CN107163933A - A kind of even porous rare earth composite material of emitting red light, preparation method and application - Google Patents
A kind of even porous rare earth composite material of emitting red light, preparation method and application Download PDFInfo
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- CN107163933A CN107163933A CN201710520271.3A CN201710520271A CN107163933A CN 107163933 A CN107163933 A CN 107163933A CN 201710520271 A CN201710520271 A CN 201710520271A CN 107163933 A CN107163933 A CN 107163933A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Abstract
A kind of even porous rare earth composite material of emitting red light, preparation method and application.The invention belongs to aerogel composite, the composite is CMC/TTA/Eu, and wherein CMC is sanlose, and TTA is the anion after 2 TTA deprotonations, and Eu is rare-earth europium ion.The Rare Earth Europium Complex of the material is connected with cellulose macromolecule network with covalent bond, and decomposition temperature is 240 DEG C.Preparation is：EuCl is added dropwise after the dissolving of sanlose powder3The aqueous solution, obtains transparent beads shape CMC/Eu3+Hydrogel；By CMC/Eu3+Hydrogel adds the aqueous solution of 2 TTA sodium salts, and stirring, collection and ethanol are exchanged, and supercritical carbon dioxide is dried etc..The composite sends pure red fluorescence under ultraviolet light, has potential application prospect in luminescence display and novel porous materials field.
Description
Technical field
The invention belongs to aerogel composite, the especially luminescent material containing lanthanide complexes and preparation.
Background technology
The characteristics of rare earth element with excitation height, fluorescence lifetime length, the spectral line of emission due to enriching, it is luminous multiple by preparing
The extensive concern of condensation material.SiO2There is great potential using value, traditional rare earth hair in fields such as catalysis, absorption, sensings
Recovery condensation material is typically chosen silica as host material.But with large biological molecule discrete phase ratio, silica matrix is simultaneously
Without excellent biocompatibility and biodegradability.Professor Zhang Lina of Wuhan University was once reported a kind of rare earth
Luminescent phosphor SrAl2O4: Eu2+, Dy3+It is doped in the biological macromolecular matrices material of cellulose, resulting recombination luminescence
Material shows potential application value (J. Mater. Chem. B, 2014,2,7559) in terms of bio-imaging.But
It is that doping way is physics, has the disadvantage, be to be combined by intermolecular force between rare-earth luminescent center and matrix, result in
The centre of luminescence is easily reunited, and also easily occurs fluorescent quenching.Sodium carboxymethylcellulose is cotton or paper pulp water-borne method or solvent method
By modifying the large biological molecule cellulose being made, there is application in food and medicine, be selected as host material preparation
Novel rare-earth luminescent composite is expected to further expand the application and preparation method of rare earth compound.
The content of the invention
It is an object of the invention to for problem present in prior art, Rare Earth Europium Complex is naturally divided greatly with cellulose
Son provides even porous aerogel composite, the preparation side of a kind of emitting red light for luminescence display field with Covalent bonding together
Method and application.
To solve above technical problem, technical scheme includes：
（One）A kind of even porous rare earth composite material of emitting red light
The chemical constituent of the composite is CMC/TTA/Eu, wherein, CMC is sanlose, and TTA is 2- thiophene first
Anion after acyl trifluoroacetone deprotonation, Eu is rare-earth europium ion, and the Rare Earth Europium Complex of the composite is with covalent bond side
Formula is connected with cellulose macromolecule network, and its decomposition temperature is 240 DEG C.
（Two）Prepare above-mentioned composite porous method
Comprise the following steps：
(1) powder of sanlose is dissolved into deionized water under agitation, then is added dropwise to EuCl3Water
In solution, transparent beads shape CMC/Eu is obtained3+Hydrogel；
（2）By CMC/Eu3+Hydrogel is added to the 2- TTA sodium salts of mass percent concentration 0.5~1.5%
The aqueous solution in, mix slowly 24h, collect hydrogel, washing；
(3) with the ethanol exchange step of various concentrations（2）Hydrogel after washing, obtains alcogel, and supercritical carbon dioxide is done
It is dry, obtain end-product.
Further, the step（1）Sanlose solution mass percent concentration be 2 ~ 6%；Described
EuCl3Molar concentration be 0.01 ~ 0.1M.
