CN105385447A - Low-cost method for preparing NaREF4 type upconversion light-emitting porous microspheres in large quantities - Google Patents
Low-cost method for preparing NaREF4 type upconversion light-emitting porous microspheres in large quantities Download PDFInfo
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- CN105385447A CN105385447A CN201510597253.6A CN201510597253A CN105385447A CN 105385447 A CN105385447 A CN 105385447A CN 201510597253 A CN201510597253 A CN 201510597253A CN 105385447 A CN105385447 A CN 105385447A
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Abstract
The present invention provides a low-cost method for preparing NaREF4 type upconversion light-emitting porous microspheres in large quantities. The method comprises the following steps: adding one or more of ammonium fluoride, ammonium bifluoride and sodium fluoride, adding a rare earth inorganic salt solid into a sodium polyacrylate solution and stirring the solution to obtain a uniform solution; and packaging the solution in a hydrothermal reactor or a microwave synthesis apparatus and performing a heating reaction to obtain an upconversion material. The method has the advantage that the upconversion light-emitting porous microspheres with water solubility are efficiently prepared in large quantities through one-step reaction. The material has the functions of upconversion light emission and mesoporous drug adsorption, so that the material has an excellent application prospect in the fields of biological imaging diagnosis and intelligent drug carriers, and a high-quality and low-cost solution is expected to be provided for the design of a tumor diagnosis and treatment integrated platform.
Description
Technical field
The present invention relates to the preparation method of porous up-conversion luminescent material, be specifically related to a large amount of synthesizing water-solubility porous NaREF of a kind of low cost
4the preparation method of type up-conversion luminescence micro-nano-sphere.
Background technology
Up-conversion refers to when being subject to excitation light irradiation, can the material of the shorter fluorescence of transmitting ratio excitation wavelength, namely absorbs low-frequency light and launches high-frequency light, therefore being called frequency upooaversion.Up-conversion luminescent material owing to can, by infrared ray excited and send visible ray, have the light injury of biological tissue low, advantages such as light penetration depth is large and be widely used in the research application of field of biology.In recent years, porous rare earth up-conversion luminescent material attracts wide attention with the huge applications potentiality in Synergistic treatment in the multimode diagnosis of tumour.
In the luminous host of various types of up-conversion luminescent material, with NaREF
4up-conversion for matrix is one of upconverting fluorescent material that luminous efficiency is the highest.NaREF known at present
4type is changed porous microsphere preparation method and mainly contain PEI/DEG system or Trisodium Citrate/EG/H
2the hydrothermal synthesis method of O system and high temperature oil phase pyrolyzing synthesis+mesoporous SiO
2method for coating etc. (non-patent literature 1 ~ 3).
Non-patent literature 1:L.Zhouetal.Nanoscale, 2014,6 (3): 1445-1452.
Non-patent literature 2:X.Quetal.RSCAdvances, 2013,3 (14): 4763-4770.
Non-patent literature 3:X.Kangetal.TheJournalofPhysicalChemistryC, 2011,115 (32): 15801-15811.
Known NaREF
4the preparation method of type microballoon has a difficult problem urgently to be resolved hurrily as follows: technique is loaded down with trivial details, and the low output of high investment, reaction raw materials and solvent toxicity are higher, higher to environmental hazard.And can reduce and drop into that to improve output be determine that this material can be marched toward the key in commercial applications stage from the laboratory study stage.
Summary of the invention
Main purpose of the present invention is the output improving porous up-conversion luminescent material, provides a kind of low cost to prepare NaREF in a large number
4the method of type up-conversion luminescence porous microsphere.It is characterized in that: fluorochemical and inorganic salt of rare earth are added in aqueous sodium polyacrylate (PAAS), stir and obtain mixing solutions; Above-mentioned mixing solutions is encapsulated in reacting by heating in teflon-lined autoclave or microwave reactor, after centrifugal, washing, drying, obtains NaREF
4porous microsphere.
Object of the present invention is achieved through the following technical solutions:
A kind of low cost prepares NaREF in a large number
4the method of type up-conversion luminescence porous microsphere: inorganic salt of rare earth and fluoride salt are added in reaction vessel, adding mass concentration is again 5% ~ 100%, relative molecular mass is that sodium polyacrylate (PAAS) aqueous solution of 200 ~ 9,000 ten thousand is as solvent, room temperature or heated and stirred 0.5 ~ 2h are to mixing, in rear immigration hydrothermal reaction kettle or microwave reactor, under temperature is 80 DEG C ~ 400 DEG C conditions, reacts 0.5 ~ 96h, can porous microsphere be obtained.
