CN112250081A - Preparation method and application of boron oxide quantum dots - Google Patents
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Abstract
The invention relates to a preparation method of boron oxide quantum dots, belonging to the technical field of quantum dot preparation. The method comprises the steps of firstly dissolving ammonium pentaborate and boric acid in deionized water, uniformly stirring to obtain an ammonium pentaborate/boric acid mixed solution, then carrying out hydrothermal reaction to obtain an initial product solution, then adding a reducing agent solution, fully stirring, and freeze-drying to obtain boron oxide quantum dot powder. The preparation method is simple, mild in condition, free of harmful byproducts in the preparation process and environment-friendly; the structure of the material is controllable through optimization of the precursor; the obtained boron oxide quantum dots have uniform size and blue fluorescence, can be used as boron-containing drugs for boron neutron capture treatment, and have large-scale production potential and wide commercial application prospect.
Description
Technical Field
The invention belongs to the technical field of quantum dot preparation, and particularly relates to a preparation method and application of boron oxide quantum dots.
Background
The boron quantum dots are a novel boron nano material, have important research significance particularly in the fields of chemical sensors, biological imaging, nano medicine, solar cells, Light Emitting Diodes (LEDs), electrocatalysis, neutron capture therapy, new energy and the like, and have potential application value in the fields of biology, medicine, energy storage devices, novel semiconductor devices and the like.
The current methods for preparing quantum dots are divided into top-down and bottom-up methods, in which in the top-down process, macromolecules are destroyed or dispersed into small-sized quantum dots by physical or chemical methods; while the bottom-up method mainly polymerizes and carbonizes a series of small molecules into quantum dots through chemical reactions. The top-down method mainly focuses on a plurality of methods such as a mechanical stripping method and a chemical stripping method, wherein the quantum dots prepared by the mechanical stripping method have the advantages of high quality, few defects and the like, but the top-down method wastes materials, and simultaneously limits the micro morphology of a target material, and cannot regulate and control the morphology by controlling the distance between atoms or ions. From bottom to top, the method mainly focuses on a hydrothermal method, an electrochemical method and other methods, and the hydrothermal method has the advantages that the method is a promising method for preparing the quantum dots, and the composition and the structure of the method are easy to control through the optimization of a precursor. In addition, chinese patent 201910555713.7 discloses a method for preparing boron quantum dots and the application thereof, which comprises dispersing boron powder in an organic solvent, stirring uniformly to obtain a mixed solution containing boron particles, adding hydrogen peroxide solution and boric acid powder, performing high-energy ultrasonic crushing to obtain a primary product solution, adding sodium borohydride, and centrifuging to obtain boron quantum dots, which are mainly used for preparing boron-containing drugs for boron neutron capture therapy. The method has the defects of material waste, limitation on the micro-morphology of the target material and the like. The boron oxide quantum dots have excellent physical and chemical properties such as small size, high crystallinity, good dispersibility and the like, and the surfaces of the boron oxide quantum dots contain rich functional groups, so that the boron oxide quantum dots are easy to be compounded with other materials for use.
Disclosure of Invention
The invention aims to provide a brand-new preparation method of boron oxide quantum dots with high yield by utilizing hydrothermal reaction and freeze drying processes, and particularly, the boron oxide quantum dots are directly obtained by taking ammonium pentaborate and boric acid as raw materials through one-step hydrothermal reaction.
The invention also provides application of the boron oxide quantum dots prepared by the method.
The invention is realized by the following technical scheme:
a preparation method of boron oxide quantum dots comprises the following steps:
(1) dissolving ammonium pentaborate and boric acid in deionized water according to a certain proportion, uniformly stirring, and filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, adding a reducing agent solution, fully stirring, and freeze-drying to obtain boron oxide quantum dot powder.
As a preferable technical scheme, in the step (1), the mass ratio of ammonium pentaborate to boric acid is 1: 0.25-1: 4.
in a preferable embodiment, in the step (1), the stirring is performed at room temperature for 0.5 to 2 hours.
