CN110835533A - Preparation method of calcium fluoride nanoparticles - Google Patents
Preparation method of calcium fluoride nanoparticles Download PDFInfo
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Abstract
The invention relates to the technical field of inorganic nano material preparation, in particular to a preparation method of calcium fluoride nano particles, which comprises the following steps: adding a solvent to the first mixture to form a mixed solution; wherein the first mixture comprises calcium hydroxide and at least one compound containing rare earth ions, the solvent being used to dissolve the first mixture; adding ammonium fluoride into the mixed solution to form a reaction solution; heating the reaction solution to a first preset temperature; and keeping the temperature of the reaction solution for a first preset time to obtain a reaction product. The calcium fluoride is prepared by directly dissolving a compound containing rare earth ions and calcium hydroxide in a solvent, adding ammonium fluoride and utilizing a coprecipitation principle. The method realizes that the process in the calcium fluoride nanoparticle method is easy to observe and regulate, the raw materials are convenient to purchase without intermediate reaction and products, and the generated nanoparticles are superfine and uniform and have excellent optical properties such as luminous intensity, high efficiency and the like.
Description
Technical Field
The invention relates to the technical field of inorganic nano material preparation, in particular to a preparation method of calcium fluoride nano particles.
Background
The fluorescence property of the substance is an important property and is widely applied to the fields of biomedicine, instrument detection, anti-fake identification and the like. The fluorescent materials widely known at present mainly comprise fluorescent protein, organic dye, semiconductor quantum dots, modified carbon nano tubes, metal nano particles, silicon quantum dots and rare earth doped luminescent materials. The rare earth up-conversion luminescent material is generally composed of a host material, an activator and a sensitizer, and the inorganic host material for up-conversion luminescence of rare earth ions comprises three main types of materials, namely polycrystalline powder, single crystal and amorphous material, mainly fluoride, oxide, halide and sulfur-containing compound with lower phonon energy. Fluoride generally has lower phonon energy and higher chemical stability, and is generally used as a host material for up-conversion luminescence, such as NaYF4，NaCeF4And LaF3And so on. Fluorite type CaF2Because of its low phonon energy, stable chemical property at normal temperature and pressure, low biological toxicity, easy elimination of human body, easily available raw material and low cost, it has extensive application prospect in the fields of nano laser, up-conversion luminescence, dental caries treatment and biological imaging, etc.
Commonly used at present for fluorite type CaF2The synthesis method mainly comprises a hydrothermal/oil-thermal method, a thermal decomposition method using calcium trifluoroacetate as a raw material and the like. The hydrothermal/oil-thermal method equipment is mainly a reaction kettle, although the operation is simple and convenient, the hydrothermal/oil-thermal method equipment is obviously not suitable for observing the phenomenon caused by the change regulation of the raw materials and the solvent in the reaction observation, and the growth regulation mechanism is more comprehensively analyzed; the thermal decomposition method using calcium trifluoroacetate as a raw material is convenient for observing and regulating the change in the corresponding growth process, but because calcium trifluoroacetate is few in users and not easy to purchase from the market, the intermediate product calcium trifluoroacetate is prepared by reacting trifluoroacetic acid and calcium carbonate, so that the drug loss is easily caused, and the final experiment repetition rate is low.
Disclosure of Invention
The technical problem to be solved by the invention is that the existing fluorite CaF2The synthesis method has the problems of complex process and low experiment repetition rate.
In order to solve the above technical problem, an embodiment of the present application discloses a method for preparing calcium fluoride nanoparticles, including:
adding a solvent to the first mixture to form a mixed solution; wherein the first mixture comprises calcium hydroxide and at least one compound containing rare earth ions, the solvent being used to dissolve the first mixture;
adding ammonium fluoride into the mixed solution to form a reaction solution;
heating the reaction solution to a first preset temperature;
and keeping the temperature of the reaction solution for a first preset time to obtain a reaction product.
Further, the compound containing rare earth ions is nitrate of rare earth ions, chlorate of rare earth ions or acetate of rare earth ions.
Further, the solvent is oleic acid or a mixture of oleic acid and octadecene.
The solvent is a mixture of oleic acid and octadecene, and the mixing ratio of the oleic acid to the octadecene is 1: 100-100: 1.
further, the first mixture further comprises a dopant, and the dopant is at least one compound containing metal ions.
