CN114806552B - Bis-silane functionalized carbon dot and preparation method and application thereof - Google Patents
Bis-silane functionalized carbon dot and preparation method and application thereof Download PDFInfo
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- CN114806552B CN114806552B CN202111176605.2A CN202111176605A CN114806552B CN 114806552 B CN114806552 B CN 114806552B CN 202111176605 A CN202111176605 A CN 202111176605A CN 114806552 B CN114806552 B CN 114806552B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 59
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 46
- 230000005284 excitation Effects 0.000 claims abstract description 32
- 229960004543 anhydrous citric acid Drugs 0.000 claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 claims description 5
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- LTRPLRHNXPTOIN-UHFFFAOYSA-N [diethoxy(methyl)silyl]methanamine Chemical compound CCO[Si](C)(CN)OCC LTRPLRHNXPTOIN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 5
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
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- 238000000034 method Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- -1 alkoxy silane Chemical compound 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- BSJLEDBWSQNUBG-UHFFFAOYSA-N diethoxysilylmethanamine Chemical compound CCO[SiH](CN)OCC BSJLEDBWSQNUBG-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000001748 luminescence spectrum Methods 0.000 description 3
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- 235000019441 ethanol Nutrition 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
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- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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Abstract
The invention provides a disilane functionalized carbon dot, a preparation method and application thereof, belonging to the technical field of luminescent materials; the preparation method comprises the following steps: adding anhydrous citric acid and a solvent into a high-pressure reaction kettle, wherein the pressure of the high-pressure reaction kettle is 1-3 MPa, and the solvent is one or a combination of a plurality of methanol, ethanol, propanol and isopropanol; adding an organosilane mixture comprising monoamino organosilane and diamino organosilane into a high-pressure reaction kettle, wherein the molar ratio of the monoamino organosilane to the diamino organosilane in the organosilane mixture is 1: (0.25-50); and placing the high-pressure reaction kettle in a baking oven at 160-210 ℃ for solvothermal reaction for 10-14 h to prepare the disilane functionalized carbon dots with different fluorescence emission wavelengths under 365nm ultraviolet excitation. The invention discloses an LED device with the double silane functional carbon dots, which has adjustable luminous wavelength and simple preparation process.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a disilane functionalized carbon dot, and a preparation method and application thereof.
Background
In recent years, with the development of semiconductor lighting technology, light emitting diodes are gradually replacing traditional lighting sources, and become green lighting sources with the most development prospect. According to the report of the blue book of the development of the semiconductor lighting industry in 2019, the current consumption of the LED general lighting product in 2019 reaches 63 hundred million/set, the current consumption permeability is 52.7%, and the electricity saving 3069 hundred million degrees and the carbon emission reduction of 2.4 hundred million tons are realized. Therefore, the development and popularization of the LED manufacturing technology are quickened, and the LED manufacturing technology has important significance for solving the problems of increasingly severe energy shortage and environmental pollution. The luminescent material is a key light conversion material in the LED lighting technology, and the luminous characteristics of the luminescent material directly influence the performance indexes such as brightness, color rendering index, color temperature, luminous efficiency and the like of the white light LED. At present, the luminescent materials adopted by commercial white light LEDs are mainly rare earth fluorescent powder, and the development of the white light LEDs can be limited due to the problems of high synthesis temperature, poor thermal stability, non-renewable rare earth and the like. Thus, the development of new alternative green, efficient solid state light emitting materials has become a new trend in LED development. The carbon dots are green pollution-free nano fluorescent materials, have the advantages of rich raw material sources, simple preparation method, good fluorescent property, easy modification and the like, and are potentially important in various fields. However, the carbon dots have the problems of aggregation-induced fluorescence quenching and the like, and the application progress of the carbon dots in photoelectric devices is restricted. At present, the main method for realizing carbon dot solid state luminescence is to disperse carbon dots in a proper matrix, and avoid quenching caused by energy transfer or reabsorption by regulating and controlling the distance between carbon dot particles. However, the method has the common problem of low carbon dot loading due to poor compatibility of the carbon dots and matrix materials, and can influence the light intensity output of the device in practical application.
