CN110699068A - Preparation method of amino-functionalized water-soluble silicon quantum dots - Google Patents
Preparation method of amino-functionalized water-soluble silicon quantum dots Download PDFInfo
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- CN110699068A CN110699068A CN201911061825.3A CN201911061825A CN110699068A CN 110699068 A CN110699068 A CN 110699068A CN 201911061825 A CN201911061825 A CN 201911061825A CN 110699068 A CN110699068 A CN 110699068A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
Abstract
The invention provides a preparation method of amino-functionalized water-soluble silicon quantum dots, which comprises the following steps of S1, adding an amino-containing organosilane coupling agent into deionized water, stirring at room temperature until a uniform precursor solution is formed, S2, transferring the precursor solution into a high-pressure reaction kettle, heating to 110 ~ 230 ℃, reacting for 3 ~ 60 hours, cooling to room temperature to obtain a silicon quantum dot crude product, S3, extracting the silicon quantum dot crude product for 3 ~ 5 times by using an organic solvent, purifying to obtain a refined quantum dot solution, and freeze-drying and grinding the refined quantum dot solution to obtain the amino-functionalized water-soluble silicon quantum dots.
Description
Technical Field
The invention relates to the technical field of preparation of nano materials, in particular to a preparation method of amino-functionalized water-soluble silicon quantum dots.
Background
The quantum dots are an important quasi-zero dimension semiconductor nano material and have unique photoelectric properties. Quantum dots generally have higher luminous efficiency, better photostability, longer fluorescence lifetime, wider absorption band, and larger stokes shift than conventional organic dyes. The excitation spectrum is wide, the emission spectrum is narrow, symmetrical and adjustable, and therefore more and more quantum dots are developed and applied to the fields of analysis and detection, photoelectric devices and biomedicine. The traditional quantum dots mostly contain heavy metals such as cadmium, lead and the like, and have strong environmental and biological toxicity. Therefore, silicon quantum dots with low price, strong bleaching resistance and good biocompatibility are gaining favor of people.
At present, silicon quantum dots with emission wavelengths from the ultraviolet to near infrared spectral region can be prepared by controlling the synthesis method and reaction conditions. The preparation method mainly comprises a laser ablation method, a mechanical ball milling method, an ion implantation method, an electrochemical corrosion method, a supercritical fluid method, a liquid phase reduction method and the like. Among them, the liquid phase reduction method, particularly the aqueous phase reduction method, is the most commonly used method for preparing water-soluble silicon quantum dots.
However, the existing hydrothermal synthesis method of silicon quantum dots requires addition of a catalyst such as ammonia (l. Yang, et al, Chemical Communications, 2016, 52, 6154-6157) in addition to a silane coupling agent; or a reducing agent or a protecting agent such as organic dyes (Y. Zhong, et al, Chemical Communications, 2016, 52, 13444-. In recent years, patent methods for synthesizing water-soluble silicon quantum dots by a hydrothermal method are disclosed, and various reducing agents or protective agents are added, such as 2016: CN105694871A (glucose or sodium ascorbate), CN105969344A (citric acid, sodium sulfite, sodium borohydride, sodium citrate, ascorbic acid, urea, thiourea, hydrazine hydrate, L-cysteine, bovine serum albumin or denatured bovine serum albumin); in 2017: CN106350061B (citric acid, sodium citrate, ascorbic acid, sodium ascorbate or sodium borohydride); in 2019: CN109777401A (sodium citrate), CN109652067A (sodium ascorbate), etc.
These additional reducing or protecting agents or catalysts not only add to the synthesis steps and costs, but also add difficulty to the purification of the product. Therefore, it is necessary to develop a simpler synthesis method.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for synthesizing amino-functionalized water-soluble silicon quantum dots by using an amino-organosilane coupling agent as a raw material in a hydrothermal mode under the condition that no reducing agent, protective agent or catalyst is additionally added. The method solves the problem that an auxiliary agent is required to be added for the synthesis of the silicon quantum dots for a long time, simplifies the synthesis process and reduces the synthesis cost.
A preparation method of amino-functionalized water-soluble silicon quantum dots comprises the following steps:
s1, adding an amino-containing organosilane coupling agent into deionized water, and stirring at room temperature until a uniform precursor solution is formed;
s2, transferring the precursor solution into a high-pressure reaction kettle, heating to 110 ~ 230 ℃, reacting for 3 ~ 60 hours, and cooling to room temperature to obtain a silicon quantum dot crude product;
and S3, extracting the crude silicon quantum dot product for 3 ~ 5 times by using an organic solvent, purifying to obtain a refined quantum dot solution, and freeze-drying and grinding the refined quantum dot solution to obtain the amino-functionalized water-soluble silicon quantum dot.
The amino-containing organosilane coupling agent in S1 is prepared by mixing one or more of 3-aminopropyltriethoxysilane, 3-propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, bis [3- (trimethoxysilyl) propyl ] ethylenediamine and other amino-containing trialkoxysilanes.
