CN109971474A - A kind of long-persistence luminous nanometer rods of hydroxide near-infrared and preparation method thereof - Google Patents
A kind of long-persistence luminous nanometer rods of hydroxide near-infrared and preparation method thereof Download PDFInfo
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- CN109971474A CN109971474A CN201910214200.XA CN201910214200A CN109971474A CN 109971474 A CN109971474 A CN 109971474A CN 201910214200 A CN201910214200 A CN 201910214200A CN 109971474 A CN109971474 A CN 109971474A
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- 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
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Abstract
The invention discloses a kind of long-persistence luminous nanometer rods of hydroxide near-infrared and preparation method thereof, shown in the long-persistence luminous nanometer rods of near-infrared such as formula (I): La (OH)3:xEu3+(Ⅰ)；Wherein, 0.5%≤x≤50%.The matrix of the long-persistence luminous nanometer rods of near-infrared provided by the invention is La (OH)3, with Eu3+For active ions.The long-persistence luminous nanometer rods stable appearance of the near-infrared, of uniform size, emission wavelength is 570~720nm, and twilight sunset duration is up to 180s, and the fields such as vitro detection, label, imaging have great application value in vivo.Different from other conventional long-persistence luminous matrix such as oxide, sulfide, nitride etc., the present invention has found long afterglow phenomenon in hydroxide matrix for the first time；Moreover, the preparation of conventional long after glow luminous material must be by certain sintering process, still, the present invention realizes long after glow luminous material is made without sintering process for the first time.
Description
Technical field
The present invention relates to luminescent material technical fields, long-persistence luminous more particularly, to a kind of hydroxide near-infrared
Nanometer rods and preparation method thereof.
Background technique
Rare earth long-afterglow luminescent material refers to that one kind can deposit part energy after absorbing the energy of sunlight or light
Storage is got up, and then slowly releases storage energy in the form of visible light under certain excitation.Long afterglow shines
Material is widely used in the fields such as low light illuminant, emergency instruction, building decoration and industrial art, in recent years, store in information,
Application is also expanded in the fields such as biological detection.
The development course of rear-earth-doped red long-afterglow is made a general survey of, matrix system mainly includes sulfide systems, titanate
System, oxysulfide system, silicate systems, there are also the long-afterglow materials of alkaline earth oxide to be in the exploratory stage,
Preparation method mainly takes high temperature sintering, in terms of preparing long-persistence nano material, mainly collosol and gel and hydro-thermal method etc.,
Morphology controllable is prepared, the long-persistence nano material of size uniformity is relatively difficult.
Therefore, it is also desirable to develop new host material or preparation method, this method can prepare stable appearance and ruler
Very little uniform long-persistence nano-luminescent materials.
Summary of the invention
The present invention is to overcome defect described in the above-mentioned prior art, provides a kind of long-persistence luminous nanometer rods of near-infrared, mentions
The long-persistence luminous nanometer rods of the near-infrared of confession are stable appearance, of uniform size using hydroxide as matrix, and twilight sunset duration is reachable
180s。
Another object of the present invention is to provide the preparation methods of the long-persistence luminous nanometer rods of above-mentioned near-infrared.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of long-persistence luminous nanometer rods of hydroxide near-infrared, as shown in formula (I):
La(OH)3: x%Eu3+(Ⅰ)；
Wherein, 0.5%≤x≤50%.
The matrix of the above-mentioned long-persistence luminous nanometer rods of near-infrared is La (OH)3, with Eu3+For active ions；The near-infrared is long
Afterglow nanometer rods stable appearance, of uniform size, emission wavelength is 570~720nm, and twilight sunset duration is up to 180s.
The long-persistence luminous nanometer rods of hydroxide near-infrared provided by the invention can in vivo vitro detection, mark
The fields such as note, imaging are widely used, and have great application value.
Different from other conventional long-persistence luminous matrix such as oxide, sulfide, nitride etc., the present invention is for the first time in hydrogen
Long-persistence luminous phenomenon is had found in matrix of oxide.And conventional long afterglow can be prepared by sintering, and hydroxide due to
The presence of hydroxide ion can not be prepared by sintering.Therefore, the present invention realizes the length of rear-earth-doped hydroxide for the first time
Afterglow, also, for the first time by the way that long after glow luminous material has been made without the preparation method of sintering.
Precipitation method synthesis can be used in the long-persistence luminous nanometer rods of near-infrared provided by the invention, obtains morphology controllable, stabilization,
The long-persistence luminous nanometer rods of near-infrared of uniform size.
X in above-mentioned formula (I) indicates rare earth ion Eu in material3+With La3+Ratio.
Preferably, 10%≤x≤20%.Rare earth ion Eu in material3+With La3+Ratio be 10%~20% when, it is obtained
The performance of the long-persistence luminous nanometer rods of near-infrared is promoted.