Further, the step（3）Ethanol concentration gradient be 5%, 25%, 45%, 65%, 85%, 100%.
Further, the step（3）CO 2 supercritical condition be 8 ~ 35Mpa, temperature be 32 ~ 46 DEG C.
The step（3）TTA sodium salts mass percent concentration be 0.5 ~ 1.5%.
（Three）The application of the luminous aerogel composite of the present invention
Red fluorescence material is used as using the aerogel composite.
The beneficial effects of the invention are as follows：
First, the good carboxymethyl cellulose macromolecular of biocompatibility and biodegradability is introduced rare-earth compound luminescent material
Material, is expected to further expand the application of rare earth luminescent material.
Secondly, compared with the mode of physical doping, the present invention, which coordinates rare-earth europium and TTA, is covalently bonded to fibre
In the plain natural macromolecular three-dimensional network of dimension, it is to avoid Rare Earth Europium Complex is analysed from matrix from leakage.Meanwhile, pass through organic ligand TTA
Absorbing ultraviolet light transmission energy makes rare-earth europium ion send feature red fluorescence.
3rd, composite of the invention obtains emission spectrum in the case where 354 nm are excited, and maximum emission peak is in 616 nm
Place, is the pure red fluorescence emission peak of typical rare-earth europium ion, excitation is very high, it is expected to be imaged material as biological
Material.Meanwhile, the decomposition temperature of the composite is 240 DEG C, can stabilization at high temperature,
4th, composite of the invention has more uniform regular macroporous structure, can be used for porous functional material.
In preparation method：1）Reaction condition is gentle, is carried out in the aqueous solution that can be at room temperature, at a normal, preparation technology compared with
To be simple；2）Solvent is made from environment-friendly water, belongs to friendly process；3）Material post processing is easy；4）Can be different
Rare earth ion and organic ligand are connected in the way of covalent bond in cellulose network skeleton, so as to realize that glow color finely may be used
The target of tune.
TTA of the present invention is the abbreviation of TTA, its molecular formula：C8H5F3O2S, molecular weight：222.18.System
In standby, the present invention uses TTA and the reacted sodium salt of sodium hydroxide.
Brief description of the drawings
Fig. 1 is the luminous composite porous aspect graph.
Fig. 2 is the composite porous figure under ultra violet lamp that lights.
Fig. 3 is the luminous composite porous scanning electron microscope (SEM) photograph.
Fig. 4 is the luminous composite porous mapping electron microscopes.
Fig. 5 is the luminous composite porous nitrogen adsorption desorption curve figure.
Fig. 6 is the luminous composite porous exciting light spectrogram under 616 nm monitorings.
Fig. 7 is the composite porous launching light spectrogram in the case where 354 nm are excited that lights.
Below in conjunction with accompanying drawing, by embodiment, the present invention will be further described, and embodiment includes but do not limit guarantor of the present invention
Protect scope.
Embodiment
（One）Prepare this luminous composite porous
Embodiment 1：
2.0 g sanloses are added to 100 mL deionized waters, stirring is to being completely dissolved.By carboxymethyl cellulose
Plain sodium salt is added dropwise to the mol/L of 100 mL 0.01 EuCl3In the aqueous solution, transparence hydrogel bead is obtained, deionization is used
Washing, obtains CMC/Eu3+Hydrogel.0.5g TTA sodium salt is weighed, is added in 100 ml deionized waters, in magnetic stirring apparatus
On be slowly stirred after 24 h, fully washed with distilled water, then exchanged with the ethanol of various concentrations gradient, obtain alcogel,
Alcogel is dried with overcritical (8.5 Mpa, 31 DEG C) carbon dioxide, finally obtains porous aerogel composites.
Embodiment 2：
3.0 g sanloses are added to 100 mL deionized waters, stirring is to being completely dissolved.By carboxymethyl cellulose
Plain sodium salt is added dropwise to the mol/L of 100 mL 0.03 EuCl3In the aqueous solution, transparence hydrogel bead is obtained, deionization is used
Washing, obtains CMC/Eu3+Hydrogel.1.0g TTA sodium salt is weighed, is added in 100 ml deionized waters, in magnetic stirring apparatus
On be slowly stirred after 24 h, fully washed with distilled water, then exchanged with the ethanol of various concentrations gradient, obtain alcogel,
Alcogel is dried with overcritical (15 Mpa, 35 DEG C) carbon dioxide, finally obtains porous aerogel composites.