RE represents the one or several among 17 kinds of rare earth elements.Inorganic salt of rare earth is 1:2.5 ~ 1:24 with the ratio of the amount of substance of fluorine element, and the concentration of inorganic salt of rare earth in reaction system is 0.1 ~ 2mol/L.
Hinge structure, tool of the present invention has the following advantages and beneficial effect:
1. in equal volume reactor, primary first-order equation can produce water-soluble NaREF in a large number
4type up-conversion luminescence micro-nano-sphere, greatly simplify process prepared by material, in a large amount of manpower and materials of saving and the consistence that can better ensure product morphology structure while the time.Apply in known porous and change microballoon synthetic method, at 40mL water heating kettle PEI/DEG system or Trisodium Citrate/EG/H
2o system, 100mL flask high temperature thermal decomposition synthesis+mesoporous SiO
2method for coating all can only obtain 1mmol product, about 0.2g (non-patent literature 1 ~ 3).And use present method, doing single sintering at 40mL reactor, can obtain 15mmol product, about 3.0g, is 15 times of currently known methods;
2. product has good meso-hole structure and water-soluble, is desirable pharmaceutical carrier;
3. not containing SiO
2deng the component only providing vesicular structure, the NaREF of present method synthesis
4mesoporous material has up-conversion fluorescence imaging mark function and Drug absorbability function simultaneously, and effective constituent is close to 100%;
4. the prices of raw and semifnished materials are cheap, and not with an organic solvent, environmental protection is desirable mass industrialized production scheme.
Accompanying drawing explanation
The NaYF of Fig. 1 prepared by the embodiment of the present invention 1
4: the X-ray diffractogram of Yb, Er.
The NaYF of Fig. 2 prepared by the embodiment of the present invention 1
4: the field emission scanning electron microscope figure of Yb, Er.
The field emission scanning electron microscope figure of Fig. 3 product prepared by the embodiment of the present invention 2.
The field emission scanning electron microscope figure of Fig. 4 product prepared by the embodiment of the present invention 3.
The porous NaYF of Fig. 5 prepared by embodiment 1
4: Yb, Er's can spectrogram.
The porous NaYF of Fig. 6 prepared by embodiment 1
4: nitrogen adsorption desorption curve (a) of Yb, Er and graph of pore diameter distribution (b).
Fig. 7 is porous NaYF prepared by embodiment 1
4: the up-conversion luminescence spectrogram of Yb, Er.
Fig. 8 is the porous NaYF of embodiment 4 preparation used
4: infrared spectrogram Yb, Er changing microballoon (b) and the PAAS aqueous solution (a).
Fig. 9 product total amount that product total amount is once obtained in 40mL reactor with copying literature protocol 1 prepared by embodiment 1 contrasts figure.Hot spot is the fluorescence that under 980nm laser radiation, material produces.
The dispersion photo in deionized water of the product of Figure 10 prepared by embodiment 1.Hot spot is the fluorescence that under 980nm laser radiation, material produces.
Embodiment
For better understanding the present invention, below in conjunction with drawings and Examples, the present invention will be further described, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
By RE (NO
3)
3(wherein RE is Y:80%, Yb:18%, Er:2%) and NH
4it is 5,000 ten thousand ~ 7,000 ten thousand that F adds 50%PAAS(relative molecular mass) the aqueous solution in, RE (NO
3)
3with NH
4the ratio of the amount of substance of F is 1:4, RE (NO
3)
3concentration in mixing solutions is 0.6mol/L.Stirred at ambient temperature 1h, loads in reactor, sealing, 220 DEG C of reaction 12h.Be cooled to room temperature, put into baking oven 70 DEG C of dry 12h after centrifuge washing, namely obtain white powder.
The XRD data of composition graphs 1 and the EDS data of Fig. 5, product is six pure side phase NaYF
4: Yb, Er.
Can judge that the product obtained is porous microsphere from Fig. 2 and Fig. 6, microballoon mean sizes is 311nm, and mean pore size is 3.4nm.
The up-conversion luminescence spectrogram of product under Fig. 7 980nm laser excitation that to be product be 1w at power, show that product is at green glow (521nm, 541nm), all there is emission peak at ruddiness (656nm) and near infrared (842nm) place.
Fig. 8 is product (b) and the infrared spectrogram of the PAAS aqueous solution (a) that uses, illustrates that its surface is covered with PAAS.
Fig. 9 is the actual contrast photo of the product adopting present method and reference 1 method to obtain in 2 40ml reactors respectively, can find out to synthesize by method of the present invention the synthetic method that the amount that obtains product reports far above document 1.
