CN111607389B - Ionic gel material based on oil-soluble carbon quantum dots and preparation method thereof - Google Patents
Ionic gel material based on oil-soluble carbon quantum dots and preparation method thereof Download PDFInfo
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Abstract
The invention provides an ionic gel material based on oil-soluble carbon quantum dots and a preparation method thereof, wherein the preparation method comprises the following steps: s1, mixing citric acid and 2-ethylhexylamine, and carrying out sealing reaction at 160-200 ℃; s2, cooling to room temperature, dialyzing in absolute ethyl alcohol, and drying to obtain oil-soluble carbon quantum dots; and S3, dissolving the high molecular polymer in an organic solvent, adding the carbon quantum dots and the ionic liquid prepared in the step S2, heating for 24-72 h at the temperature of 60-100 ℃, and drying and forming. The ionic liquid, the carbon quantum dots and the high molecular polymer show good compatibility, and meanwhile, the ionic liquid not only serves as a constituent component, but also can serve as a plasticizer of the high molecular polymer, so that the obtained ionic gel is softer, the use temperature range is wider, the dynamic performance is higher than that of the traditional polymer gel material, the mechanical performance of the ionic gel is effectively improved, and the processing and forming are convenient.
Description
Technical Field
The invention relates to the field of luminescent composite materials, in particular to a novel high-molecular polymer ionic gel material based on oil-soluble carbon quantum dots and a preparation method thereof.
Background
The ionic gel is a novel multifunctional hybrid material, and is a transparent gelatinous block material prepared by hybrid compounding of ionic liquid and silicon dioxide or organic high molecular polymer. In the ionic gel, the ionic liquid can be fixed in a solid matrix network of silicon dioxide or high molecular polymer, and the physicochemical property of the ionic liquid can regulate and control the properties of the prepared gel material. Furthermore, it is worth mentioning that ionic liquids also impart excellent ionic conductivity to the ionic gel material. Due to the remarkable advantages, the transparent ionic gel has great application potential in the field of all-solid-state devices such as supercapacitors, nanogenerators, electrochemiluminescence pools and the like.
The construction of transparent luminescent materials with adjustable luminescence by introducing luminescent components into ionic gels is a leading development in this field. So far, reported ionic gel materials based on carbon quantum dots mainly fix carbon quantum dots and ionic liquid in a silicon dioxide solid matrix network, so that the obtained materials have poor mechanical properties and are easy to break after being bent for many times, and further application of the materials in certain photoelectric device fields is limited to a certain extent.
Therefore, the invention discloses a novel ionic gel material which is constructed by adopting a high molecular polymer as a solid matrix network and compounding oil-soluble carbon quantum dots, and can effectively solve the problem of poor mechanical properties of the ionic gel material containing the carbon quantum dots in the prior art.
Disclosure of Invention
The invention provides an ionic gel material based on oil-soluble carbon quantum dots and a preparation method thereof, and aims to solve the problems that in the prior art, the ionic gel material containing the carbon quantum dots is poor in mechanical property and easy to break after being bent for multiple times, and further application of the ionic gel material in certain photoelectric device fields is limited to a certain extent.
In order to achieve the purpose, the invention provides an ionic gel material based on oil-soluble carbon quantum dots, wherein the ionic gel synthesizes the carbon quantum dots by using 2-ethylhexylamine, and uses a high molecular polymer as a solid matrix network.
Wherein the high molecular polymer comprises polymethyl methacrylate, polystyrene, polyvinylidene fluoride or polyvinylpyrrolidone.
A preparation method of an ionic gel material based on oil-soluble carbon quantum dots comprises the following steps:
s1, mixing citric acid and 2-ethylhexylamine, uniformly stirring, sealing, and reacting at 160-200 ℃ for 12-36 h;
s2, cooling to room temperature after the reaction is finished, dialyzing in absolute ethyl alcohol for 24-72 h, and drying at 70-100 ℃ for 24-72 h to obtain oil-soluble carbon quantum dots;
and S3, dissolving the high molecular polymer in an organic solvent to form a solution, then adding the carbon quantum dots and the ionic liquid prepared in the step S2, fully and uniformly stirring, pouring into a mold, heating at 60-100 ℃ for 24-72 h, and drying and forming to obtain the ionic gel material.
Wherein the dosage ratio of the citric acid to the 2-ethylhexylamine in the step S1 is 1g: 2-10 mL.
Wherein, in the step S2, the dialysis bag with the molecular weight cut-off of 500Da, 1000Da or 1500Da is selected for dialysis.
Wherein the organic solvent in step S3 comprises N, N-dimethylacetamide, tetrahydrofuran, acetone, ethanol or methanol.
Wherein the ionic liquid in the step S3 comprises 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt or 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt.