The organosilane functionalized carbon dot is a method for modifying the organosilane to the surface of the carbon dot through chemical synthesis, and is an important strategy for regulating and controlling the physicochemical properties of the carbon dot. Compared with carbon dots, the organosilane functionalized carbon dots have excellent luminescence performance, can generate Si-O-Si bonds by utilizing the hydrolytic polycondensation of the organosilane to form a three-dimensional cross-linked structure combined with CDs, can realize solid fluorescence of the carbon dots, can be directly used as an encapsulating material for constructing the LED, and is beneficial to simplifying the encapsulating process of the LED and improving the uniformity of a color conversion layer. In view of this, there have been several documents currently reporting organosilane functionalized carbon sites such as: liu Xuguang et al (Nanoscale, 2016,8 (16): 8618) treated citric acid and N- [3- (trimethoxysilyl) propyl ] ethylenediamine with a simple one-step hydrothermal process at 200deg.C for 6h to prepare liquid organosilane functionalized carbon dots having a fluorescence emission wavelength of 448 nm; xie Zheng et al (J.Mater.chem.C, 2017,5,9629-9637) reacted with citric acid and N- (. Beta. -aminoethyl) -gamma-aminopropyl trimethoxysilane by one-step hydrothermal method at 180deg.C for 12h to prepare a green organosilane functionalized carbon dot with a fluorescence emission wavelength of about 500nm under 440nm excitation; xu Bingshe et al (J.Mater. Chem. C,2017,5 (32), 8105-8111) rapidly synthesized liquid organosilicon functionalized carbon dots with a microwave-assisted hydrothermal method using citric acid and N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane within 5min, with an emission wavelength of 454nm.
However, no report exists on the prior art of disilane functionalized carbon dots with emission wavelength controllable function, and the prior art of organosilicon functionalized carbon dots usually adopts one organosilane for functionalization at a time, so that the prepared fluorescence emission wavelength is mostly not controllable by blue-green light. In addition, the existing organosilane functionalized carbon dots and the packaging material are poor in packaging performance, and poor in service performance on an LED device.
Disclosure of Invention
In order to solve at least one technical problem, the invention provides a preparation method of a disilane functionalized carbon dot, which aims to solve the technical problem that the existing preparation of an organosilicon functionalized carbon dot usually adopts one organosilane for functionalization at one time, and the prepared fluorescence emission wavelength is mostly not controllable by blue-green light.
The invention provides the following technical scheme, namely a preparation method of a disilane functionalized carbon dot, which comprises the following steps:
adding anhydrous citric acid and a solvent into a high-pressure reaction kettle, wherein the pressure of the high-pressure reaction kettle is 1-3 MPa; wherein the solvent is one or a combination of a plurality of methanol, ethanol, propanol and isopropanol;
adding an organosilane mixture comprising monoamino organosilane and diamino organosilane into a high-pressure reaction kettle, wherein the molar ratio of the monoamino organosilane to the diamino organosilane in the organosilane mixture is 1: (0.25-50); wherein the mono-amino organosilane is one of aminopropyl triethoxysilane, aminopropyl methyl diethoxysilane, aminomethyltriethoxysilane or aminomethylmethyl diethoxysilane; the diamino organosilane is one of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, N-beta- (aminoethyl) -gamma-aminopropyl triethoxy silane or N-beta- (aminoethyl) -gamma-aminopropyl methyl diethoxy silane.
And placing the high-pressure reaction kettle in a baking oven at 160-210 ℃ for solvothermal reaction for 10-14 h, and preparing the disilane functionalized carbon dots with different fluorescence emission wavelengths under 365nm ultraviolet excitation.