The mass ratio of the amino-containing organosilane coupling agent to the deionized water in S1 is 1:2 ~ 20.
The high-pressure reaction kettle in the S2 is a metal kettle with a polytetrafluoroethylene lining or a pressure-resistant pipe made of other materials.
The heating mode of the high-pressure reaction kettle in the S2 is static or dynamic heating (including stirring or turning).
The organic solvent in S3 is any one of cyclohexane, petroleum ether, ethyl acetate and dichloromethane.
The method for preparing the refined quantum dot solution by purification in the S3 is high-speed centrifugation or dialysis.
Compared with the prior art, the invention has the beneficial effects that:
1. the method does not add any reducing agent or protective agent or catalyst, reduces the number of raw materials, simplifies the synthesis steps and reduces the synthesis cost.
2. Compared with an organic reducing agent method, the silicon quantum dot prepared by the method has the advantages of simpler structure, clear and transparent solution, high quantum yield, excellent water solubility and difficult dissolution in an organic solvent, and can be purified by an organic solvent extraction method.
3. The silicon quantum dots prepared by the method have good pH stability and thermal stability, can stably exist under the conditions of pH =1 ~ 12 and-20 ~ 90 ℃, and have no obvious change in luminescence property.
4. The method directly introduces amino groups when synthesizing the silicon quantum dots, avoids a post-modification process, greatly simplifies the preparation process, and facilitates further functionalization and application of the silicon quantum dots by the surface amino groups.
Drawings
FIG. 1 shows fluorescence excitation and fluorescence emission spectra of the aqueous solution of silicon quantum dots in example 1.
FIG. 2 is a graph showing the fluorescence lifetime of the silicon quantum dots in example 1.
FIG. 3 is a graph showing the change of fluorescence intensity of the aqueous solution of silicon quantum dots with pH in example 1.
FIG. 4 is a graph showing the change of fluorescence intensity of the aqueous solution of silicon quantum dots with temperature in example 1.
Fig. 5 is an XRD pattern of the silicon quantum dot solid powder in example 2.
Fig. 6 is an ATR-IR spectrum of the silicon quantum dot solid powder in example 2.
Fig. 7 is a TEM image of the silicon quantum dots prepared in example 3.
Fig. 8 is a particle size distribution diagram of the silicon quantum dots prepared in example 3.
Detailed Description
Hereinafter, preferred examples of the invention will be described in detail. The examples are given for the purpose of better understanding the inventive content and are not intended to be limiting. Insubstantial modifications and adaptations of the embodiments in accordance with the present disclosure remain within the scope of the invention.
Example 1
A preparation method of amino-functionalized water-soluble silicon quantum dots comprises the following steps:
s1, adding 4mL of 3-aminopropyltriethoxysilane into 20mL of deionized water, and stirring at room temperature until a uniform precursor solution is formed;
s2, transferring the precursor solution into a high-pressure reaction kettle, heating to 160 ℃, reacting for 4 hours, and cooling to room temperature to obtain a silicon quantum dot crude product;
and S3, extracting the crude product by using cyclohexane for 5 times (20 mL each time), removing unreacted 3-aminopropyl triethoxysilane, and freeze-drying and grinding the purified quantum dot solution to obtain white silicon quantum dot powder.
The silicon quantum dot solution prepared in the embodiment emits bright blue fluorescence under 365nm ultraviolet light irradiation. As can be seen from the fluorescence excitation and emission spectrum of the silicon quantum dot shown in fig. 1, the maximum excitation wavelength of the aqueous solution of the silicon quantum dot prepared in this example is around 365nm, the maximum emission wavelength is around 444nm, and the emission peak is narrow.
The silicon quantum dots prepared in this example were dissolved in water to prepare a 10mg/mL aqueous solution, and the fluorescence decay curve thereof was measured, and the fluorescence lifetime thereof was measured to be 9.74 ns, as shown in fig. 2, and the silicon quantum dot solution prepared in this example was highly stable, stably existed under the conditions of pH =1 ~ 12 and 0 ~ 90 ℃, and the luminescence property was not significantly changed, as shown in fig. 3.
< example 2>
A preparation method of amino-functionalized water-soluble silicon quantum dots comprises the following steps:
s1, adding 6mL of 3-aminopropyltrimethoxysilane into 20mL of deionized water, and stirring at room temperature until a uniform precursor solution is formed;
s2, transferring the precursor solution into a high-pressure reaction kettle, heating to 180 ℃, reacting for 6 hours, and cooling to room temperature to obtain a silicon quantum dot crude product;
and S3, extracting the crude product by using cyclohexane for 5 times (20 mL each time), removing unreacted 3-aminopropyl trimethoxy silane, and freeze-drying and grinding the purified quantum dot solution to obtain white silicon quantum dot powder.