It is highly preferred that x is 20%.At this point, the long-persistence luminous nanometer rods of near-infrared are La (OH)3: 20%Eu3+。Eu3+Contain
When amount is 20%, the fluorescence and afterglow property of near-infrared long-persistence nano-luminescent materials are optimal.
The present invention also protects the preparation method of above-mentioned near-infrared long-persistence nano-luminescent materials, and the preparation method includes such as
Lower step:
S1. it prepares containing La3+With Doped ions Eu3+Mixed solution；Then adjusting pH with ammonium hydroxide is alkalinity, is reacted
Solution；
S2. the reaction solution in step S1. is reacted under the conditions of heating and stirring, is obtained more than the near-infrared length
Brightness nano luminescent material.
Preferably, mixed solution is La in step S1.3+With Doped ions Eu3+Nitrate solution.The nitrate is molten
Liquid can be dissolved in dust technology by corresponding oxide and be made.The oxide is La2O3And Eu2O3。
Preferably, the concentration of the ammonium hydroxide is 25wt.%.
It preferably, is 8~10 with the value that ammonium hydroxide adjusts pH in step S1..It is highly preferred that being adjusted in step S1. with ammonium hydroxide
The value of pH is 9.
Preferably, the temperature reacted in step S2. is 85~95 DEG C, and the time of reaction is 1.5~2.5h.It is highly preferred that
The temperature reacted in step S2. is 90 DEG C, and the time of reaction is 2h.The reaction solution for being 9 by pH is acute under 90 DEG C of water bath conditions
Strong stirring 2h, then cooled to room temperature three times with deionized water and each centrifuge washing of dehydrated alcohol are subsequently placed in baking oven
80 DEG C of dry 12h.It after drying, slightly grinds, product can be obtained.Grinding can use agate mortar.
The stirring can use magnetic stirring apparatus.Reaction in step S2. uses heatable magnetic stirring apparatus.
Compared with prior art, the beneficial effects of the present invention are:
The matrix of the long-persistence luminous nanometer rods of near-infrared provided by the invention is La (OH)3, with Eu3+For active ions.It should
Long-persistence nano-luminescent materials stable appearance, of uniform size, emission wavelength is 570~720nm, twilight sunset duration up to 180s,
The fields such as vitro detection, label, imaging have great application value in vivo.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of sample prepared by the embodiment of the present invention 1~5.
Fig. 2 is sample transmission electron microscope prepared by the embodiment of the present invention 4.
Fig. 3 is the fluorescent exciting spectrogram and fluorescence emission spectrogram of compound of sample prepared by the embodiment of the present invention 1~5.Its
In, the figure embedded in Fig. 3 is Strength Changes broken line of the fluorescence excitation spectrum of the sample of Examples 1 to 5 preparation at 395nm
Figure and Strength Changes line chart of the fluorescence emission spectrum at 695nm.
Fig. 4 is the fluorescence lifetime figure of sample prepared by the embodiment of the present invention 1~5.
Fig. 5 is the decay of afterglow figure of sample prepared by the embodiment of the present invention 1~5.
Specific embodiment
The present invention is further illustrated With reference to embodiment.
Raw material in embodiment can be by being commercially available；
Unless stated otherwise, the present invention uses reagent, method and apparatus for the art conventional reagent, method and are set
It is standby.
Embodiment 1
Weigh lanthana La2O3: 12.2175g is dissolved in preparation 0.5M La (NO in 150mL dust technology3)3Solution weighs oxygen
Change europium Eu2O3: 5.2789g is dissolved in preparation 0.5M Eu (NO in 100mL dust technology3)3Solution, above-mentioned nitrate lanthanum solution take
20mL, europium nitrate solution take 0.1mL, and mixing is added 100mL deionized water, is vigorously stirred 10min；Use NH3·H2O
(25wt.%) is vigorously stirred 2h by above-mentioned mixed solution tune pH=9, in 90 DEG C of water-baths, then, cooled to room temperature, centrifugation
Washing, deionized water and dehydrated alcohol successively respectively wash three times；The 80 DEG C of dry 12h in baking oven of the sample after being centrifuged will be washed,
Sample after drying is slightly ground；Group, which can be obtained, becomes La (OH)3: 0.5%Eu3+The europkium-activated near-infrared of trivalent it is long more than
Brightness Illuminant nanometer rods, the product issue the red long-afterglow of 695nm after the excitation of 395nm light, and decay of afterglow is exponentially regular.
Embodiment 2
The present embodiment the difference from embodiment 1 is that, take lanthanum nitrate hexahydrate 20mL, europium nitrate solution 0.2mL, rare earth ion
Eu3+With La3+Ratio be 1%；
Other raw materials and experimental implementation are same as Example 1.
Embodiment 3
The present embodiment the difference from embodiment 1 is that, take lanthanum nitrate hexahydrate 20mL, europium nitrate solution 2mL, rare earth ion
Eu3+With La3+Ratio be 10%；
Other raw materials and experimental implementation are same as Example 1.