Figure 10 is the photo that product is scattered in deionized water, can find out, product can be scattered in deionized water equably.
Embodiment 2
By RECl
3(wherein RE is Y:80%, Yb:18%, Er:2%) and NH
4it is 5,000 ten thousand ~ 7,000 ten thousand that F adds 30%PAAS(relative molecular mass) the aqueous solution in, RECl
3with NH
4the ratio of the amount of substance of F is 1:4, RECl
3concentration in mixing solutions is 0.6mol/L.Stirred at ambient temperature 1h, loads in reactor, sealing, 220 DEG C of reaction 12h.Be cooled to room temperature, put into baking oven 70 DEG C of dry 12h after centrifuge washing, namely obtain white powder.
Fig. 3 is the SEM picture of embodiment 2 products therefrom, and products therefrom is homogeneous spherical, and mean sizes is 703nm.XRD test result shows that products therefrom is six pure side phase NaREF
4, under 980nm laser radiation, product has emission peak near 521nm, 541nm and 842nm.
Embodiment 3
By RE (NO
3)
3(wherein RE is Yb:98%, Er:2%) and NH
4it is 5,000 ten thousand ~ 7,000 ten thousand that F adds 30%PAAS(relative molecular mass) the aqueous solution in, RE (NO
3)
3with NH
4the ratio of the amount of substance of F is 1:5, RE (NO
3)
3concentration in mixing solutions is 0.6mol/L.Stirred at ambient temperature 1.5h, loads in reactor, sealing, 200 DEG C of reaction 12h.Be cooled to room temperature, put into baking oven 70 DEG C of dry 12h after centrifuge washing, namely obtain white powder.
Fig. 4 is the SEM picture of 3 embodiment products therefroms, and as can be seen from the figure products therefrom is homogeneous elliposoidal.
XRD test result shows that products therefrom is six pure side phase NaREF
4, under 980nm laser radiation, product has emission peak near 521nm, 541nm and 842nm.
Embodiment 4
By RE (NO
3)
3(wherein RE is Gd:80%, Yb:18%, Ho:2%) and NH
4hF
2adding 40%PAAS(relative molecular mass is 3,000 ten thousand ~ 5,000 ten thousand) the aqueous solution in, RE (NO
3)
3with NH
4hF
2the ratio of amount of substance be 1:2.5, RE (NO
3)
3concentration in mixing solutions is 1.2mol/L.Be placed in microwave reactor, 300 DEG C of heated and stirred reaction 0.5h.Be cooled to room temperature, put into baking oven 70 DEG C of dry 12h after centrifuge washing, namely obtain white powder.
XRD test result shows that product is six pure side phase NaREF
4, under 980nm laser excitation, product all has emission peak near 365nm, 405nm.
Embodiment 5
By RE (NO
3)
3it is 2,000 ten thousand that (wherein RE is La:79%, Yb:20%, Tm:1%) and NaF add 30%PAAS(relative molecular mass) the aqueous solution in, RE (NO
3)
3be 1:4 with the ratio of the amount of substance of NaF, the concentration in the PAAS aqueous solution is 2mol/L.Stirred at ambient temperature 2h, loads in reactor, sealing, 80 DEG C of reaction 96h.Be cooled to room temperature, put into baking oven 70 DEG C of dry 12h after centrifuge washing, namely obtain white powder.
XRD test result shows that product is six pure side phase NaREF
4, under 980nm laser radiation, product all has emission peak near 365nm and 405nm.
Embodiment 6
By RE (NO
3)
3(wherein RE is Lu:80%, Yb:18%, Er:2%) and NaF add in the aqueous solution (relative molecular mass is 200) of 5%PAAS, RE (NO
3)
3be 1:4, RE (NO with the ratio of the amount of substance of NaF
3)
3concentration in mixing solutions is 1.2mol/L.Stirred at ambient temperature 1h, loads in reactor, sealing, 180 DEG C of reaction 48h.Be cooled to room temperature, put into baking oven 70 DEG C of dry 12h after washing, namely obtain white powder.
XRD test result shows that product is six pure side phase NaREF
4, under 980nm laser excitation, product all has emission peak at 542nm and 656nm place.
Embodiment 7
By RECl
3(wherein RE is La:79%, Yb:20%, Tm; 1%) and NH
4f adds in the aqueous solution (relative molecular mass is 3000) of 10%PAAS, RE (NO
3)
3with NH
4the ratio of the amount of substance of F is 1:2.5, RE (NO
3)
3concentration in mixing solutions is 0.1mol/L.Stirred at ambient temperature 1h, loads in reactor, sealing, 150 DEG C of reaction 12h.Be cooled to room temperature, put into baking oven 70 DEG C of dry 12h after washing, namely obtain white powder.
