CN109609120A - A kind of long-persistence luminous aeroge and preparation method thereof - Google Patents
A kind of long-persistence luminous aeroge and preparation method thereof Download PDFInfo
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- CN109609120A CN109609120A CN201811604077.4A CN201811604077A CN109609120A CN 109609120 A CN109609120 A CN 109609120A CN 201811604077 A CN201811604077 A CN 201811604077A CN 109609120 A CN109609120 A CN 109609120A
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- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
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Abstract
The present invention relates to a kind of long-persistence luminous aeroges and preparation method thereof, using sol-gal process, the nitrate solution of three kinds of metals (Zn, Ga, Cr) is mixed by certain molar ratio, with polyacrylic acid (PAA) for dispersing agent, propylene oxide (PO) is gel promotor, is placed in room temperature gel, then dry through alcohol solvent replacement, CO 2 supercritical, last Muffle furnace calcining, prepares the long afterglow ZnGa to glow2O4:Cr3+Aeroge.Long-persistence luminous aeroge in the present invention belongs to porous nanometer material, have high specific surface area, absorption property is preferable, and its ultraviolet light stop irradiation after, still can with continuous illumination, therefore biomedicine field have higher researching value.
Description
Technical field
The present invention relates to aerogel material technical fields, and in particular to a kind of long-persistence luminous aeroge and its preparation side
Method.
Background technique
The world is bright and colourful because of light, the just deep and fine life for changing us of the development and application of luminescent material
It is living.The research of one kind critically important as solid luminescent material, long after glow luminous material has just been opened early in 19 century 70s
Begin.It is after excitation to shine not being disappearance at once but gradually die down after external influence stops, this process is known as twilight sunset.More than length
The system of brightness luminescent material is mainly include the following types: sulfide systems, aluminates system, silicate systems, gallic acid salt system etc.
Deng.Its main preparation methods has high temperature solid phase synthesis, hydrothermal synthesis method, combustion method, sol-gel method.Long-persistence luminous material
It is ZnS system luminescent material that material early stage, which is studied more, but it have the shortcomings that it is obvious, such as the unstability of luminescent material.
ZnGa2O4It is the gallate afterglow materials of everybody extensive concern as a kind of self-activation type luminescent material.
ZnGa2O4A kind of semiconductor functionality material with spinel structure, many of structure cell be conducive to Doped ions enter and
Form luminous gap, the long afterglow of the available different luminescent colors of the incorporation of different transition metal ions or rare earth ion
Material.But existing preparation method prepares long-afterglow material, bad dispersibility, higher cost by metal chelating agent of citric acid.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of synthesis is simple, cost
Low long-persistence luminous aeroge and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions: a kind of long-persistence luminous aeroge, the aeroge
Including ZnGa2O4Crystalline material and it is entrained in ZnGa2O4Cr in crystalline material3+, the ZnGa2O4Crystalline material and Cr3+'s
Molar ratio is 1:(0.005~0.01).Cr3+Doping using gallic acid zinc as the compound of matrix, being can be with excited by visible light simultaneously
Emit the long-afterglow material of near infrared light.
A kind of preparation method of long-persistence luminous aeroge as described above, comprising the following steps:
(1) zinc nitrate, gallium nitrate and chromic nitrate are dissolved in ethyl alcohol, are uniformly mixed, deionized water and poly- third is then added
Olefin(e) acid stirs evenly, and obtains mixed solution；
(2) gel promotor is added in mixed solution, stands after stirring until being converted to gel；
(3) one layer of ethyl alcohol is covered in gel surface and carry out aging, and replace ethyl alcohol at regular intervals, then carry out dioxy
Change carbon supercritical drying, obtains aeroge crude product；
(4) aeroge crude product is calcined, obtains the long-persistence luminous aeroge.