Compared with the prior art, the preparation method has the beneficial effects that: the preparation method is simple, the raw materials are safe and pollution-free, a plurality of organosilanes are simultaneously used in the reaction process, and the effect of adjusting the fluorescence emission wavelength is realized by adjusting the molar ratio of the organosilanes participating in the reaction to obtain fluorescence from blue light to red light under the excitation of 365nm ultraviolet light.
In some of these embodiments, the molar ratio of the anhydrous citric acid to the organosilane mixture is 1: (2-20). The anhydrous citric acid and the organosilane are mixed more uniformly under the condition of 160-210 ℃ under high pressure environment under the solvent of one or a combination of methanol, ethanol, propanol and isopropanol, so that the intermolecular bonding is facilitated.
The invention also provides the disilane functionalized carbon dot prepared by the preparation method, so as to solve the technical problem that the fluorescence emission wavelength of the existing organosilicon functionalized carbon dot is mostly not controllable by blue-green light.
The invention provides the following technical scheme that the molar ratio of the monosilane to the bisamino organosilane is adjusted to be 1 (9-50), and the obtained bisilane functionalized carbon dot is green fluorescent under 365nm ultraviolet light excitation.
In some of these embodiments, the molar ratio of the mono-amino organosilane to the bis-amino organosilane selected is adjusted to 1 (1-5), resulting in fluorescence of the bis-silane functionalized carbon dots in yellow under 365nm ultraviolet excitation.
In some of these embodiments, the molar ratio of the selected mono-amino organosilane to the bis-amino organosilane is adjusted to 1 (0.25-0.5), resulting in fluorescence of the bis-silane functionalized carbon dots in red under 365nm ultraviolet excitation.
In some of these embodiments, the disilane functionalized carbon dots have an average particle size of 3.2nm, a circular distribution, and a lattice spacing of 0.22nm between lattice fringes of the graphite layer.
In some of these embodiments, the mono-amino organosilane and the di-amino organosilane are each attached to the surface of the carbon dot in the form of an amide bond to enhance the surface state richness of the di-silane functionalized carbon dot.
The invention also provides application of the double-silane functionalized carbon dot to an LED device, so as to solve the technical problems of poor integral packaging performance of the traditional organosilane functionalized carbon dot and a packaging material and poor use performance of the traditional organosilane functionalized carbon dot on the LED device.
The use of bis-silane functionalized carbon dots in LED devices by self-polymerization or copolymerization with an alkoxysilane coupling agent to form films or coatings.
In some embodiments, the prepared disilane functionalized carbon dots are coated into a 360nm LED chip, and the LED chip is placed in an oven environment at 25-80 ℃ to be cured into a film, so that a yellow LED device is obtained.
In some embodiments, the prepared disilane functionalized carbon dots are coated into a 450nm blue light LED chip, and the blue light LED chip is placed in an oven environment at 25-80 ℃ to be cured into a film, so that a white light LED device is obtained
Compared with the prior art, the beneficial effects of the application of the disilane functionalized carbon dots on the LED device are as follows:
1. the method has different curing rates according to the change of the mole ratio and the type of the silane, and can flexibly select the optimal disilane functionalized carbon dots for LED manufacturing and other purposes in practical application.
2. The disilane functionalized carbon dots form a film or a coating through self-polymerization or copolymerization with other alkoxy silane, so that the problems of poor compatibility, poor dispersibility, low load and the like of the traditional fluorescent material and the packaging material are solved, and the integrated packaging is realized.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a high power transmission electron microscope image and a particle size distribution diagram of a bis-silane functionalized carbon dot prepared in example 6 of the present invention;
FIG. 2 is a schematic and block diagram of the synthesis of bis-silane functionalized carbon dots prepared in example 6 of the present invention;
FIG. 3 is a graph showing fluorescence spectra of bis-silane functionalized carbon dots prepared in example 6 of the present invention at different concentrations;
FIG. 4 is a graph showing the luminescence spectrum of a yellow LED prepared from bis-silane functionalized carbon dots prepared in example 6 of the present invention and the operational picture;
fig. 5 is a color coordinate, a light emission spectrum and a picture of the white LED of the bis-silane functionalized carbon point prepared in example 6 of the present invention in operation.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are exemplary and intended to illustrate embodiments of the invention and should not be construed as limiting the invention.
