CN107602757B - Preparation method of carbon quantum dot/acrylate copolymer fluorescent composite material - Google Patents
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Abstract
The invention belongs to the field of nano composite material research, and particularly relates to a preparation method of a carbon quantum dot/acrylate copolymer fluorescent composite material, which comprises the following steps: preparing nitrogen-doped carbon quantum dots, passivating, preparing a solid organic-inorganic hybrid carbon quantum dot material with stable carbon quantum dot dispersion in the hydrolysis process of organosilane based on the passivated nitrogen-doped carbon quantum dots, and introducing the obtained solid organic-inorganic hybrid carbon quantum dot material into an acrylate copolymer through in-situ polymerization.
Description
Technical Field
The invention belongs to the field of nano composite material research, and particularly relates to a preparation method of a carbon quantum dot/acrylate copolymer fluorescent composite material.
Background
Among all the fluorescent carbon materials, most of research efforts are focused on the field of carbon quantum dots because of the controllability of their structure, the adjustability of luminescence, and the possibility of mass production. Carbon quantum dots (CDs) are an environment-friendly fluorescent nano material with similar optical performance to semiconductor quantum dots, have the size of less than 10nm, are approximately quasi-spherical in microcosmic view, are rich in organic functional groups on the surface, and have incomparable advantages of good biocompatibility, easiness in large-scale synthesis and functional modification, low preparation cost, mild reaction conditions and the like besides the advantages of the traditional semiconductor quantum dots such as excellent optical performance, small size and the like.
Recent research shows that CDs have a behavior of photoinitiated electron transfer, which indicates that CDs have potential application value in the fields of battery technology, photovoltaic equipment, light capture materials and the like; the surface of CDs can be subjected to various functional modifications through reasonable design, so that the photoelectric property of CDs is influenced; the fluorescent material is expected to solve the defects of the traditional fluorescent material in light stability and toxicity, and is an emerging fluorescent material.
Disclosure of Invention
The invention provides a preparation method of a carbon quantum dot/acrylate copolymer fluorescent composite material, which comprises the following steps:
preparing nitrogen-doped carbon quantum dots, passivating, preparing a solid organic-inorganic hybrid carbon quantum dot material with stable carbon quantum dot dispersion in the hydrolysis process of organosilane based on the passivated nitrogen-doped carbon quantum dots, introducing the obtained solid organic-inorganic hybrid carbon quantum dot material into an acrylate copolymer through in-situ polymerization,
the specific operation is as follows:
(1) preparation and passivation of carbon quantum dots
Preparing glucose and NH3And NaOH solution, performing ultrasonic treatment until the solution is brownish red, adjusting the pH value of the solution to be neutral after suspension steaming, adding ethanol, stirring, adding excessive anhydrous magnesium sulfate, stirring fully, standing to remove salt and water to obtain an ethanol solution of the carbon quantum dots,
adding excessive anhydrous magnesium sulfate, stirring thoroughly, removing water (filtering solid impurities after stirring and standing); the salt is difficult to dissolve in ethanol and is separated out, the separated salt is settled after standing for a period of time (at least 24 hours),
passivation: adding KH550, KH570, EtOH and water into the obtained ethanol solution of the carbon quantum dots, heating and stirring, removing the solvent to obtain a solid organic-inorganic hybrid carbon quantum dot material,
wherein, because the energy for carbonizing the carbon source is less by the ultrasonic method, the sodium hydroxide is adopted to be beneficial to the preparation of carbon points under the alkali-assisted condition,
the reaction system comprises carbon quantum dots and incompletely carbonized glucose impurities, active groups rich on the surfaces of the carbon quantum dots can be well dispersed in ethanol, and incompletely carbonized glucose and the like are insoluble or slightly soluble in ethanol, so that the non-carbonized impurities and water in the system are removed by adding anhydrous magnesium sulfate,
adding KH550, KH570, EtOH and water according to the volume ratio of (KH550+ KH 570): EtOH: water 5: 75: 25,
heating to 80 ℃, stirring for 2 hours,
the fluorescence performance of the carbon quantum dots can be enhanced after the surface passivation (see figure 6);
(2) preparation of carbon quantum dot/acrylate copolymer fluorescent composite material
Mixing and fully dispersing acrylate monomers, an initiator, a solvent and the solid organic-inorganic hybrid carbon quantum dot material obtained in the step (1), heating and polymerizing,
wherein the acrylate monomer is methyl methacrylate, butyl methacrylate or the mixture of the methyl methacrylate and the butyl methacrylate,
the initiator is BPO, the solvent is toluene,
the dosage ratio of the solid organic-inorganic hybrid carbon quantum dot material to the solvent is 0.1 g/mL.