The present invention is dispersing agent using polyacrylic acid, and propylene oxide is " proton capture agent " to prepare colloidal sol, makes colloidal sol grain
The dispersibility of son is more preferable more evenly, and avoids keeping experimentation more green safe using base catalyst.Polyacrylic acid is as one
Kind polymer, has long chain structure, and micelle reaches dispersion purpose in its branch chain growth.And propylene oxide is used as " proton capture
Following opening can occur for agent ":
Therefore colloidal sol can gradually meta-alkalescence.ZnGa2O4:Cr3+Long-afterglow material can be widely applied to security fields, traffic neck
Domain, military field, building field, appliance field etc., due to its porosity, also adsorbable drug becomes luminescence probe, is applied
To fields such as bio-imaging labels.
Preferably, the mass ratio of the zinc nitrate, gallium nitrate and chromic nitrate is 1:1:(0.005~0.01).
Preferably, the deionized water of addition and the volume ratio of zinc nitrate are (10~13): 1；
The volume ratio of the polyacrylic acid and zinc nitrate that are added is (3~4.5): 1；
The rate of stirring described in step (1) is 300~1000r/min, mixing time 15min-30min.
Preferably, the gel promotor is propylene oxide, the additional amount of the propylene oxide and mole of deionized water
Than for (0~1.5): 0.15, and the additional amount of propylene oxide is not 0；
Stirring rate in step (2) is 300~1000r/min, mixing time 15min-30min.
Preferably, in step (3), an ethyl alcohol to be replaced every 8~12h, is replaced 3~5 times, aging can be such that skeleton enhances,
It is not easy to crack.
Preferably, dry 38~43 DEG C of temperature, 7.5~9.5MPa of pressure of the CO 2 supercritical, the time is 3~
4h。
Preferably, the temperature of the calcining is 600~1200 DEG C, and calcination time is 1~6h.
Compared with prior art, the beneficial effects of the present invention are embodied in following several respects:
(1) method of the invention can be used for the doping of different transition metal ions or rare earth ion, such as Eu2+, Mn2+,
The long-afterglow material of available difference luminescent color；
(2) sintering temperature needed for the sample that sol-gel method is prepared is lower than conventional solid-state method, and granular size, sample
Density is controllable, and the sample purity prepared is high, and uniformity is good；
(3) the invention proposes a kind of new collosol-gelatum system for preparing long after glow luminous material, that is, polypropylene is utilized
Acid is dispersing agent, and propylene oxide is " proton capture agent " to prepare colloidal sol, it is more preferable more evenly to make the dispersibility of sol particles, and keep away
Exempt to keep experimentation more green safe using base catalyst.ZnGa2O4:Cr3+Long-afterglow material is widely used to lead safely
Domain, field of traffic, military field, building field, appliance field etc., due to its porosity, also adsorbable drug, which becomes to shine, to be visited
Needle is applied to the fields such as bio-imaging label.
Detailed description of the invention
The scanning electron microscope diagram and scanning transmission electron microscope figure of 1 sample of Fig. 1 embodiment；
The Mapping of 1 sample of Fig. 2 embodiment schemes；
The X-ray diffractogram of 1 sample of Fig. 3 embodiment；
The fluorescence spectra emission figure of 1 sample of Fig. 4 embodiment.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
By 2.98g zinc nitrate [Zn (NO3)2·6H2O] and 2.56g gallium nitrate [Ga (NO3)3·xH2O] it is dissolved in 30 milliliters of second
It in alcohol, stirs evenly, adds 0.03g chromic nitrate [Cr (NO3)3·9H2O] stirring it is uniform to solution.It is added into mixed solution
3.78ml propylene oxide (PO) is added after 30min is stirred at room temperature, after 3min in 2ml deionized water and 2.31ml polyacrylic acid (PAA)
It is placed at room temperature for gel.One layer of ethyl alcohol is spread to the upper surface of gained wet gel and carries out aging, carries out ethyl alcohol after three days at normal temperature
Solvent replacement, each 8-12h replace 3-5 times, carry out CO 2 supercritical drying later, and the condition for reaching above-critical state is
40 DEG C of temperature, pressure 9MPa, ZnGa has been obtained after dry2O4:Cr3+Aeroge.Aeroge is placed in 800 DEG C of Muffle furnaces and is calcined
2h finally obtains ZnGa2O4:Cr3+Long-persistence luminous aeroge.