Example 1
0.003mol of anhydrous citric acid and 0.1mol of absolute ethyl alcohol are weighed and put into a high-pressure reaction kettle with the pressure of 1-3 MPa, 0.0021mol of aminopropyl triethoxysilane and 0.0198mol of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane are added into the high-pressure reaction kettle, the constant temperature reaction is carried out for 14 hours in a 160 ℃ oven, and the double-silane functionalized carbon point is obtained after cooling to room temperature and is green fluorescent under 365nm ultraviolet light excitation.
Example 2
0.003mol of anhydrous citric acid and 0.1mol of absolute ethanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.0063mol of aminopropyl triethoxysilane and 0.0154mol of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane are added into the high-pressure reaction kettle, the mixture is reacted for 12 hours at a constant temperature in a 185 ℃ oven, and the mixture is cooled to room temperature to obtain a disilane functionalized carbon dot which is yellow fluorescent under 365nm ultraviolet excitation.
Example 3
0.003mol of anhydrous citric acid and 0.1mol of absolute ethanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.0147mol of aminopropyl triethoxysilane and 0.0066mol of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane are added into the high-pressure reaction kettle, the mixture is reacted for 10 hours at the constant temperature in a baking oven at the temperature of 210 ℃, and the mixture is cooled to the room temperature to obtain the disilane functionalized carbon dots which are red fluorescent under the excitation of 365nm ultraviolet light.
Example 4
0.0015mol of anhydrous citric acid and 0.05mol of absolute ethanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.0021mol of aminopropyl triethoxysilane and 0.0203mol of N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxy silane are added into the reaction kettle, the reaction is carried out for 14 hours at a constant temperature in a 160 ℃ oven, and the reaction kettle is cooled to room temperature, so that the disilane functionalized carbon dots are obtained, and the disilane functionalized carbon dots are green fluorescent under 365nm ultraviolet light excitation.
Example 5
0.0015mol of anhydrous citric acid and 0.05mol of methanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.0063mol of aminopropyl triethoxysilane and 0.0158mol of N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane are added into the reaction kettle, the reaction is carried out for 12 hours at a constant temperature in a 185 ℃ oven, and the reaction kettle is cooled to room temperature, so that the disilane functionalized carbon dots are obtained, and the disilane functionalized carbon dots are yellow fluorescent under 365nm ultraviolet excitation.
Example 6
0.0015mol of anhydrous citric acid and 0.05mol of methanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.0147mol of aminopropyl triethoxysilane and 0.0068mol of N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane are added into the reaction kettle, the reaction is carried out for 14 hours at the constant temperature in a baking oven at the temperature of 210 ℃, and the disilane functionalized carbon dots are obtained after cooling to the room temperature, and are red fluorescent under the excitation of 365nm ultraviolet light.
FIG. 1 shows a high power transmission electron microscope image and a particle size distribution diagram of the bis-silane functionalized carbon dots prepared in example 6, and it can be seen from the image that the average particle size of the bis-silane functionalized carbon dots is about 3.2nm, the bis-silane functionalized carbon dots are distributed circularly and uniformly, and the inter-plane distance of lattice fringes of the graphite layer is 0.22nm.
FIG. 2 shows a schematic and structural diagram of the bis-silane functionalized carbon dots prepared in example 6, and it can be seen from the figure that two silanes are respectively connected to the surface of the carbon dots in the form of amide bonds, thereby increasing the abundance of the surface states of the bis-silane functionalized carbon dots; in specific practice, the disilane functionalized carbon dots can be polymerized or copolymerized with other alkoxy silane to form a film or coating, so that the problems of poor compatibility between the organosilane functionalized carbon dots and packaging materials, poor dispersibility, low load and the like are solved, and the integrated packaging is realized.