The invention has the beneficial effects that:
the nitrogen-doped carbon quantum dots are prepared by adopting a one-step ultrasonic method, the cost is low, the environment is protected, the used composite silane is self-assembled with the carbon quantum dots in the hydrolysis condensation process, and the obtained solid organic-inorganic hybrid carbon quantum dots can be used as polymerization components to participate in polymerization, so that the compatibility with a polymer matrix is improved, the fluorescence quenching caused by the agglomeration of the carbon quantum dots due to large surface activity is prevented, and the optical performance of the carbon quantum dots is effectively stabilized. In addition, the introduction amount of the organic-inorganic hybrid carbon quantum dots is smaller in the system, so that concentration induced fluorescence quenching is avoided;
during the hydrolysis and condensation of the organosilane, part of amine groups or other groups form covalent bonds with active components (hydroxyl and carboxyl) on carbon points; many alkoxy groups are hydrolyzed to form a very reactive intermediate silanol, and the silanol group is condensed with other silanol groups or hydroxyl groups to form bonds. Double bonds introduced by gamma-methacryloxypropyltrimethoxysilane in the system participate in polymerization, and amino introduced by 3-aminopropyltriethoxysilane and an initiator are homolytically cracked to form free radicals in the polymerization process to act, so that the compatibility of the organosilicon carbon dots and the acrylate copolymer can be better improved, and the fluorescent enhancement can be possibly performed to a certain extent. In addition, the organic-inorganic hybrid carbon quantum dots play a role similar to cross-linking dots in the system, and are beneficial to improving the strength of the system.
Drawings
FIG. 1 is a high-resolution transmission electron micrograph (a) and a particle size distribution chart (b) of carbon quantum dots prepared in step (1) of example 1;
fig. 2 is a nuclear magnetic spectrum (b) of the carbon quantum dot prepared in the step (1) of example 1, and an infrared spectrum (a) of the solid organic-inorganic hybrid carbon quantum dot material prepared in the step (1) of example 1;
FIG. 3a is an atomic mechanical microscope photograph of solid organic-inorganic hybrid carbon quantum dots prepared in step (1) of example 1; FIG. 3b is a digital photograph of the solid organic-inorganic hybrid carbon quantum dot prepared in step (1) of example 1 under excitation wavelength of 365nm (left: liquid, bottom right: solid) and visible light irradiation (top right);
FIG. 4 is a transmission electron microscope image of the carbon quantum dot/acrylic ester copolymer fluorescent composite material prepared in step (2) of example 1;
FIG. 5 is a fluorescence spectrum of the carbon quantum dot/acrylic ester copolymer fluorescent nanocomposite prepared in the step (2) of example 1 (the top left inset is a digital photograph under irradiation of visible light (top) and excitation wavelength 365nm (bottom),
as can be seen from fig. 5, fluorescence studies of the prepared nano-fluorescent composite material showed excellent emission performance due to proper preservation of PL properties of the embedded CDs dots, which generate higher energy photons during irradiation due to more efficient energy transfer to excited state after carbon dots are embedded in the polymer; in solution, the non-radiative deactivation pathways are more efficient due to the proximity of solvent molecules, whereas in the case of solid composites, these processes are minimized;
in fig. 6, a and b are fluorescence spectra of the carbon quantum dot and the solid organic-inorganic hybrid carbon quantum dot prepared in step (1) of example 1, respectively.