The silicon quantum dot powder prepared in the embodiment emits bright blue light under 365nm ultraviolet irradiation, and XRD (X-ray diffraction) is similar to SiO2The broad diffraction peak of (1) is amorphous, see fig. 4. The IR spectrum of the silicon quantum dot powder prepared in this example is shown in FIG. 5, in which 1002 cm-1The absorption peak is attributed to the stretching vibration of Si-O-Si, which proves the successful condensation of the organic silicon; 3350 cm-1，3285 cm-1Bimodal and 1590 cm-1Strong absorption peaks at (A) are respectively assigned to-NH2The stretching vibration and the deformation vibration prove that a large amount of-NH is reserved on the surface of the prepared silicon quantum dot2。
< example 3>
A preparation method of amino-functionalized water-soluble silicon quantum dots comprises the following steps:
s1, adding 4mL of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane into 20mL of deionized water, and stirring at room temperature until a uniform precursor solution is formed;
s2, transferring the precursor solution into a high-pressure reaction kettle, heating to 180 ℃, reacting for 24 hours, and cooling to room temperature to obtain a silicon quantum dot crude product;
and S3, extracting the crude product for 5 times (20 mL each time) by using petroleum ether, removing unreacted N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and freeze-drying and grinding the purified quantum dot solution to obtain yellowish silicon quantum dot powder.
The TEM image of the silicon quantum dots prepared in the example is shown in FIG. 6, and the TEM image shows that the prepared silicon quantum dots are uniform in size and have an average particle size of about 2 nm.
The above embodiments are merely illustrative of the technical solutions and features of the present invention, and the purpose thereof is to better enable those skilled in the art to practice the invention, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention are within the scope of the present invention, wherein the prior art is not described in detail.
Claims (7)
1. A preparation method of amino-functionalized water-soluble silicon quantum dots is characterized by comprising the following steps:
s1, adding an amino-containing organosilane coupling agent into deionized water, and stirring at room temperature until a uniform precursor solution is formed;
s2, transferring the precursor solution into a high-pressure reaction kettle, heating to 110 ~ 230 ℃, reacting for 3 ~ 60 hours, and cooling to room temperature to obtain a silicon quantum dot crude product;
and S3, extracting the crude silicon quantum dot product for 3 ~ 5 times by using an organic solvent, purifying to obtain a refined quantum dot solution, and freeze-drying and grinding the refined quantum dot solution to obtain the amino-functionalized water-soluble silicon quantum dot.
2. The method for preparing amino-functionalized water-soluble silicon quantum dots according to claim 1, wherein the amino-containing organosilane coupling agent in S1 is one or more of 3-aminopropyltriethoxysilane, 3-propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and bis [3- (trimethoxysilyl) propyl ] ethylenediamine.
3. The method for preparing the amino-functionalized water-soluble silicon quantum dot according to claim 1, wherein the mass ratio of the amino-containing organosilane coupling agent to the deionized water in S1 is 1:2 ~ 20.
4. The method for preparing amino-functionalized water-soluble silicon quantum dots according to claim 1, wherein the high-pressure reaction kettle in S2 is a metal kettle with a polytetrafluoroethylene lining.
5. The method for preparing the amino-functionalized water-soluble silicon quantum dot according to claim 1, wherein the heating mode of the high-pressure reaction kettle in S2 is static or dynamic heating.
6. The method for preparing amino-functionalized water-soluble silicon quantum dots according to claim 1, wherein the organic solvent in S3 is any one of cyclohexane, petroleum ether, ethyl acetate and dichloromethane.
7. The method for preparing amino-functionalized water-soluble silicon quantum dots according to claim 1, wherein the purification method in S3 is high-speed centrifugation or dialysis.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112300795A (en) * | 2020-09-30 | 2021-02-02 | 江苏大学 | Preparation method and application of molecular imprinting fluorescent probe based on silicon quantum dots |
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| CN102173420A (en) * | 2011-03-04 | 2011-09-07 | 中国科学院理化技术研究所 | Surface modification method for silicon quantum dots |
| US20140339499A1 (en) * | 2011-11-30 | 2014-11-20 | University Of Washington Through Its Center For Commercialization | Surface-passivated silicon quantum dot phosphors |
| CN107213911A (en) * | 2016-03-22 | 2017-09-29 | 北京化工大学 | The preparation method of CQDs/TNS and SiQDs/TNS composite photo-catalysts |
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Patent Citations (4)
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|---|---|---|---|---|
| JP2009124067A (en) * | 2007-11-19 | 2009-06-04 | Konica Minolta Medical & Graphic Inc | Core/shell silicon quantum dot and biosubstance labeling agent using the same |
| CN102173420A (en) * | 2011-03-04 | 2011-09-07 | 中国科学院理化技术研究所 | Surface modification method for silicon quantum dots |
| US20140339499A1 (en) * | 2011-11-30 | 2014-11-20 | University Of Washington Through Its Center For Commercialization | Surface-passivated silicon quantum dot phosphors |
| CN107213911A (en) * | 2016-03-22 | 2017-09-29 | 北京化工大学 | The preparation method of CQDs/TNS and SiQDs/TNS composite photo-catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112300795A (en) * | 2020-09-30 | 2021-02-02 | 江苏大学 | Preparation method and application of molecular imprinting fluorescent probe based on silicon quantum dots |
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