Further, the metal ions include: li+、Na+、K+、Mn2+、Ce3+、Gd3+、Y3+And Sr2+At least one of (1).
Further, the adding a solvent to the first mixture to form a mixed solution includes:
adding a solvent to the first mixture to form a second mixture;
heating the second mixture to a second preset temperature under vacuum conditions;
and keeping the second mixture warm for a second preset time.
Further, the heating the reaction solution to a first preset temperature includes:
introducing protective gas into the reaction solution;
heating the reaction solution to a first preset temperature.
Further, the first preset temperature is 200-400 ℃; and/or the presence of a gas in the gas,
the second preset temperature is 50-200 ℃.
Further, the preparation method further comprises the following steps: adding a detergent into the reaction product, and centrifuging and washing the reaction product.
By adopting the technical scheme, the preparation method of the calcium fluoride nano-particles has the following beneficial effects:
according to the preparation method of the calcium fluoride nano-particles, the compound containing the rare earth ions and the calcium hydroxide are directly dissolved in the solvent, then the ammonium fluoride is added, and the rare earth ions, the calcium ions and the fluorine ions can react at high temperature to generate the rare earth ion doped calcium fluoride precipitate by utilizing the coprecipitation principle. The method realizes that the process in the calcium fluoride nanoparticle method is easy to observe and regulate, the raw materials are convenient to purchase without intermediate reaction and products, and the generated nanoparticles are superfine and uniform and have excellent optical properties such as luminous intensity, high efficiency and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a flow chart of a method for preparing calcium fluoride nanoparticles provided in an embodiment of the present application;
FIG. 2 is a flow chart of a process for adding a solvent to a first mixture as provided in an example of the present application;
FIG. 3 is an XRD diffractogram of calcium fluoride nanoparticles obtained in accordance with an embodiment of the present application;
FIG. 4 is an EDX spectrum of calcium fluoride nanoparticles obtained in one embodiment of the present application;
FIG. 5 is a graph comparing calcium fluoride nanoparticles obtained at different reaction durations according to one embodiment of the present application;
FIG. 6 is a TEM image of the calcium fluoride nanoparticles obtained in one embodiment of the present application;
FIG. 7 is a graph of the near infrared fluorescence spectra of calcium fluoride nanoparticles obtained with different neodymium-doped concentrations in accordance with an embodiment of the present application;
FIG. 8 is an XRD diffraction pattern of calcium fluoride nanoparticles obtained with different lithium ion doping concentrations according to one embodiment of the present application;
FIG. 9 is a TEM image of the calcium fluoride nanoparticles obtained in one embodiment of the present application;
FIG. 10 is a graph showing the particle size distribution of calcium fluoride nanoparticles obtained in one embodiment of the present application;
FIG. 11 is a graph of the near infrared fluorescence spectra of calcium fluoride nanoparticles obtained with different cerium doping concentrations in accordance with one embodiment of the present application;
fig. 12 is an XRD diffractogram of calcium fluoride nanoparticles obtained with different lithium ion doping concentrations according to an embodiment of the present application;
FIG. 13 is a TEM image of calcium fluoride nanoparticles obtained according to an example of the present application;
FIG. 14 is a graph showing the particle size distribution of calcium fluoride nanoparticles obtained in one embodiment of the present application;
fig. 15 is a graph of near infrared fluorescence spectra of calcium fluoride nanoparticles obtained with different cerium doping concentrations in accordance with an embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the present application. In the description of the present application, it is to be understood that the terms "upper", "lower", "top", "bottom", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present application and simplifying the description, and do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Moreover, the terms "first," "second," and the like are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the application described herein are capable of operation in sequences other than those illustrated or described herein.
Commonly used at present for fluorite type CaF2The synthesis method mainly comprises a hydrothermal/oil-thermal method, a thermal decomposition method using calcium trifluoroacetate as a raw material and the like. The method has the problems of complex preparation process, difficult observation and analysis, low experiment repetition rate and the like.
As shown in fig. 1, an embodiment of the present application provides a method for preparing calcium fluoride nanoparticles, including:
s101: a solvent is added to the first mixture to form a mixed solution.