XRD test result shows that products therefrom is NaREF
4, under 980nm laser excitation, product all has emission peak at 542nm and 656nm place.
Embodiment 8
By RE (CH
3cOO)
3(wherein RE is Gd:80%, Yb:18%, Er:2%) and NH
4hF
2adding 100%PAAS(relative molecular mass is 9,000 ten thousand) in, RE (NO
3)
3with NH
4hF
2the ratio of amount of substance be 1:24, RE (NO
3)
3concentration in mixing solutions is 1.2mol/L.Be placed in microwave reactor 400 DEG C reaction 1h.Be cooled to room temperature, put into baking oven 70 DEG C of dry 12h after centrifuge washing, namely obtain white powder.
XRD test result shows that product is six pure side phase NaREF
4, under 980nm laser excitation, product all has emission peak at 542nm and 656nm place.
Embodiment 9
By RE (NO
3)
3(wherein RE is Y:80%, Nd:18%, Er:2%) and NH
4it is 8,000 ten thousand that F adds 70%PAAS(relative molecular mass) the aqueous solution in, RE (NO
3)
3with NH
4the ratio of the amount of substance of F is 1:12, RE (NO
3)
3concentration in mixing solutions is 1.2mol/L.Stir 0.5h under 80 DEG C of heating, load in reactor, sealing, 200 DEG C of reaction 24h.Washing and drying, namely obtains white powder.
XRD test result shows that products therefrom is six pure side phase NaREF
4, under 800nm laser excitation, product all has emission peak at 542nm and 656nm place.
Claims (11)
1. a low cost prepares NaREF in a large number
4the method of type up-conversion luminescence porous microsphere, is characterized in that: fluorochemical and inorganic salt of rare earth are added in aqueous sodium polyacrylate (PAAS), stirs and obtains mixing solutions; Above-mentioned mixing solutions is encapsulated in reacting by heating in teflon-lined autoclave or microwave reactor, after centrifugal, washing, drying, obtains NaREF
4porous microsphere.
2. the preparation method of porous microsphere according to claim 1, is characterized in that, described fluorochemical is at least one in Neutral ammonium fluoride, ammonium bifluoride, Sodium Fluoride.
3. the preparation method of porous microsphere according to claim 1, is characterized in that, the mass concentration of described aqueous sodium polyacrylate (PAAS) is 5% ~ 100%, and relative molecular mass is 200 ~ 9,000 ten thousand.
4. the preparation method of porous microsphere according to claim 1, is characterized in that, described inorganic salt of rare earth is at least one in rare earth chloride, rare earth nitrate and lanthanon acetate.
5. the preparation method of porous microsphere according to claim 1, is characterized in that, described rare earth is at least one in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium.
6. the preparation method of porous microsphere according to claim 1, is characterized in that, the volumetric molar concentration of described inorganic salt of rare earth in mixing solutions is 0.1 ~ 2mol/L.
7. the preparation method of porous microsphere according to claim 1, is characterized in that, described inorganic salt of rare earth is 1:2.5 ~ 1:24 with the ratio of the amount of substance of described fluorochemical.
8. the preparation method of porous microsphere according to claim 1, is characterized in that, described reacting by heating is carried out in teflon-lined autoclave or microwave reactor.
9. the preparation method of porous microsphere according to claim 1, is characterized in that, the temperature of reaction of described reacting by heating is 80 DEG C ~ 400 DEG C, and the reaction times is 0.5 ~ 96h.
10. the preparation method of porous microsphere according to claim 1, is characterized in that, described porous microsphere size is between 100nm ~ 5um.
The preparation method of 11. porous microspheres according to claim 1, is characterized in that, the pore dimension of described porous microsphere is between 1nm ~ 200nm.
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Cited By (2)
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| CN105713603A (en) * | 2016-03-23 | 2016-06-29 | 江西理工大学 | Method for preparing MF2 type water-soluble mesoporous light-emitting nanospheres in efficient and green mode |
| CN116265568A (en) * | 2022-09-09 | 2023-06-20 | 南京市第一医院 | Green fluorescent infrared up-conversion mesoporous nanomaterial and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713603A (en) * | 2016-03-23 | 2016-06-29 | 江西理工大学 | Method for preparing MF2 type water-soluble mesoporous light-emitting nanospheres in efficient and green mode |
| CN116265568A (en) * | 2022-09-09 | 2023-06-20 | 南京市第一医院 | Green fluorescent infrared up-conversion mesoporous nanomaterial and preparation method thereof |
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Application publication date: 20160309 |