Embodiment 3：
4.0 g sanloses are added to 100 mL deionized waters, stirring is to being completely dissolved.By carboxymethyl cellulose
Plain sodium salt is added dropwise to the mol/L of 100 mL 0.06 EuCl3In the aqueous solution, transparence hydrogel bead is obtained, deionization is used
Washing, obtains CMC/Eu3+Hydrogel.1.5g TTA sodium salt is weighed, is added in 100 ml deionized waters, in magnetic stirring apparatus
On be slowly stirred after 24 h, fully washed with distilled water, then exchanged with the ethanol of various concentrations gradient, obtain alcogel,
Alcogel is dried with overcritical (20 Mpa, 36 DEG C) carbon dioxide, finally obtains porous aerogel composites.
Embodiment 4：
6.0 g sanloses are added to 100 mL deionized waters, stirring is to being completely dissolved.By carboxymethyl cellulose
Plain sodium salt is added dropwise to the mol/L of 100 mL 0.1 EuCl3In the aqueous solution, transparence hydrogel bead is obtained, deionized water is used
Wash, obtain CMC/Eu3+Hydrogel.1.5g TTA sodium salt is weighed, is added in 100 ml deionized waters, on magnetic stirring apparatus
It is slowly stirred after 24 h, is fully washed with distilled water, is then exchanged with the ethanol of various concentrations gradient, alcogel is obtained, alcohol
Gel is dried with overcritical (25 Mpa, 40 DEG C) carbon dioxide, finally obtains porous aerogel composites.
（Two）It is luminous it is composite porous in the sunlight and the photo under uviol lamp
Fig. 1,2 for the luminous porous aerogel composite respectively in the sunlight and the photo under ultra violet lamp, from figure
It can be found that in the sunlight, the porous aerogel composite that lights is white coccoid.Under ultra violet lamp, light porous
Aerogel composite launches red fluorescence.
（Three）Luminous composite porous pattern
It is small using the luminous porous aerogel of NOVA/NANOSEM-450 field emission scanning electron microscopes observation of FEI Co. of the U.S.
The section of ball, it can be found that the bead shows similar cellular regular macroporous structure from Fig. 3.It can be sent out from Fig. 4
Existing, Rare Earth Europium Complex is evenly distributed in cellulose macromolecule network.The nitrogen adsorption of luminous porous aerogel composite
Desorption curve is obtained on Micromeritics ASAP 2010, and test temperature is taken out true before 77 K, test under 323K
Sky reaches 3 × 10 until vacuum-3Torr .Fig. 5 shows that the absorption that typical large pore material is presented in the luminescent material takes off
Attached performance, it is consistent with Fig. 3 result.
（Four）Luminous composite porous fluorescence property
Fig. 6 and Fig. 7 are the excitation and emission spectras of luminous porous aerogel composite, are can be found that from Fig. 6：Rare-earth europium from
4f → 4f transition of son does not occur in excitation spectrum, illustrates that TTA forms covalent complex with rare-earth europium ion, by having
Machine part TTA absorbs ultraviolet light and transmission energy.Fig. 7 is that luminous porous aerogel composite is sent out in the case where 363 nm are excited
Spectrum is penetrated, maximum emission peak is the red emission peak of typical rare-earth europium ion, shows the color of resulting materials at 616 nm
Purity is high, with monochromaticjty.In Fig. 7 emission spectrum, TTA emission peak is not observed yet, TTA parts are further illustrated
Covalent bond mould assembly complex is formd with rare-earth europium ion, Rare Earth Europium Complex is bonded to cellulose network so as to reach
In purpose.
The F-4600 sepectrophotofluorometers that above fluorescence spectrum experiments are produced using Hitachi, Ltd (Hitachi) are complete
Into.