Detailed Description
Example 1
(1) Preparation and passivation of carbon quantum dots
Preparing 50mL of transparent solution containing 4.5g of glucose, 4.5mL of ammonia water with the mass concentration of 28% and 1g of NaOH by using water as a solvent, performing ultrasonic treatment at room temperature (25 ℃) for 12 hours until the solution is brownish red, performing suspension evaporation until the volume of the solution is 30mL, adjusting the pH to 7 by using dilute hydrochloric acid, dropwise adding 100mL of ethanol, stirring, adding excessive anhydrous magnesium sulfate, fully stirring, standing for 24 hours to remove salt and water to obtain an ethanol solution of carbon quantum dots,
FIG. 1 is a high resolution transmission electron microscope image (JEM-2100) and a particle size distribution image of the carbon quantum dots prepared as described above, and it can be seen that the obtained carbon quantum dots are spherical-like nanoparticles having an average particle size of 3.5nm, and a transmission electron microscope image of a larger magnification shows that the center of the carbon quantum dots is a distinct crystal structure, the crystal lattice is coherent and clear, the crystal lattice size is about 0.214nm, and is close to planar aromatic carbon or (102) sp2Graphitic carbon, which means that the structure of the carbon quantum dots prepared as described above resembles crystalline graphitic carbon,
FIG. 2(b) is a nuclear magnetic spectrum of the carbon quantum dots prepared as described above, and sp is shown in peaks at δ 90 to 180ppm and δ 8 to 80ppm2Hybridized carbon and sp3Hybridized carbon, which also verifies the presence of planar aromatic carbons or (102) sp in the "carbon dot structure" described above2The presumption of graphitic carbon "is that,
passivation: adding 25mL of deionized water, 75mL of the ethanol solution of the carbon quantum dots prepared in the step (1) after the concentration is adjusted, 2.35g of KH550 and 2.65g of KH570 into a 250mL beaker, controlling the concentration of the carbon quantum dots in the obtained mixed solution to be 20mg/mL, heating to 80 ℃, stirring for 2 hours, and removing the solvent to obtain the solid organic-inorganic hybrid carbon quantum dot material.
FIG. 2(a), curve 1728cm for SiCDs-1Due to amide bonds (-CONH-), indicating an amidation reaction between organosilanes and CDs,
as can be seen from FIG. 3(a), the surface roughness of the sample is between 1 nm and 5nm, and no obvious phase separation occurs, so that after the carbon quantum dots are estimated to be stabilized by strong Si-O-Si bonding, no serious agglomeration phenomenon occurs, the dispersion is relatively uniform, and in addition, the point is more intuitively observed by a high-power scanning electron microscope picture;
fig. 6 shows that the solid organic-inorganic hybrid carbon quantum dot material not only well maintains the fluorescence property of the carbon quantum dot, but also enhances the fluorescence intensity by 9.8% before and after passivation treatment;
(2) preparation of carbon quantum dot/acrylate copolymer fluorescent composite material
Adding 8mL of methyl methacrylate, 2mL of butyl methacrylate and 3mL of toluene solvent (0.3 g of the solid organic-inorganic hybrid carbon quantum dot material obtained in the step (1) is dispersed in the toluene solvent) and initiator BPO accounting for 0.1% of the weight of the system into a three-neck flask, firstly carrying out ultrasonic treatment on the system for 30 minutes, placing the flask in a water bath for prepolymerization at 78 ℃ for 6 hours after the initiator BPO is completely dissolved, finally reacting the prepolymerization product at 60 ℃ in a closed environment for 24 hours to complete polymerization (when the viscosity of the system is mutated, namely the polymerization is completed),
as can be seen from FIG. 4, the solid organic-inorganic hybrid carbon quantum dots are well dispersed in the polymer matrix, which is attributed to the fact that double bonds introduced by gamma-methacryloxypropyltrimethoxysilane in the system participate in polymerization, and amino groups introduced by 3-aminopropyltriethoxysilane and free radicals formed by initiator homolytic cleavage during polymerization act, so that the compatibility of the organic-inorganic hybrid carbon quantum dots and acrylate copolymers can be better improved, and in addition, the effect on fluorescence enhancement can be achieved.
Comparative example 1
Adding 8mL of methyl methacrylate, 2mL of butyl methacrylate, 3mL of toluene solvent and initiator BPO accounting for 0.1 percent of the weight of the system into a three-neck flask, firstly carrying out ultrasonic treatment on the system for 30 minutes, placing the flask into a water bath for prepolymerization at 78 ℃ for 4 hours after the initiator BPO is completely dissolved, finally reacting the prepolymerization product at 60 ℃ for 24 hours to generate the mutation of the viscosity of the system, namely finishing the polymerization,
compared with example 1, in the comparative experiment, the solid organic-inorganic hybrid carbon quantum dots are not added into the system, and the polymerization completion time is obviously shortened, so that the solid organic-inorganic hybrid carbon quantum dots in example 1 are supposed to act on free radicals formed by homolytic cracking of an initiator, so that the solid organic-inorganic hybrid carbon quantum dots are dispersed more uniformly.