Embodiment 4
The present embodiment the difference from embodiment 1 is that, take lanthanum nitrate hexahydrate 20mL, europium nitrate solution 4mL, rare earth ion
Eu3+With La3+Ratio be 20%；
Other raw materials and experimental implementation are same as Example 1.
Embodiment 5
The present embodiment the difference from embodiment 1 is that, take lanthanum nitrate hexahydrate 20mL, europium nitrate solution 10mL, rare earth ion
Eu3+With La3+Ratio be 50%；
Other raw materials and experimental implementation are same as Example 1.
Structural characterization and performance test
X-ray diffraction detection uses Bruker-D8 ADVANCE X-ray diffractometer；The detection of transmission electron microscope picture is using prompt
Gram Talos F200S Flied emission transmission electron microscope；Excitation spectrum detection uses Edinburg FLS-980 Fluorescence Spectrometer；Hair
Spectral detection is penetrated using Edinburg FLS-980 Fluorescence Spectrometer；Decay of afterglow spectral detection uses Edinburg FLS-980 fluorescence light
Spectrometer；Thermoluminescence detection is using FJ-427A TL meter (Beijing, China).
According to X-ray diffraction test result, as shown in Figure 1, as can be seen from the figure the product of Examples 1 to 5 preparation is
La(OH)3, product is consistent with standard card peak position.Through transmissioning electric mirror test, as shown in Fig. 2, sample made from embodiment 4 is to receive
Rice is rodlike.The consistent appearance of the sample of other embodiments and embodiment 4.
The fluorescence spectra of the doping trivalent europium ion of Examples 1 to 5 is as shown in figure 3, show the nano luminescent material
Excitation peak position is located at 395nm, and transmitting peak position is located at 695nm；Wherein, fluorescence emission spectrum is measured at excitation wavelength 395nm
, moreover, nano luminescent material fluorescence made from embodiment 4 is most strong.
The fluorescence lifetime figure of Fig. 4 is measured at excitation wavelength 395nm, launch wavelength 695nm, can from figure
Out, embodiment 3 and embodiment 4 are better than embodiment 1, embodiment 2 and embodiment 5；It is taken respectively using the sample of Examples 1 to 5
0.080g, which is irradiated under the ultraviolet lamp of 254nm after 20min, monitors lower test in launch wavelength 695nm, obtains Fig. 5, can from figure
To find out, the Eu of single doping 20%3+When sample persistence be up to 180s.By comparing Examples 1 to 5 it is found that doping
Amount is optimal for 20% sample comprehensive performance.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (7)
1. a kind of long-persistence luminous nanometer rods of hydroxide near-infrared, which is characterized in that as shown in formula (I):
La(OH)3:xEu3+(Ⅰ)；
Wherein, 0.5%≤x≤50%.
2. the long-persistence luminous nanometer rods of hydroxide near-infrared according to claim 1, which is characterized in that 10%≤x≤
20%.
3. the long-persistence luminous nanometer rods of hydroxide near-infrared according to claim 2, which is characterized in that x 20%.
4. the preparation method of any one of claims 1 to 3 long-persistence luminous nanometer rods of hydroxide near-infrared, feature exist
In including the following steps:
S1. it prepares containing La3+With Doped ions Eu3+Mixed solution；Then adjusting pH with ammonium hydroxide is alkalinity, obtains reaction solution；
S2. the reaction solution in step S1. is reacted under the conditions of heating and stirring, obtains the near-infrared long afterglow hair
Light nanometer rods.
5. the preparation method according to claim 4, which is characterized in that mixed solution is La in step S1.3+And Doped ions
Eu3+Nitrate solution.
6. the preparation method according to claim 4, which is characterized in that in step S1. with ammonium hydroxide adjust pH value be 8~
10。
7. the preparation method according to claim 4, which is characterized in that the temperature reacted in step S2. is 85~95 DEG C, instead
The time answered is 1.5~2.5h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941676A (en) * | 2010-08-26 | 2011-01-12 | 吉林大学 | Method for preparing Ln2O3:RE<3+> and Ln2O3:RE<3+>@SiO2 monodisperse rare earth nano particles |
| CN109181696A (en) * | 2018-10-26 | 2019-01-11 | 广东工业大学 | A kind of red long-persistence nano-luminescent materials |
-
2019
- 2019-03-20 CN CN201910214200.XA patent/CN109971474A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941676A (en) * | 2010-08-26 | 2011-01-12 | 吉林大学 | Method for preparing Ln2O3:RE<3+> and Ln2O3:RE<3+>@SiO2 monodisperse rare earth nano particles |
| CN109181696A (en) * | 2018-10-26 | 2019-01-11 | 广东工业大学 | A kind of red long-persistence nano-luminescent materials |
Non-Patent Citations (1)
| Title |
|---|
| HUSSAIN, SK. KHAJA等: "La(OH)(3):Eu3+ and La2O3:Eu3+ nanorod bundles: growth mechanism and luminescence properties", 《CRYSTENGCOMM 》 * |
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Application publication date: 20190705 |