In an embodiment of the present application, the first mixture includes calcium hydroxide and at least one compound containing rare earth ions to provide calcium ions and rare earth ions for the reaction. In the first mixture, the compound containing rare earth ions may be one compound containing one kind of rare earth ions, may also be one compound containing a plurality of kinds of rare earth ions, and may also be a combination of a plurality of kinds of compounds containing rare earth ions. Rare earth ion RE3+In the form of soluble salts with hydrogenThe calcium oxide is mixed to form a first mixture. Optionally, containing RE3+The soluble salt is RE (NO)3)3、RECl3Or RE (CH)3COO)3. Rare earth ion RE3+Can be Nd3+、Yb3+、Er3+、Ho3+、Pr3+And Tm3+And the like. In some embodiments, the first mixture further comprises a dopant for controlling the size of the nanoparticles produced by the final reaction and improving their light emitting properties. The dopant is at least one metal ion-containing compound, and each metal ion-containing compound contains at least one metal ion. Optionally, the metal ions include: li+、Na+、K+、Mn2+、Ce3+、Gd3+、Y3+And Sr2+At least one of (1). Optionally, the components in the first mixture are calculated according to the mass percentage: 1-10% of compound containing rare earth ions, 10-95% of calcium hydroxide and 0-90% of compound containing metal ions. The above component ratios may vary depending on the size and performance requirements of the synthesized nanoparticles. The solvent is used to dissolve the first mixture, and the solvent is selected to make the reaction product particles uniform. Optionally, the solvent is oleic acid, and in some embodiments, the solvent may also be a combination of oleic acid and other organic solvents, for example, a mixture of oleic acid and octadecene. Optionally, the mixing ratio of oleic acid to octadecene is 1: 100-100: 1. preferably, the mixing ratio of the oleic acid to the octadecene is 2: 3.
in the embodiment of the present application, a solvent is added to the first mixture and then the mixture is processed to obtain a mixed solution, please refer to fig. 2, and fig. 2 is a flowchart of the processing performed after the solvent is added to the first mixture according to the embodiment of the present application. Adding a solvent to the first mixture to form a mixed solution comprising:
s201: a solvent is added to the first mixture to form a second mixture.
S203: the second mixture is heated under vacuum to a second predetermined temperature.
S205: the second mixture is allowed to warm for a second predetermined period of time.
In the embodiment of the application, the solvent is added into the first mixture to form the second mixture, and the second mixture is placed in a vacuum environment, so that the oleic acid can be prevented from being oxidized, and in addition, moisture and the like in the medicine can be removed in the vacuumizing process. And stirring the second mixture, heating the second mixture to a preset temperature under a vacuum condition, and keeping the temperature for a preset time. The above process enables the first mixture to be rapidly dissolved in the solvent. Optionally, the heating process may be a continuous heating process, or may be a multi-stage heating process, for example, heating the second mixture to an intermediate temperature lower than the second preset temperature, holding the temperature for a period of time, then reheating to the second preset temperature, and holding the temperature for a period of time. It should be noted that the above heating process is not limited to two stages, but may be a plurality of stages. Optionally, the second preset temperature is 40-200 ℃, and the second preset time is 10-50 min. After the first mixture is dissolved in the solvent to form a clear mixed solution, the mixed solution is cooled to room temperature.
S103: and adding ammonium fluoride into the mixed solution to form a reaction solution.
In the embodiment of the present application, the ammonium fluoride added to the mixed solution is added in the form of an ammonium fluoride solution, and optionally, the ammonium fluoride solution is an aqueous solution of ammonium fluoride. In some embodiments, the solution of ammonium fluoride solids in an organic solvent may also be used. Preferably, the ammonium fluoride solution is a solution of ammonium fluoride dissolved in anhydrous methanol or deionized water. Adding an ammonium fluoride solution into the mixed solution to form a reaction solution, wherein the mass ratio of the first mixture to the ammonium fluoride in the reaction solution is 1: 1-1: 5, preferably, the ratio of the amount of the first mixture to the amount of the ammonium fluoride is 1: 2.5.
in the examples of the present application, the reaction solution was heated and stirred under vacuum for a certain period of time. Optionally, the heating temperature is 30-50 ℃, and the reaction time is 10-50 min. Then the solution is further heated to 90-150 ℃ to remove the water and part of the organic solvent in the solution.