Comparative example 2
When the carbon quantum dots are passivated, the dosage of the coupling agent is approximately halved, and the rest of the operation is the same as that of the example 1:
preparing 50mL of transparent solution containing 4.5g of glucose, 4.5mL of ammonia water with the mass concentration of 28% and 1g of NaOH by using water as a solvent, performing ultrasonic treatment at room temperature (25 ℃) for 12 hours until the solution is brownish red, performing suspension evaporation until the volume of the solution is 30mL, adjusting the pH to 7 by using dilute hydrochloric acid, dropwise adding 100mL of ethanol, stirring, adding excessive anhydrous magnesium sulfate, fully stirring, standing for 24 hours to remove salt and water to obtain an ethanol solution of carbon quantum dots,
passivation: adding 25mL of deionized water, 75mL of the ethanol solution of the carbon quantum dots prepared by adjusting the concentration, 1.2g of KH550 and 1.35g of KH570 into a 250mL beaker, controlling the concentration of the carbon quantum dots in the obtained mixed solution to be 20mg/mL, heating to 80 ℃, stirring for 2 hours, and removing the solvent to obtain the solid organic-inorganic hybrid carbon quantum dot material.
The solid organic-inorganic hybrid carbon quantum dot material obtained in the comparative example is detected by the same operation as that shown in the attached figure 6, and the fluorescence intensity of the carbon quantum dot is not changed before and after passivation treatment.
Claims (8)
1. A preparation method of a carbon quantum dot/acrylate copolymer fluorescent composite material is characterized by comprising the following steps: the preparation method comprises the steps of preparing nitrogen-doped carbon quantum dots, passivating, preparing a solid organic-inorganic hybrid carbon quantum dot material with the carbon quantum dots dispersed stably in the hydrolysis process of organosilane based on the passivated nitrogen-doped carbon quantum dots, and introducing the obtained solid organic-inorganic hybrid carbon quantum dot material into an acrylate copolymer through in-situ polymerization;
wherein the nitrogen-doped carbon quantum dots are made of NH3Is a nitrogen source;
the organosilanes are KH550 and KH 570.
2. The method of preparing a fluorescent composite of claim 1, wherein: the preparation method comprises the specific steps of,
(1) preparation and passivation of carbon quantum dots
Preparing glucose and NH3And NaOH solution, performing ultrasonic treatment until the solution is brownish red, adjusting the pH value of the solution to be neutral after suspension steaming, adding ethanol, stirring, adding anhydrous magnesium sulfate, stirring fully, standing, removing salt and water to obtain an ethanol solution of the carbon quantum dots,
adding KH550, KH570, EtOH and water into the obtained ethanol solution of the carbon quantum dots, heating and stirring, and removing the solvent to obtain a solid organic-inorganic hybrid carbon quantum dot material;
(2) preparation of carbon quantum dot/acrylate copolymer fluorescent composite material
And (2) mixing and fully dispersing an acrylate monomer, an initiator, a solvent and the solid organic-inorganic hybrid carbon quantum dot material obtained in the step (1), and heating for polymerization.
3. The method of preparing a fluorescent composite of claim 2, wherein: in the step (1), the volume ratio of KH550, KH570, EtOH and water is (KH550+ KH 570): EtOH: water 5: 75: 25.
4. the method of preparing a fluorescent composite of claim 2, wherein: in the step (1), the temperature is raised to 80 ℃ and the mixture is stirred for 2 hours.
5. The method of preparing a fluorescent composite of claim 2, wherein: the acrylate monomer in the step (2) is methyl methacrylate, butyl methacrylate or a mixture of methyl methacrylate and butyl methacrylate.
6. The method of preparing a fluorescent composite of claim 2, wherein: the initiator in the step (2) is BPO.
7. The method of preparing a fluorescent composite of claim 2, wherein: the solvent in the step (2) is toluene.
8. The method of preparing a fluorescent composite of claim 2, wherein: in the step (2), the dosage ratio of the solid organic-inorganic hybrid carbon quantum dot material to the solvent is 0.1 g/mL.
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| CN109100340B (en) * | 2018-08-23 | 2020-10-16 | 浙江理工大学 | Preparation method of implantable sensor modified by cadmium sulfide quantum dots |
| CN110540622A (en) * | 2019-08-09 | 2019-12-06 | 苏州星烁纳米科技有限公司 | Preparation method of quantum dot composite and quantum dot composite prepared by same |
| CN110511739A (en) * | 2019-09-20 | 2019-11-29 | 深圳扑浪创新科技有限公司 | A kind of preparation method of acrylic polymer coated quantum dots |
| CN111603570B (en) * | 2020-07-06 | 2021-04-30 | 南京工业大学 | Carbon-point-modified hollow copolymer nano particle, preparation method and application thereof, drug delivery system and application thereof |
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