Fig. 3 shows fluorescence spectra of the bis-silane functionalized carbon dots prepared in example 6 at different concentrations, and it can be seen from the graph that the emission peak of the bis-silane functionalized carbon dots gradually red shifts with increasing concentration, and according to the light emission characteristic, the concentration of the bis-silane functionalized carbon dots can be adjusted to manufacture yellow LED and white LED. It should be noted that the bis-silane functionalized carbon dots of the present application have different curing rates depending on the molar ratio and the kind of silane used; in practical application, the most suitable disilane functionalized carbon dots can be flexibly selected according to the characteristics to manufacture LEDs or other purposes.
Preparation of a yellow LED: and (3) coating the prepared disilane functionalized carbon dots into a 360nm LED chip, and placing the LED chip in an oven environment at 25-80 ℃ to be cured into a film to obtain a yellow LED device.
Fig. 4 shows the luminescence spectrum of a yellow LED prepared from the disilane functionalized carbon dots prepared in example 6 and a picture thereof in operation, the emission wavelength of the fluorescent film thereof under 365nm excitation being about 550nm.
Preparation of a white light LED: and (3) coating the prepared disilane functionalized carbon dots into a 450nm blue light LED chip, and placing the blue light LED chip in an oven environment at 25-80 ℃ to be cured into a film to obtain a white light LED device.
Fig. 5 shows the color coordinates (a), the luminescence spectrum and the picture (b) of the white LED with the bis-silane functionalized carbon dots prepared in example 6, the color coordinates (0.31, 0.33) of the white LED device are very close to the color coordinates (0.33 ) of the pure white light, the color rendering index is 81.6, and the requirement of indoor illumination is met.
Example 7
0.01mol of anhydrous citric acid and 0.3mol of propanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.0022mol of aminopropyl methyl diethoxy silane and 0.0198mol of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane are added into the high-pressure reaction kettle, the constant temperature reaction is carried out for 14 hours in a 160 ℃ oven, and the double-silane functionalized carbon point is obtained after cooling to room temperature, and the double-silane functionalized carbon point is green fluorescent under 365nm ultraviolet light excitation.
Example 8
0.01mol of anhydrous citric acid and 0.3mol of propanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.0069mol of aminopropyl methyl diethoxy silane and 0.0154mol of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane are added into the reaction kettle, the reaction is carried out for 12 hours at a constant temperature in a 185 ℃ oven, and the bis-silane functionalized carbon point is obtained after cooling to room temperature, and the bis-silane functionalized carbon point is yellow fluorescent under 365nm ultraviolet excitation.
Example 9
Weighing 0.01mol of anhydrous citric acid and 0.3mol of propanol in a high-pressure reaction kettle with the pressure of 1-3 MPa, adding 0.0161mol of aminopropyl methyl diethoxy silane and 0.0066mol of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane into the reaction kettle, reacting the mixture for 10 hours at a constant temperature in a baking oven at 210 ℃, and cooling the mixture to room temperature to obtain a disilane functionalized carbon point which is red fluorescent under 365nm ultraviolet excitation.
Example 10
0.003mol of anhydrous citric acid and 0.1mol of isopropanol are weighed and put into a high-pressure reaction kettle with the pressure of 1-3 MPa, 0.0022mol of aminomethyltriethoxysilane and 0.0203mol of N-beta- (aminoethyl) -gamma-aminopropyl triethoxysilane are added into the high-pressure reaction kettle, the high-pressure reaction kettle reacts for 14 hours at a constant temperature in a 160 ℃ oven, and the high-pressure reaction kettle is cooled to room temperature to obtain disilane functionalized carbon dots which are green fluorescent under 365nm ultraviolet light excitation.
Example 11
0.003mol of anhydrous citric acid and 0.1mol of isopropanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.0069mol of aminomethyltriethoxysilane and 0.0158mol of N-beta- (aminoethyl) -gamma-aminopropyl triethoxysilane are added into the high-pressure reaction kettle, the high-pressure reaction kettle reacts for 12 hours at a constant temperature in a 185 ℃ oven, and the high-pressure reaction kettle is cooled to room temperature to obtain disilane functionalized carbon dots which are yellow fluorescent under 365nm ultraviolet light excitation.
