CN115197703A - Alkali-assisted method for preparing lanthanum-based rare earth nanoparticles - Google Patents
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Abstract
The invention discloses a method for preparing a lanthanum-based rare earth nano material with the assistance of alkali. The method comprises the following steps: adding a matrix cation salt into a solvent, heating and dehydrating in vacuum, cooling to a certain temperature, adding an alkali solution for reaction, reacting for a certain time, dehydrating again, heating in an inert atmosphere for reaction, cooling, and precipitating to obtain the lanthanum-based rare earth luminescent nano material. The lanthanum-based rare earth nano material prepared by the method has the advantages of adjustable size, narrow size distribution, good dispersity and high crystallinity, and has excellent luminous performance, and the shape of the lanthanum-based rare earth nano material can be a short rod, an ellipsoid or a sphere.
Description
Technical Field
The invention belongs to the technical field of preparation of rare earth luminescent nano materials, and particularly relates to a method for preparing a lanthanum-based rare earth nano material with controllable crystalline phase, controllable size, narrow size distribution, good dispersibility and excellent luminescent performance by alkali assistance.
Background
Trivalent rare earth ion (RE) 3+ ) Has rich magnetic and optical properties due to the unique 4f electronic structure, and the 17 rare earth elements have similar ionic radii and similar chemical properties, so that the rare earth element is easy to dope or constructThe forms of core-shell structure and the like are integrated together to obtain the nanometer material with various functions. In addition, due to RE 3+ The excitation wavelength of the light source is generally in a near infrared region with deeper tissue penetration depth, and the light emission has the advantages of large Stokes shift, narrow half-peak width, long service life and the like, so that the light source based on RE (rare earth) is based on 3+ The nano-material has been widely researched and applied in solar cells, biosensing, optogenetics, biomedical imaging (especially near-infrared two-region imaging) and treatment in recent years.
The rare earth luminescent nano material mainly relates to three elements of a substrate, a sensitizer and a luminescent center, and the selection of a proper substrate material is the first step for ensuring effective luminescence. In order to minimize the losses due to non-radiative transitions while increasing radiative transitions, the ideal host material should have a lower phonon energy. Compared with oxide, the phonon energy of fluoride is only 350cm -1 And has high chemical stability, so that the material is often used as a matrix material in rare earth luminescence research, such as LaF 3 、NdF 3 、GdF 3 、CaF 2 And the like. In addition to phonon energy, the crystal structure of the matrix also has an effect on the rare earth luminous efficiency. Generally, the selection of a low symmetry host material is more advantageous for achieving efficient light emission than a high symmetry host material. The complex fluoride has lower symmetry than that of single fluoride due to the existence of other complex cations, and is the most widely studied matrix material at present, wherein NaYF in hexagonal phase 4 、NaGdF 4 And NaYbF 4 Is the main representative. Although hexagonal phase NaLaF 4 Has lower phonon energy (about 290 cm) -1 ) But due to La 3+ And F - Has stronger binding capacity, so that LaF is easier to obtain in the synthesis process 3 But not NaLaF 4 . To prepare the hexagonal phase of NaLaF 4 (β-NaLaF 4 ) Nanomaterial, researchers have tried different approaches. For example by doping with different concentrations of rare earth ions (mainly Nd) 3+ -Tb 3+ ) beta-NaLaF can be synthesized by adopting a solvothermal method 4 Material (J.Mater.chem.C, 2017,5,9188), but this method does not yield high crystalline phase purity beta-NaLaF 4 And (3) nano materials. In addition, researchers have synthesized pure β -NaLaF by a Liquid-Solid-Solution (LSS) method 4 (adv. Mater.,2007,19,3304), but the synthesis generally requires longer preparation time and produces larger material sizes (>100 nm) against its further biological applications. Although there are researchers using oleylamine to synthesize ultra-small size by controlling the composition of solvent: (<5 nm) of beta-NaLaF 4 Material (chem. Mater.,2019,31,4779), but the ultra-small nanoparticles have large specific surface area and excessive surface defects, which is not favorable for further doping luminescent ions to realize effective rare earth ion luminescence. Recently, although some researchers have utilized Cs + The beta-NaLaF with uniform size and moderate grain diameter is prepared in an auxiliary way 4 Nanomaterials (chem. Mater.,2019,31,9497), but the required preparation temperatures are higher.