S105: heating the reaction solution to a first preset temperature;
in the embodiment of the present application, the reaction solution is heated to a first preset temperature to generate a target product, and optionally, the first preset temperature is 200 ℃ to 400 ℃. And introducing protective gas into the reaction solution during heating to prevent the oleic acid from being oxidized. When the temperature reaches about 300 ℃, the reaction solution is easy to boil due to vacuum pumping, so that the reaction solution can be prevented from boiling by introducing the protective gas flow. Optionally, the shielding gas is nitrogen or an inert gas, preferably argon.
S107: and keeping the temperature of the reaction solution for a first preset time to obtain a reaction product.
In the embodiment of the application, the reaction solution is heated to a first preset temperature under a protective atmosphere, and then the reaction product is obtained after the temperature is maintained for a first preset time. Optionally, the second preset time period is 10min to 120 min. And centrifuging the reaction solution after the reaction is finished by using a high-speed centrifuge to obtain a reaction product.
The preparation method also comprises the following steps: adding a detergent into the reaction product, and centrifugally washing the reaction product.
In the embodiment of the application, a detergent is added into the reaction product, and the reaction product is centrifugally washed to remove the organic solvent and other impurities on the surface of the reaction product. Optionally, the detergent is cyclohexane, absolute ethyl alcohol and the like. And (2) alternately centrifuging and washing for a plurality of times by using cyclohexane and absolute ethyl alcohol, placing the obtained nano particles into a vacuum drying oven, drying at 50-120 ℃, and finally sealing and storing the dried fluorite calcium fluoride nano particles doped with rare earth ions. In the final product, RE3+As activators and sensitizers, CaF2As a host lattice, doped metal ions, etc. are dopants.
In the examples of the present application, by including RE3+Soluble compound and calcium hydroxide are dissolved in oleic acid and octadecene, ammonium fluoride is uniformly dispersed in the system by utilizing a solvent system of the calcium hydroxide dissolved in the oleic acid and the octadecene, and RE is uniformly dispersed at high temperature by utilizing a coprecipitation principle3+，Ca2+And F-Will react to form RE3+Precipitating the doped calcium fluoride. Due to the large steric effect of oleic acid, the oleic acid precipitates at high temperature to form ultra-small ultra-uniform particlesUniform fluorite type calcium fluoride nano-particles, and the size of the nano-particles is regulated and controlled due to different reaction temperatures and time. The method realizes that the process in the calcium fluoride nanoparticle method is easy to observe and regulate, the adopted raw materials are non-toxic and green, the sources are rich and easy to obtain, no intermediate reaction or product is generated, the cost is low, the synthesis process is simple, the implementation is easy, the safety is high, the diameter of the generated nanoparticle is less than 10nm, the size is uniform, the product quality is stable, the process repeatability is good, the crystallinity and the stability of the calcium fluoride prepared by the preparation method are good, and the calcium fluoride has excellent optical properties such as luminous intensity and high efficiency. It has rich application foreground in nanometer laser, up-conversion luminescence, decayed tooth treatment, medicine transmission, biological imaging and other fields.
Based on the above alternative embodiments, three alternative embodiments are described below.
Example 1:
1) weighing 0.06mmol of neodymium acetate tetrahydrate, 0.94mmol of Ca (OH)2Then, the mixture was put into a 250ml three-necked flask, and a total of 8ml of oleic acid and 12ml of octadecene were added as a solvent.
2) Connecting one of the flask openings with a vacuum pump, sealing the other two flask openings with rubber plugs, and inserting a thermocouple thermometer; thereafter, the vacuum pump and the stirrer were turned on, and the vacuum pressure was maintained at 0.1Pa and the stirring rate was 200 revolutions per minute.
3) Opening the heating jacket, heating to 70 deg.C for 10min, heating to 150 deg.C for 20min to form clear and transparent solution, and cooling to room temperature.
4) Weighing 2.5mmol NH4F, adding 10ml of anhydrous methanol to prepare a solution; 10ml NH to be prepared under stirring4And F, adding the absolute methanol solution into the system in the room temperature state in the step 3).
5) Reacting the solution system obtained in the step 4) for 30 minutes at 40 ℃ under stirring and vacuum conditions, and then heating to 100 ℃ for 10 minutes to remove methanol and water vapor.