Example 12
0.003mol of anhydrous citric acid and 0.1mol of isopropanol are weighed into a high-pressure reaction kettle, 0.0161mol of aminomethyltriethoxysilane and 0.0068mol of N-beta- (aminoethyl) -gamma-aminopropyl triethoxysilane are added into the high-pressure reaction kettle, the high-pressure reaction kettle is subjected to constant-temperature reaction in an oven at 210 ℃ for 10 hours, and the high-pressure reaction kettle is cooled to room temperature to obtain disilane functionalized carbon dots which are red fluorescent under 365nm ultraviolet light excitation.
Example 13
0.003mol of anhydrous citric acid, 0.05mol of absolute ethyl alcohol and 0.05mol of methanol are weighed into a high-pressure reaction kettle with the pressure of 1-3 MPa, 0.0147mol of aminomethyl diethoxy silane and 0.0068mol of N-beta- (aminoethyl) -gamma-aminopropyl methyl diethoxy silane are added into the high-pressure reaction kettle, the constant temperature reaction is carried out for 12 hours in a 185 ℃ oven, and the double-silane functionalized carbon point is obtained after cooling to room temperature, and the double-silane functionalized carbon point is red fluorescent under 365nm ultraviolet light excitation.
Example 14
0.003mol of anhydrous citric acid, 0.05mol of absolute ethyl alcohol and 0.05mol of propanol are weighed into a high-pressure reaction kettle with the pressure of 1-3 MPa, 0.0147mol of aminomethyl diethoxy silane and 0.0068mol of N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane are added into the high-pressure reaction kettle, the constant temperature reaction is carried out for 12 hours in a 185 ℃ oven, and the double-silane functionalized carbon point is obtained after cooling to room temperature, and the double-silane functionalized carbon point is red fluorescent under 365nm ultraviolet light excitation.
Example 15
0.003mol of anhydrous citric acid, 0.05mol of methanol and 0.05mol of isopropanol are weighed into a high-pressure reaction kettle with the pressure of 1-3 MPa, 0.0147mol of aminomethyl diethoxy silane and 0.0068mol of N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane are added into the high-pressure reaction kettle, the mixture is reacted for 14 hours at a constant temperature in a 160 ℃ oven, and the mixture is cooled to room temperature to obtain disilane functionalized carbon dots which are red fluorescent under 365nm ultraviolet light excitation.
Example 16
0.003mol of anhydrous citric acid and 0.1mol of absolute ethanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.0147mol of aminopropyl methyl diethoxy silane and 0.0068mol of N-beta- (aminoethyl) -gamma-aminopropyl triethoxy silane are added into the high-pressure reaction kettle, the mixture is reacted for 10 hours at the constant temperature in a baking oven at the temperature of 210 ℃, and the mixture is cooled to the room temperature to obtain the disilane functionalized carbon dots which are red fluorescent under the excitation of 365nm ultraviolet light.
Example 17
0.003mol of anhydrous citric acid and 0.1mol of absolute ethanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.0147mol of aminopropyl methyl diethoxy silane and 0.0068mol of N-beta- (aminoethyl) -gamma-aminopropyl triethoxy silane are added into the high-pressure reaction kettle, the mixture is reacted for 13 hours at a constant temperature in a 180 ℃ oven, and the mixture is cooled to room temperature to obtain a disilane functionalized carbon dot which is red fluorescent under 365nm ultraviolet excitation.
Comparative example 1
0.003mol of anhydrous citric acid and 0.1mol of absolute ethanol are weighed and put into a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.021mol of aminopropyl triethoxysilane is added into the high-pressure reaction kettle, the mixture is reacted for 12 hours at the constant temperature in a baking oven at 190 ℃, and the mixture is cooled to the room temperature to obtain the yellowish green fluorescent bis-silane functionalized carbon dot.