Disclosure of Invention
One of the purposes of the invention is to provide a lanthanum-based rare earth luminescent nano material with adjustable size, narrow size distribution, good dispersibility and excellent luminescent performance.
The second purpose of the invention is to provide a mild preparation method of a high-quality lanthanum-based rare earth nano material, so as to overcome the defects and shortcomings of the existing synthesis technology and realize the purposes of controllable crystal phase, uniform size, good dispersibility and excellent luminescence performance of the rare earth nano material.
The lanthanum-based rare earth luminescent nano material provided by the invention is prepared by a high-temperature double decomposition method, and the specific preparation method comprises the following steps: adding salt containing matrix cations into a solvent, heating and dehydrating in vacuum, cooling to a certain temperature, adding an alkali solution for reaction, reacting for a certain time, dehydrating again, heating in an inert atmosphere for reaction, cooling, and precipitating to obtain the lanthanum-based rare earth luminescent nano material.
Further, the specific process is as follows:
s1, weighing a certain amount of salt containing matrix cations in a glass container;
s2, adding a high-boiling-point solvent;
s3, stirring, heating and dehydrating under a vacuum state until all metal ion salts are completely dissolved to form a transparent uniform solution;
s4, preparing an alkali solution with a certain concentration;
s5, slowly adding the alkali solution prepared in the S4 into the S3 solution when the solution is cooled to a certain temperature;
s6, reacting the mixed solution obtained in the step S5 at a certain temperature for a certain time;
s7, heating and dehydrating the mixed solution obtained in the step S6 in a vacuum state till the mixed solution is completely dehydrated, and then heating and reacting for a period of time in an inert atmosphere;
s8, cooling to finish the reaction;
s9, after the reaction liquid is cooled to room temperature, taking a part of the solution into a centrifuge tube, adding excessive ethanol, centrifuging, removing supernatant, and dissolving precipitate with cyclohexane;
and S10, repeating the step S9 for at least three times to finally obtain the stable rare earth nanocrystal solution.
The substrate material in the lanthanum-based rare earth luminescent nano material prepared by the invention is mainly lanthanum-based nanocrystals.
In the above method S1, the matrix cation comprises La 3+ And at least one complexing ion; the compound ion is selected from at least one of alkali metal ions and alkaline earth metal ions;
the La 3+ May contain La 3+ Salts and hydrates thereof, e.g. La 3+ Oleate, nitrate, chloride and hydrates thereof.
The alkali metal ion or alkaline earth metal ion may also be provided in the form of a salt containing the alkali metal ion or alkaline earth metal ion and a hydrate thereof, such as sodium, potassium and calcium oleates, nitrates, chlorides and hydrates thereof.
Specific such salts containing a matrix cation include, but are not limited to: lanthanum chloride hexahydrate, and the composition of at least one of: sodium oleate, sodium chloride, calcium chloride dihydrate.
Further, the salt containing a matrix cation is LaCl 3 ·6H 2 O and sodium oleate according to the mass ratio of 1:1-1:5 (e.g., 1:2).
In the above method S1, a salt containing a sensitizer ion and/or a luminescence center ion may be further added; the sensitizer ion is selected from at least one of: ce 3+ 、Gd 3+ 、Nd 3+ 、Yb 3+ 、Er 3+ (ii) a The luminescence center ion is selected from at least one of the following: ce 3+ 、Nd 3+ 、Eu 3+ 、Gd 3+ 、Tb 3+ 、Dy 3+ 、Ho 3+ 、Tm 3+ 、Yb 3+ 、Er 3+ 、Cr 3+ 、Mn 2+ 。
The salt containing the sensitizer ion and the luminescence center ion includes salts containing rare earth ions and transition metal ions and hydrates thereof, such as chlorides, nitrates, acetates and hydrates thereof of manganese, chromium and lanthanide. Specific examples include, but are not limited to, manganese acetate, chromium chloride, neodymium chloride hexahydrate, erbium acetate, and the like.
In the method S2, the high-boiling point solvent includes one or more of oleic acid, octadecene, oleylamine, and the like, or a derivative or an analogue of the above solvent. Specific embodiments include, but are not limited to: the volume ratio of the oleic acid to the 1-octadecene is 1:4.
In the method S3, the temperature for heating and dehydrating is 120-150 ℃.