In the preferable technical scheme, in the step (2), the hydrothermal reaction is carried out under the condition of heat preservation for 10-16 h at the temperature of 180-200 ℃.
As a preferable technical scheme, in the step (2), the reducing agent is hydrazine hydrate, sodium borohydride or a mixture of the hydrazine hydrate and the sodium borohydride in any proportion.
In the preferable technical scheme, in the step (2), the temperature of freeze drying is-45 to-51 ℃, and the time of freeze drying is 24 to 48 hours.
Furthermore, the invention also provides application of the boron oxide quantum dots prepared by the method in preparing boron-containing medicines for boron neutron capture treatment.
In order to verify the effect of the method, the X-ray diffraction pattern, the transmission electron microscope picture and the particle size distribution diagram of the boron oxide quantum dots prepared by the method are measured. FIG. 2 is an X-ray diffraction diagram of boron oxide quantum dots, and it can be seen from the diagram that the phase of the prepared boron oxide quantum dots is elemental boron oxide; FIG. 3 is a Raman picture of the boron oxide quantum dot prepared in the present invention, and FIG. 4 is an infrared picture of the boron oxide quantum dot prepared in the present invention, from which it can be seen that the boron oxide quantum dot obtained contains abundant B-O bonds; FIG. 5 is a transmission electron microscope picture of boron oxide quantum dots prepared in the present invention, and FIG. 6 is a distribution graph of particle size of boron oxide quantum dots prepared in the present invention, from which it can be seen that a large number of boron oxide quantum dots with uniform size are prepared, with an average particle size of about 6.4 nm; fig. 7 is a fluorescence excitation emission spectrum of the boron oxide quantum dot prepared in the present invention, and a spectrum of the fluorescence spectrum with a change in excitation wavelength, from which it can be seen that the obtained boron oxide quantum dot has a blue fluorescence effect, and from which it can be seen that with an increase in excitation wavelength, the wavelength of emitted light is red-shifted and the fluorescence intensity is gradually reduced.
The boron oxide quantum dots and the carbon quantum dots have similar in-vivo and in-vitro photoinduced characteristics, can target brain tumor tissues and enrich in focus positions, and the boron oxide quantum dots in healthy tissues can be rapidly metabolized and discharged from organisms. Therefore, the boron-containing compound can be used as a boron-containing medicament for boron neutron capture treatment, and has the potential of large-scale production and wide commercial application prospect.
The invention has the beneficial effects that: (1) the preparation method is simple, mild in condition, free of harmful byproducts in the preparation process and environment-friendly; (2) the structure of the material is controllable through optimization of the precursor; (3) the obtained boron oxide quantum dots have uniform size and blue fluorescence, can be used as boron-containing drugs for boron neutron capture treatment, and have large-scale production potential and wide commercial application prospect.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the embodiments or the prior art descriptions will be briefly introduced, wherein the drawings are used for providing further explanation of the present invention and form a part of the present application, and the exemplary embodiments and the explanation of the present invention are used for explaining the present invention and do not form a limitation to the present invention.
FIG. 1 is a process flow diagram of the preparation method of the present invention;
FIG. 2 is an X-ray diffraction pattern of boron oxide quantum dots prepared in the present invention;
FIG. 3 is a Raman and infrared image of boron oxide quantum dots prepared in the present invention;
FIG. 4 is an infrared image of boron oxide quantum dots prepared in the present invention;
FIG. 5 is a transmission electron microscope picture and a particle size distribution diagram of boron oxide quantum dots prepared in the present invention;
FIG. 6 is a graph showing a distribution of particle sizes of boron oxide quantum dots prepared in the present invention;
FIG. 7 is a fluorescence excitation emission spectrum of the boron oxide quantum dot prepared in the present invention, a spectrum of the fluorescence spectrum varying with the excitation wavelength.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following detailed description of the invention will be given for clearness and completeness. It should be noted that the following examples are only preferred technical solutions of the present invention, and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
(1) Dispersing 1.6g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 0.5 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 12 h;
then adding 0.5mL of sodium borohydride solution, stirring for 1h, and centrifuging at 3500rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-45 ℃ for 24 hours to obtain boron oxide quantum dot powder.