Wherein the mass ratio of the carbon quantum dots, the ionic liquid and the high molecular polymer is 1g: 20-80 g:20 to 80g.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, 2-ethylhexylamine is used as a raw material for synthesizing the carbon quantum dots for the first time, on one hand, the carbon quantum dots can be used as a surface protective agent for modifying carbon quantum, so that the carbon quantum dots have oil solubility, can be dissolved and dispersed in various organic solvents to form a transparent and stable solution, and meanwhile, the carbon quantum dots can be compatible with ionic liquid and high molecular polymers; on the other hand, the method can be simultaneously used as a reaction medium, so that the use of an additional solvent is avoided, and the preparation process of the carbon quantum dots is simplified.
2. The carbon quantum dot material obtained by the method has excellent fluorescence performance, the luminescence of the carbon quantum dot material has excitation wavelength dependency, and the effective regulation and control of the luminescence color from blue to green can be realized.
3. The transparent luminescent ion gel material prepared by using the carbon quantum dots has excellent mechanical stability and luminescent color adjustability, and the application of the ion gel material in the field of photoelectric devices is greatly expanded.
The ionic liquid, the carbon quantum dots and the high molecular polymer show good compatibility, and meanwhile, the ionic liquid is used as a constituent component and also can be used as a plasticizer of the high molecular polymer, so that the obtained ionic gel is softer, the use temperature range is wider, the dynamic performance is higher than that of the traditional polymer gel material, the elongation at break is 290%, good ductility is shown, the mechanical property of the ionic gel is effectively improved, and the ionic gel is convenient to process and form.
Drawings
FIG. 1 is a transmission electron microscope image of oil-soluble carbon quantum dots of the present invention;
FIG. 2 is an absorption spectrum of the oil-soluble carbon quantum dots of the present invention;
FIG. 3 is a photoluminescence spectrum of oil-soluble carbon quantum dots of the present invention at different excitation wavelengths;
FIG. 4 is a scanning electron microscope image of an ionic gel (CDs-EHA/[ BMIm ] [ TFSA ]/PMMA) according to the present invention;
FIG. 5 is a photoluminescence spectrum of ionic gel (CDs-EHA/[ BMIm ] [ TFSA ]/PMMA) of the present invention at different excitation wavelengths;
FIG. 6 is a graph of stress-strain curves for ionic gels of the invention (CDs-EHA/[ BMIm ] [ TFSA ]/PMMA).
Detailed Description
The present invention will be described in detail below with reference to the attached drawings and specific embodiments, and the embodiments described herein are only for illustrating and explaining the present invention, but not for limiting the present invention. The drugs used in the examples are all available from reagent companies.
Example 1
Adding 1g of citric acid into 3mL of 2-ethylhexylamine, stirring and mixing uniformly, pouring the mixed solution into a high-temperature reaction kettle, sealing, placing in an oven, heating to 200 ℃ for reaction for 12h, cooling to room temperature after the reaction is finished, placing the obtained liquid product into a dialysis bag with the molecular weight cutoff of 500Da, dialyzing in absolute ethyl alcohol (purity of 99.95%) for 24h, and drying the ethanol solution of the carbon quantum dots in the dialysis bag at 80 ℃ for 24h to obtain the oil-soluble carbon quantum dots (CDs-EHA).
Dissolving 2g of polymethyl methacrylate (PMMA) in 10mL of DMF to form a transparent solution, then adding 0.05g of prepared CDs-EHA and 1g of 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ([ BMIm ] [ TFSA ]) ionic liquid into the PMMA solution, fully stirring and uniformly mixing, pouring into a glass mold, heating at 80 ℃ for 36h, drying and forming to obtain an ionic gel material (CDs-EHA/[ BMIm ] [ TFSA ]/PMMA).
As shown in fig. 1, the transmission electron microscope image of the oil-soluble carbon quantum dot prepared in this example shows that the carbon quantum dot has a spheroidal shape and a particle size distribution of 8-15 nm, and thus it can be confirmed that a new oil-soluble carbon quantum dot is successfully synthesized by the method of the present invention.
The absorption spectrum of the oil-soluble carbon quantum dot prepared in this example as shown in fig. 2 shows that the carbon quantum dot solution exhibits significant optical absorption intensity in the wavelength range of 200-500 nm, wherein the two absorption peak positions are at 239nm and 362nm, respectively.
As shown in fig. 3, a photoluminescence spectrum of the oil-soluble carbon quantum dot prepared in this embodiment under different excitation wavelengths is shown, and it can be seen from the graph that photoluminescence of the prepared carbon quantum dot has excitation wavelength dependency, and when the excitation wavelength is 360nm, an emission peak position is located at 440nm, and is blue light; when the excitation wavelength is 440nm, the emission peak position is 519nm, which is green light.
As shown in the scanning electron microscope image of the ionic gel (CDs-EHA/[ BMIm ] [ TFSA ]/PMMA) prepared in the embodiment, the surface of the ionic gel material is smooth and flat when observed from the microscopic size, which shows that the CDs-EHA, [ BMIm ] [ TFSA ] and PMMA have good compatibility, and the CDs-EHA can be uniformly dispersed and fixed in the ionic gel material.