Fig. 1 is long afterglow ZnGa respectively2O4:Cr3+SEM and the TEM figure of luminous aeroge.As we can see from the figure
ZnGa2O4:Cr3+Aeroge has typical spheroidal particle packed structures, and cluster combines closely.Fig. 2 is long afterglow
ZnGa2O4:Cr3+The Mapping figure of luminous aeroge.Therefrom it can be found that the atomic percent of Zn is 63.11%；The original of Ga
Sub- percentage is 28.71%；The atomic percent of Cr is 8.18%.This illustrates Cr3+Not with solvent replacement and CO2It is super to face
Boundary is dry and is lost.Fig. 3 is long afterglow ZnGa2O4:Cr3+The X-ray diffractogram of luminous aeroge.The corresponding card of this figure is
ZnGa2O438-1240 belongs to cubic system spinel structure.There is not Cr in XRD diffraction pattern3+, first is that because Cr3+?
Enter ZnGa2O4Lattice in, second is that because of Cr3+Doping concentration it is too small, there is not apparent diffraction maximum.Fig. 4 is long
Twilight sunset ZnGa2O4:Cr3+The fluorescence spectra of luminous aeroge.The ZnGa of 800 DEG C of calcinings as can be seen from FIG.2O4:Cr3+Aeroge
There is apparent emission peak in 810nm or so, compared to the ZnGa of high temperature solid-state method preparation2O4:Cr3+Occur for particle red
It moves.
Embodiment 2
Using preparation method same as Example 1, the difference is that the preparation condition used is different, specifically include with
Lower step:
(1) 0.01mol zinc nitrate hexahydrate, 0.01mol nitric hydrate gallium and 0.00005mol Chromium nitrate (Cr(NO3)3),nonahydrate is molten
It in ethyl alcohol, is uniformly mixed, 0.1mol deionized water and 0.03mol polyacrylic acid is then added, in 300r/min stirring rate
Lower stirring 30min, obtains mixed solution；
(2) 0.0067mol propylene oxide is added in mixed solution, 30min is stirred under 300r/min stirring rate, so
It is stood afterwards until being converted to gel；
(3) one layer of ethyl alcohol is covered in gel surface and carry out aging, replace an ethyl alcohol every 8h, replace 5 times, then carry out
CO 2 supercritical is dry, and temperature is 43 DEG C, pressure 7.5MPa, time 4h and obtains aeroge crude product；
(4) aeroge crude product is subjected to calcining 4h under the conditions of 600 DEG C, obtains the long-persistence luminous aeroge.
It is detected, the long-persistence luminous aeroge sample purity being prepared is high, and uniformity is good, and the aeroge sample is
Excited by visible light and the long-afterglow material for emitting near infrared light.
Embodiment 3
Using preparation method same as Example 1, the difference is that the preparation condition used is different, specifically include with
Lower step:
(1) 0.01mol zinc nitrate hexahydrate, 0.01mol nitric hydrate gallium and 0.0001mol Chromium nitrate (Cr(NO3)3),nonahydrate are dissolved in
It in ethyl alcohol, is uniformly mixed, 0.13mol deionized water and 0.045mol polyacrylic acid is then added, in 1000r/min stirring rate
Lower stirring 15min, obtains mixed solution；
(2) 1.5mol propylene oxide is added in mixed solution, 15min is stirred under 1000r/min stirring rate, then
It stands until being converted to gel；
(3) cover one layer of ethyl alcohol in gel surface and carry out aging, replace an ethyl alcohol every 12h, replace 3 times, then into
Row CO 2 supercritical is dry, and temperature is 38 DEG C, pressure 9.5MPa, time 3h and obtains aeroge crude product；
(4) aeroge crude product is subjected to calcining 2h under the conditions of 1200 DEG C, obtains the long-persistence luminous aeroge.
It is detected, the long-persistence luminous aeroge sample purity being prepared is high, and uniformity is good, and the aeroge sample is
Excited by visible light and the long-afterglow material for emitting near infrared light.