The process flow is shown in figure 1.
Example 2
(1) Dispersing 1.6g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 200 ℃, and keeping the temperature for 16 h; then adding 0.5mL of hydrazine hydrate solution, stirring for 1h, and centrifuging at 3500rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-45 ℃ for 24 hours to obtain boron oxide quantum dot powder.
Example 3
(1) Dispersing 1.6g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 0.5 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 12 h;
then adding 0.5mL of hydrazine hydrate and 0.5mL of sodium borohydride mixed solution, stirring for 1h, and centrifuging at 3500rpm for 15min to obtain a boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-45 ℃ for 24 hours to obtain boron oxide quantum dot powder.
Example 4
(1) Dispersing 3.2g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 0.5 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 200 ℃, and keeping the temperature for 12 h; then adding 1.0mL of sodium borohydride solution, stirring for 1h, and centrifuging for 15min at the rotating speed of 5000rpm to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at a drying temperature of-48 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 5
(1) Dispersing 3.2g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 0.5 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 200 ℃, and keeping the temperature for 12 h; then adding 0.5mL of hydrazine hydrate solution, stirring for 1h, and centrifuging for 15min at the rotating speed of 5000rpm to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at a drying temperature of-48 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 6
(1) Dispersing 3.2g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 2.0h, and the oxygen removal time is 1.0 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 200 ℃, and keeping the temperature for 16 h; then adding a mixed solution of 1.0mL of sodium borohydride and 0.5mL of hydrazine hydrate, stirring for 1h, and centrifuging at the rotating speed of 5000rpm for 15min to obtain a boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at a drying temperature of-48 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 7
(1) Dispersing 4.8g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 2.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 12 h; then adding 0.5mL of hydrazine hydrate solution, stirring for 1h, and centrifuging at 3500rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-50 ℃ for 24 hours to obtain boron oxide quantum dot powder.
Example 8
(1) Dispersing 4.8g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 2.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 12 h; then adding 0.5mL of sodium borohydride solution, stirring for 1h, and centrifuging at 3500rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-50 ℃ for 24 hours to obtain boron oxide quantum dot powder.
Example 9
(1) Dispersing 4.8g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 2.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 12 h; then adding 0.5mL of hydrazine hydrate and 0.5mL of sodium borohydride mixed solution, stirring for 1h, and centrifuging at 3500rpm for 15min to obtain a boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-50 ℃ for 24 hours to obtain boron oxide quantum dot powder.
Example 10
(1) Dispersing 6.4g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 2.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 200 ℃, and keeping the temperature for 12 h; then adding 1.0mL of sodium borohydride solution, stirring for 1h, and centrifuging at 6000rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-51 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 11
(1) Dispersing 6.4g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 200 ℃, and keeping the temperature for 12 h; then adding 1.0mL of hydrazine hydrate solution, stirring for 1h, and centrifuging at 6000rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-51 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 12
(1) Dispersing 6.4g of ammonium pentaborate and 1.6g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 200 ℃, and keeping the temperature for 12 h; then adding a mixed solution of 1.0mL of sodium borohydride and 1.0mL of hydrazine hydrate, stirring for 1h, and centrifuging at 6000rpm for 15min to obtain a boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-51 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 13
(1) Dispersing 1.6g of ammonium pentaborate and 3.2g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 12 h; then adding 1.0mL of sodium borohydride solution, stirring for 1h, and centrifuging at 6000rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at a drying temperature of-48 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 14
(1) Dispersing 1.6g of ammonium pentaborate and 3.2g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 0.5h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 12 h; then adding 1.0mL of hydrazine hydrate solution, stirring for 1h, and centrifuging at 6000rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at a drying temperature of-48 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 15
(1) Dispersing 1.6g of ammonium pentaborate and 3.2g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 0.5h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 12 h; then adding a mixed solution of 1.0mL of sodium borohydride and 1.0mL of hydrazine hydrate, stirring for 1h, and centrifuging at 6000rpm for 15min to obtain a boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at a drying temperature of-48 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 16
(1) Dispersing 1.6g of ammonium pentaborate and 4.8g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 0.5h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 12 h; then adding 0.5mL of sodium borohydride solution, stirring for 1h, and centrifuging at 3500rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-50 ℃ for 24 hours to obtain boron oxide quantum dot powder.