6) Introducing argon flow with slow flow rate into the solution system obtained after the step 5), heating to 250 ℃, keeping the temperature for 30 minutes, and naturally cooling to room temperature to obtain the calcium fluoride-containing nanoparticle reaction liquid.
7) Centrifuging the reaction solution obtained in the step 6) by using a high-speed centrifuge to obtain a precipitate, alternately centrifuging and washing for 2 times by using cyclohexane and absolute ethyl alcohol, placing the obtained nano particles in a vacuum drying oven, drying at 60 ℃, and finally sealing and storing the nano particles.
Obtained Nd3+The X-ray diffraction pattern of the doped calcium fluoride nanoparticles is shown in fig. 3, where fig. 3 shows that the ratio of oleic acid to octadecene is in the range of 1: and (3) an XRD diffraction pattern of calcium fluoride nano-particles obtained by reacting for 90 minutes at the temperature of 20 and 300 ℃ proves that the crystal phase of the product is calcium fluoride. As shown in fig. 4, fig. 4 shows that the ratio of oleic acid to octadecene is in the range of 1: and (2) performing EDX (electron-ray diffraction) energy spectrum diagram of calcium fluoride nano particles obtained by reacting for 90 minutes at the temperature of 20 and 300 ℃, and performing EDS (electron-ray diffraction) component analysis to obtain calcium element, wherein neodymium element and fluorine element successfully enter the generated particles. As shown in FIG. 5, transmission electron microscopy at different reaction temperatures and times yielded Nd of about 5nm in different sizes3+Doped calcium fluoride nanoparticles. Fig. 5 shows the ratio of calcium hydroxide to solvent at 1: 20, Transmission Electron Microscope (TEM) pictures of the calcium fluoride nanoparticles obtained at different temperatures and reaction times under a 20nm scale. FIG. 5a shows that the reaction mixture was reacted at 250 ℃ for 30 minutes to obtain calcium fluoride particles having an average particle size of 2.2 nm. FIG. 5b shows that the reactants were reacted at 300 ℃ for 90 minutes to obtain calcium fluoride particles having an average particle size of 4.6 nm. Wherein the product obtained under the conditions corresponding to figure (5b) is of uniform size and larger particles. As shown in fig. 6, the ratio of calcium hydroxide to solvent was in the range of 1: 25, TEM picture of calcium fluoride nanoparticles obtained by reacting at 300 ℃ for 90 minutes under a 20nm scale. As shown in FIG. 7, FIG. 7 is a graph of the near-infrared fluorescence spectrum of calcium fluoride nanoparticles with different neodymium-doped concentrations under 800nm excitation, which shows that the nanoparticles convert the near-infrared fluorescence under 808nm excitation.
Example 2:
1) 0.06mmol of neodymium acetate tetrahydrate, 0.3mmol of LiOH and 0.84mmol of Ca (OH)2 are weighed into a 250ml three-neck flask, and 8ml of oleic acid and 12ml of octadecene are added as solvents.
2) Connecting one of the flask openings with a vacuum pump, sealing the other two flask openings with rubber plugs, and inserting a thermocouple thermometer; thereafter, the vacuum pump and the stirrer were turned on, and the vacuum pressure was maintained at 0.1Pa and the stirring rate was 200 revolutions per minute.
3) Opening the heating jacket, heating to 70 deg.C for 10min, heating to 150 deg.C for 20min to form clear and transparent solution, and cooling to room temperature.
4) Weighing 2.5mmol NH4F, adding 10ml of anhydrous methanol to prepare a solution; 10ml NH to be prepared under stirring4And F, adding the absolute methanol solution into the system in the room temperature state in the step 3).
5) Reacting the solution system obtained in the step 4) for 30 minutes at 40 ℃ under stirring and vacuum conditions, and then heating to 100 ℃ for 10 minutes to remove methanol and water vapor.
6) Introducing argon flow with slow flow rate into the solution system obtained after the step 5), heating to 300 ℃, keeping the temperature for 90 minutes, and naturally cooling to room temperature to obtain the calcium fluoride-containing nanoparticle reaction liquid.
7) Centrifuging the reaction solution obtained in the step 6) by using a high-speed centrifuge to obtain a precipitate, alternately centrifuging and washing for 2 times by using cyclohexane and absolute ethyl alcohol, placing the obtained nano particles in a vacuum drying oven, drying at 60 ℃, and finally sealing and storing the nano particles.