In the method S3, rare earth nanoparticles can be added, so that the finally obtained lanthanum-based rare earth luminescent nano material is a core/shell type nano crystal.
In the above method S4, the alkali solution is a methanol solution in which a metal hydroxide, such as potassium hydroxide, sodium hydroxide, etc., and ammonium fluoride are dissolved. The concentration of the metal hydroxide in the methanol solution in which the metal hydroxide and ammonium fluoride are dissolved may be 0.05 to 1M, and the concentration of the ammonium fluoride may be 0.15 to 0.4M.
In the above method S5, the cooling temperature is 20 to 60 ℃, preferably 50 ℃.
In the method S6, the reaction temperature is 20-60 ℃, preferably 50 ℃, and the reaction time is 30min-24h, preferably 30min.
In the method S7, the reaction temperature is in the range of 290-310 ℃, preferably 290 ℃, and the reaction time is in the range of 45-90min, preferably 60min.
The invention can prepare different luminescent rare earth nano materials by changing reaction conditions, including the species and proportion of rare earth ions, alkali metal ions or alkaline earth metal ions in S1.
The invention can prepare rare earth nano materials with different luminescence properties by changing reaction conditions, including a seed epitaxial growth method and the like.
The rare earth luminescent nanocrystals with different morphologies and compositions can be prepared by changing reaction conditions including the type and concentration of the alkali in S4.
The invention can obtain the rare earth luminescent nanocrystals with different sizes by changing the reaction conditions, including the composition and the ratio of the solvent in S2, and the reaction temperature and the reaction time in S6 and S7.
The lanthanum-based rare earth luminescent nano material prepared by the method also belongs to the protection scope of the invention.
The lanthanum-based rare earth nano material prepared by the method has the advantages of adjustable size, narrow size distribution, good dispersity and high crystallinity, and has excellent luminous performance, and the shape of the lanthanum-based rare earth nano material can be a short rod, an ellipsoid or a sphere.
The method for preparing the lanthanum-based rare earth luminescent nano material has the characteristics of short time consumption, simple and convenient operation, mild conditions and the like, the preparation of the high-quality lanthanum-based rare earth nano material can be directly realized through the high-temperature double decomposition reaction under the assistance of alkali, the obtained nano crystal has controllable crystalline phase, adjustable size, narrow size distribution, good dispersibility and excellent luminescent performance, more options are provided for the selection of the matrix of the rare earth nano material, and the excellent luminescent performance of the material provides more selectivity for the rare earth nano material in biomedical application, particularly in the field of near-infrared two-zone imaging, so that the lanthanum-based rare earth luminescent nano material has wide application prospect and market prospect.
Drawings
FIG. 1 is a transmission electron micrograph (A) and a histogram (B) of length distribution and a histogram (C) of width distribution of a sample obtained in example 1 of the present invention.
FIG. 2 is an electron diffraction photograph of a sample obtained in example 1 of the present invention.
FIG. 3 is a transmission electron micrograph (A) and a particle size distribution histogram (B) of the sample obtained in example 2 of the present invention.
FIG. 4 is an electron diffraction photograph of a sample obtained in example 2 of the present invention.
FIG. 5 is a TEM image of a sample obtained in example 3 of the present invention (A), and a histogram (B) and a histogram (C) of its length distribution and width distribution.
FIG. 6 is an electron diffraction photograph of a sample obtained in example 3 of the present invention.
FIG. 7 is a graph showing UV-VIS absorption spectra of samples obtained in examples 2 to 3 of the present invention at the same concentrations.
FIG. 8 is a spectrum of emission light of the sample obtained in examples 2-3 of the present invention at the same concentration excited by a laser at 808 nm.