Example 17
(1) Dispersing 1.6g of ammonium pentaborate and 4.8g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 0.5h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 12 h; then adding 0.5mL of hydrazine hydrate solution, stirring for 1h, and centrifuging at 3500rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-50 ℃ for 24 hours to obtain boron oxide quantum dot powder.
Example 18
(1) Dispersing 1.6g of ammonium pentaborate and 4.8g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 180 ℃, and keeping the temperature for 10 hours; then adding 0.5mL of hydrazine hydrate and 0.5mL of sodium borohydride mixed solution, stirring for 1h, and centrifuging at 3500rpm for 15min to obtain a boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-50 ℃ for 24 hours to obtain boron oxide quantum dot powder.
Example 19
(1) Dispersing 1.6g of ammonium pentaborate and 6.4g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 200 ℃, and keeping the temperature for 10 hours; then adding 1.0mL of hydrazine hydrate solution, stirring for 1h, and centrifuging at 6000rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-51 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 20
(1) Dispersing 1.6g of ammonium pentaborate and 6.4g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 200 ℃, and keeping the temperature for 10 hours; then adding 0.5mL of sodium borohydride solution, stirring for 1h, and centrifuging at 6000rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-51 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Example 21
(1) Dispersing 1.6g of ammonium pentaborate and 6.4g of boric acid in 20mL of deionized water, uniformly stirring, and then filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution, wherein the stirring time is 1.0h, and the oxygen removal time is 1 h;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, setting the temperature to be 200 ℃, and keeping the temperature for 10 hours; then adding 1.0mL of hydrazine hydrate solution and 0.5mL of sodium borohydride solution, stirring for 1h, and centrifuging at 6000rpm for 15min to obtain boron oxide quantum dot solution;
(3) and (3) freezing the boron oxide quantum dot solution in a refrigerator, and then drying the boron oxide quantum dot solution in a freeze dryer at the drying temperature of-51 ℃ for 48 hours to obtain boron oxide quantum dot powder.
Claims (7)
1. The preparation method of the boron oxide quantum dot is characterized by comprising the following steps:
(1) dissolving ammonium pentaborate and boric acid in deionized water according to a certain proportion, uniformly stirring, and filling inert gas to remove oxygen to obtain an ammonium pentaborate/boric acid mixed solution;
(2) further carrying out hydrothermal reaction to obtain a primary product solution, adding a reducing agent solution, fully stirring, and freeze-drying to obtain boron oxide quantum dot powder.
2. The method for preparing boron oxide quantum dots according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of ammonium pentaborate to boric acid is 1: 0.25-1: 4.
3. the method for preparing boron oxide quantum dots according to claim 1 or 2, wherein: in the step (1), stirring is carried out at room temperature for 0.5-2 h.
4. The method for preparing boron oxide quantum dots according to claim 1 or 2, wherein: in the step (2), the hydrothermal reaction is carried out under the condition of heat preservation for 10-16 h at 180-200 ℃.
5. The method for preparing boron oxide quantum dots according to claim 1 or 2, wherein: in the step (2), the reducing agent is hydrazine hydrate, sodium borohydride or a mixture of the hydrazine hydrate and the sodium borohydride in any proportion.
6. The method for preparing boron oxide quantum dots according to claim 1 or 2, wherein: in the step (2), the temperature of freeze drying is-45 to-51 ℃, and the time of freeze drying is 24 to 48 hours.
7. Use of boron oxide quantum dots prepared according to any one of claims 1 to 6 in the preparation of boron-containing medicaments for boron neutron capture therapy.
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