
| Zou et al. | A water-dispersible dye-sensitized upconversion nanocomposite modified with phosphatidylcholine for lymphatic imaging | |
| CN104357931B (en) | A kind of fluorescence salix monogolica regenerated celulose fibre and preparation method thereof | |
| CN104498037B (en) | Conversion nano granule and preparation method thereof on the water solublity that a kind of PAMAM modifies | |
| CN104452101B (en) | A kind of Static Spinning fluorescence PVA nano fibrous membrane and preparation method thereof | |
| Lu et al. | Green anhydrous assembly of carbon dots via solar light irradiation and its multi-modal sensing performance | |
| Roeinfard et al. | Synthesis of graphene quantum dots decorated with Se, Eu and Ag as photosensitizer and study of their potential to use in photodynamic therapy | |
| CN104388088B (en) | Conversion nano granule and preparation method thereof on the water solublity of a kind of Fluorescence Increasing | |
| Li et al. | Influence of silica surface coating on operated photodynamic therapy property of Yb3+-Tm3+: Ga (III)-doped ZnO upconversion nanoparticles | |
| Ansari et al. | Highly colloidal luminescent porous Tb-doped gadolinium oxide nanoparticles: Photophysical and luminescent properties | |
| Yan et al. | Hydrothermal synthesis of NaYF4: Yb3+, Tm3+ upconversion microparticles and their effects on polymerization for stereolithography | |
| CN104386665A (en) | Preparation method and bioapplication of single photon/double photon amorphous carbon dot | |
| CN104357934B (en) | A kind of fluorescence Lyocell fiber and preparation method thereof | |
| Anh et al. | High monodisperse nanospheres Gd2O3: Yb3+, Er3+ with strong upconversion emission fabricated by synergistic chemical method | |
| Chen et al. | Photodynamic and photothermal synergistic behavior of triphenylamine-porphyrin nanoparticles for DNA interaction, cellular cytotoxicity and localization | |
| Ibrayev et al. | Optical properties of N-and S-doped carbon dots based on citric acid and L-cysteine | |
| Watkins et al. | Fluorescence behaviour and singlet oxygen production of aluminium phthalocyanine in the presence of upconversion nanoparticles | |
| CN108714223B (en) | Contrast agent with magnetic resonance and fluorescence dual imaging characteristics and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Hu Jigang Inventor before: Zhao Bing |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170823 Address after: 050051, 9, Yuhua West Road, 3 West Hebei, Shijiazhuang Province Patentee after: Hu Jigang Address before: Xiangcheng District Yuyao road Suzhou City, Jiangsu province 215001 yuan and an intersection of Cambridge Riverbank Garden 5 2101 Patentee before: Zhao Bing |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180702 Address after: 226223 the two groups of Yongfeng village, North New Town, Qidong, Jiangsu Patentee after: Qidong Changlong vegetable and fruit professional cooperative Address before: 050051 No. 3 Yuhua West Road, Qiaoxi District, Shijiazhuang, Hebei, 3 Patentee before: Hu Jigang |