The obtained Nd is an activator3+The concentration of (A) is 6% fixed, and Li is doped differently+The X-ray diffraction pattern of the calcium fluoride nanoparticles at the concentration is shown in FIG. 8, in which FIG. 8 shows the pattern of the activator Nd3+At a fixed concentration of 6%, the oleic acid and octadecene ratio was in the range of 1: different Li dopings obtained by reaction at 20, 300 ℃ for 90 minutes+XRD diffractogram of calcium fluoride nanoparticles at concentration, indicating doped Li+Successfully enters the calcium fluoride crystal and changes the diffraction angle of the diffraction intensity of the original crystal lattice. Demonstration of doped Li+Successfully enters the calcium fluoride crystal and changes the diffraction angle of the diffraction intensity of the original crystal lattice. Activator Nd3+Has a concentration of 6%, doped with Li+The transmission electron microscope observation at a concentration of 30% is shown in FIG. 9. FIG. 9 shows the application of Nd as an activator3+Has a concentration of 6%, doped with Li+Concentration 30%, oleic acid and octadecene ratio in 1: reacting at 20, 300 ℃ for 90 minutes to obtain calcium fluoride nano particlesTEM image of a radio-electron microscope. In the activator Nd3+Has a concentration of 6%, doped with Li+The size distribution of the nanoparticles in the TEM image of calcium fluoride nanoparticles obtained at a concentration of 30% is shown in FIG. 10, where FIG. 10 shows the distribution of the nanoparticles in the activator Nd3+Has a concentration of 6%, doped with Li+Concentration 30%, oleic acid and octadecene ratio in 1: and (3) reacting at the temperature of 20 ℃ and 300 ℃ for 90 minutes to obtain the size distribution of the calcium fluoride nanoparticles in a TEM picture of a transmission electron microscope. The dimensional change is larger compared to fig. 5. In the activator Nd3+The concentration of (A) is 6%, and Li is doped differently+The near infrared fluorescence spectrum of the calcium fluoride nanoparticles at the concentration under the excitation of 808nm is shown in figure 11, and figure 11 shows that the calcium fluoride nanoparticles are excited by an activating agent Nd3+With a concentration of 6% and different doping of Ce3+Near infrared fluorescence spectrum of calcium fluoride nanoparticles at concentration under 800nm excitation, 30% Li+Doping phase is Li-free+The doping is enhanced by about 4 times.
Example 3:
1) 0.06mmol of neodymium acetate tetrahydrate, 0.5mmol of cerium acetate tetrahydrate and 0.44mmol of Ca (OH)2 are weighed into a 250ml three-neck flask, and 8ml of oleic acid and 12ml of octadecene are added as solvents.
2) Connecting one of the flask openings with a vacuum pump, sealing the other two flask openings with rubber plugs, and inserting a thermocouple thermometer; thereafter, the vacuum pump and the stirrer were turned on, and the vacuum pressure was maintained at 0.1Pa and the stirring rate was 200 revolutions per minute.
3) Opening the heating jacket, heating to 70 deg.C for 10min, heating to 150 deg.C for 20min to form clear and transparent solution, and cooling to room temperature.
4) Weighing 2.5mmol NH4F, adding 10ml of anhydrous methanol to prepare a solution; 10ml NH to be prepared under stirring4And F, adding the absolute methanol solution into the system in the room temperature state in the step 3).
5) Reacting the solution system obtained in the step 4) for 30 minutes at 40 ℃ under stirring and vacuum conditions, and then heating to 100 ℃ for 10 minutes to remove methanol and water vapor.
6) Introducing argon flow with slow flow rate into the solution system obtained after the step 5), heating to 300 ℃, keeping the temperature for 90 minutes, and naturally cooling to room temperature to obtain the calcium fluoride-containing nanoparticle reaction liquid.
7) Centrifuging the reaction solution obtained in the step 6) by using a high-speed centrifuge to obtain a precipitate, alternately centrifuging and washing for 2 times by using cyclohexane and absolute ethyl alcohol, placing the obtained nano particles in a vacuum drying oven, drying at 60 ℃, and finally sealing and storing the nano particles.