Comparative example 2
0.003mol of anhydrous citric acid and 0.1mol of absolute ethanol are weighed in a high-pressure reaction kettle with the pressure of 1MPa to 3MPa, 0.022mol of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane is added into the high-pressure reaction kettle, the constant temperature reaction is carried out for 12 hours in a 190 ℃ oven, and the green fluorescent bis-silane functionalized carbon point is obtained after the reaction is cooled to room temperature.
The bis-silane functionalized carbon dots prepared in examples 1 to 17 and comparative examples 1 and 2 were subjected to fluorescence spectrum test to obtain emission peak information and fluorescent color under 365nm ultraviolet lamp irradiation, and the results are shown in the following table.
TABLE 1 fluorescence emission peaks of bis-silane functionalized carbon dots and fluorescence colors thereof
| Sequence number | Emission peak/nm (365 nm excitation) | Fluorescent color |
| Example 1 | 531 | Green colour |
| Example 2 | 561 | Yellow colour |
| Example 3 | 611 | Red color |
| Examples4 | 530 | Green colour |
| Example 5 | 560 | Yellow colour |
| Example 6 | 609 | Red color |
| Example 7 | 531 | Green colour |
| Example 8 | 569 | Yellow colour |
| Example 9 | 602 | Red color |
| Example 10 | 531 | Green colour |
| Example 11 | 570 | Yellow colour |
| Example 12 | 604 | Red color |
| Comparative example 1 | 544 | Green colour |
| Comparative example 2 | 529 | Green colour |
From the above table, it can be seen that:
1. by using the aminopropyl triethoxysilane of the monoamino organosilane alone in comparative example 1 and the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane of the bisamino organosilane alone in comparative example 2, only the available organosilane functionalized carbon dots have green fluorescence emission wavelength under 365nm ultraviolet excitation and cannot be regulated; however, by mixing aminopropyl triethoxysilane of the monoamino organosilane of examples 1 to 3 with N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane of the diamino organosilane, the obtained bis-silane functionalized carbon dots have green, yellow and red fluorescence under 365nm ultraviolet light excitation and realize the effect of having a fluorescence emission wavelength controllable function by adjusting the molar ratio selected by the monoamino organosilane and the bis-amino organosilane.
2. From the test results of examples 1 to 17, it can be derived from the preparation method of the present application that the molar ratio of the mono-amino organosilane to the bis-amino organosilane selected from among the mono-amino organosilane and the N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, the N- β - (aminoethyl) - γ -aminopropyl methyldimethoxy silane, the bis-amino organosilane selected from among the N- β - (aminoethyl) - γ -aminopropyl triethoxy silane and the N- β - (aminoethyl) - γ -aminopropyl methyldiethoxy silane is adjusted such that the resulting bis-silane functionalized carbon dots have a fluorescence emission wavelength controllable function under 365nm ultraviolet light.
3. By listing the synthetic schematic and structural diagram of the disilane functionalized carbon dots prepared by one of the methods, namely the synthetic schematic and structural diagram of the disilane functionalized carbon dots obtained by the test of the embodiment 6, it can be seen from the figure that the two silanes are respectively connected to the surface of the carbon dots in the form of amide bonds, so that the richness of the surface state of the disilane functionalized carbon dots is increased; it can be known that: the disilane functionalized carbon dots can be self-polymerized or copolymerized with other alkoxy silane to form a film or a coating, and have different curing rates according to the change of the mole ratio and the types of silane used, so that in practical application, the most suitable disilane functionalized carbon dots can be flexibly selected for manufacturing LEDs or other purposes according to the characteristics, the problems of poor compatibility between the organosilane functionalized carbon dots and packaging materials, poor dispersibility, low load capacity and the like are solved, and integrated packaging is realized.