FIG. 9 shows photographs taken with a near-infrared camera of example 2 (A) and example 3 (B) of the present invention at the same concentration when excited with a 808nm laser.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1 preparation of lanthanum-based rare earth luminescent nanomaterial
S1, weighing 0.3534g LaCl 3 ·6H 2 O and 0.6089g sodium oleate in a 100mL three-neck round bottom glass flask;
s2, adding 8mL of oleic acid and 32mL of 1-octadecene;
s3, stirring and heating to 150 ℃ in a vacuum state for dehydration until all metal ion salts are completely dissolved to form a transparent uniform solution;
s4, preparing 20mL of methanol solution containing 0.1M of potassium hydroxide and 0.2M of ammonium fluoride;
s5, dropwise adding the solution prepared by the S4 into the S3 solution when the solution is cooled to 50 ℃;
s6, reacting the mixed solution obtained in the S5 at 50 ℃ for 30min;
s7, heating the mixed solution obtained in the step S6 to 110 ℃ in a vacuum state, dehydrating completely, and heating to 290 ℃ in an inert atmosphere to react for 1h;
s8, cooling to finish the reaction;
s9, after the reaction liquid is cooled to room temperature, putting 1mL of solution into a centrifuge tube, adding 2mL of ethanol, centrifuging, removing supernate and dissolving precipitate with 1mL of cyclohexane;
and S10, repeating the step S9 for three times to finally obtain the stable rare earth luminescent nanocrystal solution.
Characterized by Transmission Electron Microscopy (TEM), and lanthanum-based nanocrystal NaLaF shown in figure 1 4 The transmission electron micrograph (A) and the particle size distribution histogram (B) thereof. As can be seen from electron microscope photographs, the lanthanum-based nanocrystal is in a short rod shape, has an average particle size of 57.4 +/-5.0 nm in length and 27.5 +/-3.6 nm in width, and has good monodispersity. The electron diffraction photograph in fig. 2 shows that the lanthanum-based nanocrystal particles have high crystallinity and are in a hexagonal phase.
Example 2 preparation of Neodymium-containing rare earth nanomaterials
S1, weighing 0.3587g NdCl 3 ·6H 2 O is put in a 100mL three-neck round bottom glass flask;
s2, adding 8mL of oleic acid and 32mL of 1-octadecene;
s3, stirring and heating to 150 ℃ in a vacuum state for dehydration until all metal ion salts are completely dissolved to form a transparent uniform solution;
s4, preparing 20mL of methanol solution containing 0.1M of sodium hydroxide and 0.2M of ammonium fluoride;
s5 to S10, same as in example 1.
Characterized by a Transmission Electron Microscope (TEM), and the attached figure 3 shows neodymium-containing rare earth nanocrystal NaNdF 4 The transmission electron micrograph (A) and the particle size distribution histogram (B) thereof. As can be seen from electron microscope photographs, the nanocrystals are spherical, have an average particle size of 8.7 +/-0.8 nm and have good monodispersity. The electron diffraction photograph in fig. 4 shows that the nanocrystalline particles are highly crystalline and in the hexagonal phase. The solid line in fig. 7 is the uv-vis absorption spectrum of the nanocrystal. As can be seen, the nano material is at 730nm, 808nm and 860nThe absorption is stronger around m. The solid line in FIG. 8 is the emission spectrum of the cyclohexane solution of the nanocrystals under the excitation of 808nm laser, which shows that the Nd-containing nanocrystals have strong emission in the range of 850-900nm, 1000-1100nm and 1300-1400 nm. FIG. 9 (A) is a photograph taken with a near infrared camera when a cyclohexane solution of the material is excited by a laser beam of 808nm, and it can be seen from the photograph that the material emits light in the near infrared region strongly with the laser beam of 808 nm.
Example 3 preparation of lanthanum-based rare earth luminescent nanomaterial
S1, weighing 0.3534g LaCl 3 ·6H 2 O and 0.6089g sodium oleate in a 100mL three-neck round bottom glass flask;
s2, adding 8mL of oleic acid and 32mL of 1-octadecene;
s3, stirring and heating to 150 ℃ under a vacuum state for dehydration until all metal ion salts are completely dissolved to form a transparent uniform solution, adding 10mL of cyclohexane solution containing 0.64mmol of the nano-particles prepared in example 2, and continuing to heat and stir under the vacuum state until the cyclohexane is completely removed;
s4 to S10, same as in example 1.