As shown in FIG. 5, the photoluminescence spectra of the ionic gel (CDs-EHA/[ BMIm ] [ TFSA ]/PMMA) prepared in this example under different excitation wavelengths are shown, and it can be seen from the figure that the prepared ionic gel has the same photoluminescence behavior as CDs-EHA and also has excitation wavelength dependence, and when the excitation wavelength is 360nm, the emission peak position is at 439nm and is blue light; when the excitation wavelength was 440nm, the emission peak position was at 518nm, which is green light, indicating that the luminescence properties of CDs-EHA were not affected by the surrounding environment.
The stress-strain curve of the ionic gel (CDs-EHA/[ BMIm ] [ TFSA ]/PMMA) prepared by the present example as shown in FIG. 6 shows that the prepared ionic gel has a large elongation at break (290%), and exhibits good ductility; in addition, the ionic gel material has no fracture phenomenon after being bent for many times, which shows that the mechanical property of the material is stable.
Example 2
1g of Polystyrene (PS) was dissolved in 10mL of Tetrahydrofuran (THF) to form a transparent solution, and then 0.05g of CDs-EHA and 1g of BMIm TFSA ionic liquid prepared in example 1 were added to the above PS solution, and after thoroughly mixing, they were poured into a glass mold, heated at 80 ℃ for 36 hours, dried and molded to obtain an ionic gel material (CDs-EHA/[ BMIm ] [ TFSA ]/PS).
Example 3
1g of polyvinylidene fluoride (PVDF) was dissolved in 10mL of N, N-Dimethylacetamide (DMF) to form a transparent solution, and then 0.05g of CDs-EHA prepared in example 1 and 1g of [ BMIm ] [ TFSA ] ionic liquid were added to the above PVDF solution, and after thoroughly stirring and mixing, the mixture was poured into a glass mold, heated at 80 ℃ for 36 hours, and dried to form an ionic gel material (CDs-EHA/[ BMIm ] [ TFSA ]/PVDF).
Example 4
1g of polyvinylpyrrolidone (PVP) was dissolved in 10mL of ethanol to form a clear solution, and then 0.05g of CDs-EHA and 1g of BMIm TFSA ionic liquid prepared in example 1 were added to the above PVP solution, and after thoroughly stirring and mixing, the mixture was poured into a glass mold, heated at 80 ℃ for 36 hours, and dried and shaped to obtain an ionic gel material (CDs-EHA/[ BMIm ] [ TFSA ]/PVP).
The optimal dosage ratio of the citric acid to the 2-ethylhexylamine is 1g:3mL; the optimal reaction temperature is 200 ℃ when the oil-soluble carbon quantum dots are prepared, the optimal reaction time is 12h, and a dialysis bag with the molecular weight cut-off of 500Da, 1000Da or 1500Da is selected for dialysis, wherein the optimal molecular weight cut-off is 500Da.
The ionic liquid comprises 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ([ BMIm ] [ TFSA ]), and also comprises 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ([ EMIm ] [ TFSA ]).
The organic solvent of the invention comprises acetone or methanol besides N, N-Dimethylacetamide (DMF), tetrahydrofuran (THF) and ethanol.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (5)
1. A preparation method of an ionic gel material based on oil-soluble carbon quantum dots is characterized by comprising the following steps:
s1, mixing citric acid and 2-ethylhexylamine, uniformly stirring, sealing, and reacting at 160-200 ℃ for 12-36 h;
s2, cooling to room temperature after the reaction is finished, dialyzing in absolute ethyl alcohol for 24-72 h, and drying at 70-100 ℃ for 24-72 h to obtain oil-soluble carbon quantum dots;
s3, dissolving polymethyl methacrylate in N, N-dimethylacetamide to form a solution, then adding the carbon quantum dots and the ionic liquid prepared in the step S2, fully and uniformly stirring, pouring into a mold, heating at 60-100 ℃ for 24-72 h, and drying and forming to obtain an ionic gel material;
the ionic liquid is 1-ethyl-3-methylimidazolium diimidate or 1-butyl-3-methylimidazolium diimidate.
2. The preparation method of the oil-soluble carbon quantum dot-based ionic gel material as claimed in claim 1, wherein the ratio of the citric acid to the 2-ethylhexylamine in step S1 is 1g:2 to 10mL.
3. The preparation method of the oil-soluble carbon quantum dot-based ionic gel material, according to claim 1, wherein the dialysis bag with the molecular weight cutoff of 500Da, 1000Da or 1500Da is selected in the step S2.
4. The preparation method of the oil-soluble carbon quantum dot-based ionic gel material according to claim 1, wherein the mass ratio of the carbon quantum dots to the ionic liquid to the polymethyl methacrylate is 1:20 to 80:20 to 80g.
5. An ionic gel material prepared by the preparation method of the ionic gel material based on the oil-soluble carbon quantum dots according to any one of claims 1 to 4.
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