By listing the fluorescence spectra of one of the bis-silane functionalized carbon dots prepared by the method of the present application at different concentrations, i.e., the fluorescence spectra of the bis-silane functionalized carbon dots obtained by the test of example 6 at different concentrations, it can be known from the combination of fig. 3 to 5: with the increase of the concentration, the emission peak of the disilane functionalized carbon dots gradually shifts to red, and according to the luminescence characteristic, the concentration of the disilane functionalized carbon dots can be adjusted to manufacture yellow light LEDs and white light LEDs.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. The preparation method of the disilane functionalized carbon dot is characterized by comprising the following steps:
adding anhydrous citric acid and a solvent into a high-pressure reaction kettle, wherein the pressure of the high-pressure reaction kettle is 1-3 MPa; wherein the solvent is one or a combination of a plurality of methanol, ethanol, propanol and isopropanol;
adding an organosilane mixture comprising monoamino organosilane and diamino organosilane into a high-pressure reaction kettle, wherein the molar ratio of the anhydrous citric acid to the organosilane mixture is 1: (2-20) the molar ratio of the monoamino-based organosilane to the diamino-based organosilane in the organosilane mixture is 1: (0.25-50); wherein the mono-amino organosilane is one of aminopropyl triethoxysilane, aminopropyl methyl diethoxysilane, aminomethyltriethoxysilane or aminomethylmethyl diethoxysilane; the diamino organosilane is one of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, N-beta- (aminoethyl) -gamma-aminopropyl triethoxy silane or N-beta- (aminoethyl) -gamma-aminopropyl methyl diethoxy silane;
and placing the high-pressure reaction kettle in a baking oven at 160-210 ℃ for solvothermal reaction for 10-14 h, and preparing the disilane functionalized carbon dots with different fluorescence emission wavelengths under 365nm ultraviolet excitation.
2. The disilane functionalized carbon dot prepared by the preparation method according to claim 1, wherein the molar ratio of the selected mono-amino organosilane to the selected di-amino organosilane is adjusted to be 1 (9-50), and the obtained disilane functionalized carbon dot shows green fluorescence under 365nm ultraviolet light excitation.
3. The disilane functionalized carbon dot prepared by the preparation method according to claim 1, wherein the molar ratio of the selected mono-amino organosilane to the selected di-amino organosilane is adjusted to 1 (1-5), and the obtained disilane functionalized carbon dot is yellow in fluorescence under 365nm ultraviolet light excitation.
4. The bis-silane functionalized carbon dot prepared by the preparation method according to claim 1, wherein the molar ratio of the selected mono-amino organosilane to the bis-amino organosilane is adjusted to be 1 (0.25-0.5), and the obtained bis-silane functionalized carbon dot shows red fluorescence under 365nm ultraviolet light excitation.
5. The bis-silane functionalized carbon dot according to claim 3, wherein the bis-silane functionalized carbon dot has an average particle diameter of 3.2nm, is circularly distributed, and has a lattice spacing of 0.22nm among lattice fringes of a graphite layer.
6. The bis-silane functionalized carbon dot of claim 3, wherein the mono-amino organosilane and the bis-amino organosilane are each attached to the surface of the carbon dot in the form of an amide bond to enhance the surface state richness of the bis-silane functionalized carbon dot.
7. Use of the bis-silane functionalized carbon dot according to any of claims 3 to 6 in LED devices, wherein the bis-silane functionalized carbon dot is used in LED devices by self-polymerization or copolymerization with an alkoxysilane coupling agent to form a film or coating.
8. The application of the disilane functionalized carbon dots on an LED device according to claim 7, wherein the prepared disilane functionalized carbon dots are coated on a 360nm LED chip, and the LED chip is cured and formed into a film in an oven environment at 25-80 ℃ to obtain a yellow LED device.
9. The application of the disilane functionalized carbon dots on an LED device according to claim 7, wherein the prepared disilane functionalized carbon dots are coated on a 450nm blue light LED chip, and the blue light LED chip is placed in an oven environment at 25-80 ℃ to be solidified into a film, so that a white light LED device is obtained.
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