The obtained Nd is an activator3+Is 6% fixed, and different Ce is doped3+The X-ray diffraction pattern of the calcium fluoride nanoparticles at the concentration is shown in FIG. 12, and FIG. 12 shows the diffraction pattern at the activator Nd3+At a fixed concentration of 6%, the oleic acid and octadecene ratio was in the range of 1: different Li dopings obtained by reaction at 20, 300 ℃ for 90 minutes+XRD diffractogram of calcium fluoride nanoparticles at concentration, indicating doped Ce3+The successful access to the calcium fluoride crystal and the change of the diffraction angle of the diffraction intensity of the original crystal lattice prove that the doped Ce3+Successfully enters the calcium fluoride crystal and changes the diffraction angle of the diffraction intensity of the original crystal lattice. Activator Nd3+Is 6%, doped with Ce3+The concentration was 30%, and the observation by transmission electron microscope was shown in FIG. 13. FIG. 13 shows the application of Nd as an activator3+Is 6%, doped with Ce3+Concentration 30%, oleic acid and octadecene ratio in 1: and (3) performing a reaction at 300 ℃ for 90 minutes to obtain a TEM picture of the calcium fluoride nanoparticles. In the activator Nd3+Is 6%, doped with Ce3+The size distribution of the nanoparticles in the TEM image of calcium fluoride nanoparticles obtained at a concentration of 30% is shown in FIG. 14, which shows the distribution of the nanoparticles in the activator Nd3+Is 6%, doped with Ce3+Concentration 30%, oleic acid and octadecene ratio in 1: and (3) reacting at the temperature of 20 ℃ and 300 ℃ for 90 minutes to obtain the size distribution of the calcium fluoride nanoparticles in a TEM picture of a transmission electron microscope. The dimensional change is larger compared to fig. 5. In the activator Nd3+With a concentration of 6% and different doping of Ce3+The near infrared fluorescence spectrum of the calcium fluoride nanoparticles at the concentration under the excitation of 808nm is shown in figure 15, and the graph 15 shows that the calcium fluoride nanoparticles are excited by an activating agent Nd3+With a concentration of 6% and different doping of Ce3+Near infrared fluorescence spectrum of calcium fluoride nanoparticles at concentration under 800nm excitation, 50% Ce3+Light intensity ratio under doping is Ce-free3+The doping is enhanced by a factor of 11.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method for preparing calcium fluoride nanoparticles, comprising:
adding a solvent to the first mixture to form a mixed solution; wherein the first mixture comprises calcium hydroxide and at least one compound containing rare earth ions, the solvent being used to dissolve the first mixture;
adding ammonium fluoride into the mixed solution to form a reaction solution;
heating the reaction solution to a first preset temperature;
and keeping the temperature of the reaction solution for a first preset time to obtain a reaction product.
2. The method according to claim 1, wherein the compound containing rare earth ions is a nitrate, a chlorate or an acetate of rare earth ions.
3. The method of claim 2, wherein the solvent is oleic acid or a mixture of oleic acid and octadecene.
4. The method according to claim 3, wherein the solvent is a mixture of oleic acid and octadecene, and the mixing ratio of oleic acid to octadecene is 1: 100-100: 1.
5. the method of claim 1 or 4, wherein the first mixture further comprises a dopant, the dopant being at least one metal ion-containing compound.
6. According to claimThe method of claim 5, wherein the metal ions comprise: li+、Na+、K+、Mn2+、Ce3+、Gd3+、Y3+And Sr2+At least one of (1).
7. The method of claim 1, wherein adding a solvent to the first mixture to form a mixed solution comprises:
adding a solvent to the first mixture to form a second mixture;
heating the second mixture to a second preset temperature under vacuum conditions;
and keeping the second mixture warm for a second preset time.
8. The method of claim 7, wherein the heating the reaction solution to a first predetermined temperature comprises:
introducing protective gas into the reaction solution;
heating the reaction solution to a first preset temperature.
9. The method for preparing the composite material according to claim 8, wherein the first preset temperature is 200 ℃ to 400 ℃; and/or the presence of a gas in the gas,
the second preset temperature is 50-200 ℃.
10. The method of manufacturing according to claim 9, further comprising: adding a detergent into the reaction product, and centrifuging and washing the reaction product.
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