Claims (8)
1. a kind of long-persistence luminous aeroge, which is characterized in that the aeroge includes ZnGa2O4It crystalline material and is entrained in
ZnGa2O4Cr in crystalline material3+, the ZnGa2O4Crystalline material and Cr3+Molar ratio be 1:(0.005~0.01).
2. a kind of preparation method of long-persistence luminous aeroge as described in claim 1, which is characterized in that including following step
It is rapid:
(1) zinc nitrate, gallium nitrate and chromic nitrate are dissolved in ethyl alcohol, are uniformly mixed, deionized water and polyacrylic acid is then added,
It stirs evenly, obtains mixed solution；
(2) gel promotor is added in mixed solution, stands after stirring until being converted to gel；
(3) one layer of ethyl alcohol is covered in gel surface and carry out aging, and replace ethyl alcohol at regular intervals, then carry out carbon dioxide
Supercritical drying obtains aeroge crude product；
(4) aeroge crude product is calcined, obtains the long-persistence luminous aeroge.
3. a kind of preparation method of long-persistence luminous aeroge according to claim 2, which is characterized in that the nitric acid
Zinc, gallium nitrate and chromic nitrate mole are 1:1:0.005~0.01.
4. a kind of preparation method of long-persistence luminous aeroge according to claim 2, which is characterized in that addition it is described
Deionized water and zinc nitrate molar ratio are (10~13): 1；
The molar ratio of the polyacrylic acid and zinc nitrate that are added is (3~4.5): 1；
The rate of stirring described in step (1) is 300~1000r/min, and mixing time is 15~30min.
5. a kind of preparation method of long-persistence luminous aeroge according to claim 2, which is characterized in that the gel promotees
It is propylene oxide into agent, the additional amount of the propylene oxide and the molar ratio of deionized water are (0~1.5): 0.15, and epoxy third
The additional amount of alkane is not 0；
Stirring rate in step (2) is 300~1000r/min, and mixing time is 15~30min.
6. a kind of preparation method of long-persistence luminous aeroge according to claim 2, which is characterized in that in step (3),
An ethyl alcohol is replaced every 8~12h, is replaced 3~5 times.
7. a kind of preparation method of long-persistence luminous aeroge according to claim 2, which is characterized in that the titanium dioxide
38~43 DEG C, 7.5~9.5MPa of pressure of the temperature of carbon supercritical drying, the time is 3~4h.
8. a kind of preparation method of long-persistence luminous aeroge according to claim 2, which is characterized in that the calcining
Temperature is 600~1200 DEG C, and calcination time is 1~6h.
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| CN112725414A (en) * | 2020-12-21 | 2021-04-30 | 中国科学院宁波材料技术与工程研究所慈溪生物医学工程研究所 | Long-afterglow molecular beacon probe, and construction method and application thereof |
| CN114507517A (en) * | 2022-03-04 | 2022-05-17 | 浙江大学 | Broadband near-infrared fluorescent powder based on spinel structure and preparation method and application thereof |
| CN115108822A (en) * | 2022-07-14 | 2022-09-27 | 南京工业大学 | Photo-thermal regulation ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ Method for producing aerogels |
| CN115141030A (en) * | 2022-06-30 | 2022-10-04 | 南京工业大学 | One kind (LaCeSmEuNd) 2 Zr 2 O 7 Preparation method of high-entropy oxide ceramic aerogel |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112725414A (en) * | 2020-12-21 | 2021-04-30 | 中国科学院宁波材料技术与工程研究所慈溪生物医学工程研究所 | Long-afterglow molecular beacon probe, and construction method and application thereof |
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| CN114507517A (en) * | 2022-03-04 | 2022-05-17 | 浙江大学 | Broadband near-infrared fluorescent powder based on spinel structure and preparation method and application thereof |
| CN115141030A (en) * | 2022-06-30 | 2022-10-04 | 南京工业大学 | One kind (LaCeSmEuNd) 2 Zr 2 O 7 Preparation method of high-entropy oxide ceramic aerogel |
| CN115108822A (en) * | 2022-07-14 | 2022-09-27 | 南京工业大学 | Photo-thermal regulation ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ Method for producing aerogels |
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