Claims (7)
1. a kind of even porous rare earth composite material of emitting red light, it is characterized in that：The chemical constituent of the composite is CMC/
TTA/Eu, wherein, CMC is sanlose, and TTA is the anion after 2- TTA deprotonations, Eu
For rare-earth europium ion, the Rare Earth Europium Complex of the composite is covalently connected with cellulose macromolecule network, its point
It is 240 DEG C to solve temperature.
2. a kind of preparation method of porous rare earth composite as claimed in claim 1, comprises the following steps：
(1) powder of sanlose is dissolved into deionized water under agitation, then is added dropwise to EuCl3It is water-soluble
In liquid, transparent beads shape CMC/Eu is obtained3+Hydrogel；
（2）By CMC/Eu3+Hydrogel is added to the 2- TTA sodium salts of mass percent concentration 0.5~1.5%
In the aqueous solution, mix slowly 24h, collect hydrogel, washing；
(3) with the ethanol exchange step of various concentrations（2）Hydrogel after washing, obtains alcogel, and supercritical carbon dioxide is done
It is dry, obtain end-product.
3. the preparation method of the porous rare earth composite according to claim 2, it is characterized in that：The step（1）'s
The mass percent concentration of sanlose solution is 2 ~ 6%；Described EuCl3Molar concentration be 0.01 ~ 0.1M.
4. the preparation method of the porous rare earth composite according to claim 2 or 3, it is characterized in that：The step
（3）Ethanol concentration gradient be 5%, 25%, 45%, 65%, 85%, 100%.
5. the preparation method of the porous rare earth composite according to claim 2 or 3, it is characterized in that：The step
（3）CO 2 supercritical condition be 8 ~ 35Mpa, temperature be 32 ~ 46 DEG C.
6. the preparation method of the porous rare earth composite according to claim 4, it is characterized in that：The step（3）'s
CO 2 supercritical condition is 8 ~ 35Mpa, and temperature is 32 ~ 46 DEG C.
7. a kind of application of porous rare earth composite as described in claim 1, it is characterized in that：It is used as red fluorescence material
Material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108468214A (en) * | 2018-01-22 | 2018-08-31 | 东莞市联洲知识产权运营管理有限公司 | A kind of fluorescent fiber element base fiber containing multistage hole of the high fastness of high load and preparation method thereof |
| CN111036667A (en) * | 2019-11-23 | 2020-04-21 | 山东碧泉环境工程技术有限公司 | Method for repairing heavy metal contaminated soil |
| CN112300410A (en) * | 2020-11-05 | 2021-02-02 | 云南师范大学 | Hydrogel composite material with porous structure and preparation and application thereof |
| CN112321851A (en) * | 2020-11-05 | 2021-02-05 | 云南师范大学 | Lignin rare earth composite luminescent material and preparation and application thereof |
| CN114276801A (en) * | 2021-12-23 | 2022-04-05 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Cellulose-based binuclear rare earth organic polymer composite material with controllable fluorescence and preparation method and application thereof |
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- 2017-06-30 CN CN201710520271.3A patent/CN107163933B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108468214A (en) * | 2018-01-22 | 2018-08-31 | 东莞市联洲知识产权运营管理有限公司 | A kind of fluorescent fiber element base fiber containing multistage hole of the high fastness of high load and preparation method thereof |
| CN111036667A (en) * | 2019-11-23 | 2020-04-21 | 山东碧泉环境工程技术有限公司 | Method for repairing heavy metal contaminated soil |
| CN112300410A (en) * | 2020-11-05 | 2021-02-02 | 云南师范大学 | Hydrogel composite material with porous structure and preparation and application thereof |
| CN112321851A (en) * | 2020-11-05 | 2021-02-05 | 云南师范大学 | Lignin rare earth composite luminescent material and preparation and application thereof |
| CN112300410B (en) * | 2020-11-05 | 2022-07-15 | 云南师范大学 | Hydrogel composite material with porous structure and preparation and application thereof |
| CN114276801A (en) * | 2021-12-23 | 2022-04-05 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Cellulose-based binuclear rare earth organic polymer composite material with controllable fluorescence and preparation method and application thereof |
| CN114921241A (en) * | 2022-04-14 | 2022-08-19 | 新疆农业大学 | Preparation method and application of manganese-containing complex cellulose-based fluorescent functional material |
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