Characterized by Transmission Electron Microscopy (TEM), and lanthanum-based core/shell nanocrystal NaNdF is shown in figure 5 4 @NaLaF 4 The transmission electron micrograph (A) and the length distribution histogram (B) and the width distribution histogram (C) thereof. As can be seen from electron micrographs, the lanthanum-based nanocrystal is ellipsoidal, has an average particle size of 17.0 +/-2.3 nm in length and 12.6 +/-1.9 nm in width, and has good monodispersity. The electron diffraction photograph in fig. 6 shows that the lanthanum-based nanocrystal particles have high crystallinity and are in a hexagonal phase. The dotted line in fig. 7 is the uv-vis absorption spectrum of the lanthanum-based nanocrystal; as can be seen from the figure, the lanthanum-based core/shell nanomaterial has strong absorption at about 730nm, 808nm, and 860nm, and the absorption is equivalent to that in example 2. The dotted line in fig. 8 is the emission spectrum of the cyclohexane solution of lanthanum-based nanocrystals under the excitation of 808nm laser; as can be seen, the lanthanum-based core/shell nanocrystals exhibited significantly enhanced emission intensities in the 850-900nm, 1000-1100nm and 1300-1400nm ranges as compared to the emission intensity of example 2. FIG. 9 (A) shows that when the cyclohexane solution of the material is excited by 808nm laser, a near infrared camera is usedThe photo was taken. As can be seen, the material emits light in the near infrared region more strongly than that of example 2 under the laser of 808 nm.
Claims (10)
1. A preparation method of lanthanum-based rare earth luminescent nano material is prepared by a high-temperature double decomposition method, and comprises the following steps: mixing the salt containing the matrix cations with a solvent, heating and dehydrating in vacuum, cooling, adding an alkali solution for reaction, reacting for a certain time, dehydrating again, heating and reacting under an inert atmosphere, cooling, and precipitating to obtain the lanthanum-based rare earth luminescent nano material.
2. The method of claim 1, comprising the steps of:
s1, weighing matrix cation salt in a container;
s2, adding a high-boiling-point solvent;
s3, stirring, heating and dehydrating under a vacuum state until all the salt is completely dissolved to form a transparent uniform solution;
s4, preparing an alkali solution;
s5, slowly adding the alkali solution prepared by the S4 into the S3 solution after the solution is cooled;
s6, reacting the mixed solution obtained in the S5 for a certain time;
s7, heating and dehydrating the mixed solution obtained in the step S6 in a vacuum state till the mixed solution is completely dehydrated, and then heating and reacting for a period of time in an inert atmosphere;
s8, cooling to finish the reaction;
s9, after the reaction liquid is cooled to room temperature, taking a part of the solution into a centrifuge tube, adding excessive ethanol, centrifuging, removing supernatant, and dissolving the precipitate with cyclohexane;
and S10, repeating the step S9 for at least three times to finally obtain the stable rare earth nanocrystal solution.
3. The method according to claim 1 or 2, characterized in that: in S1, the matrix cation comprises La 3+ And at least one complexing ion; the compound ion is selected from alkali goldAt least one of a metal ion and an alkaline earth metal ion;
the La 3+ To contain La 3+ Salts and hydrates thereof, e.g. La 3+ Oleate, nitrate, chloride and hydrates thereof;
the alkali metal ion or alkaline earth metal ion is provided in the form of a salt containing an alkali metal ion or alkaline earth metal ion and a hydrate thereof, such as sodium, potassium and calcium oleates, nitrates, chlorides and hydrates thereof;
specific such salts containing a matrix cation include, but are not limited to: lanthanum chloride hexahydrate, and the composition of at least one of: sodium oleate, sodium chloride, calcium chloride dihydrate.
4. A method according to claim 2 or 3, characterized in that: in the S1, a salt containing a sensitizer ion and/or a luminescence center ion is also added; the sensitizer ion is selected from at least one of: ce 3+ 、Gd 3+ 、Nd 3+ 、Yb 3+ 、Er 3+ (ii) a The doping ions are selected from at least one of the following: ce 3+ 、Nd 3+ 、Eu 3+ 、Gd 3+ 、Tb 3+ 、Dy 3+ 、Ho 3+ 、Tm 3+ 、Yb 3+ 、Er 3+ 、Cr 3+ 、Mn 2+ ；
The salt containing the sensitizer ion and the luminescence center ion includes salts containing rare earth ions and transition metal ions and hydrates thereof, such as chlorides, nitrates, acetates and hydrates thereof of manganese, chromium and lanthanide.
5. The method according to any one of claims 2-4, wherein: in the S2, the high-boiling-point solvent comprises one or a mixture of more of oleic acid, octadecene and oleylamine, or derivatives and analogues of the solvent; in particular to a mixed solvent of oleic acid and 1-octadecene with the volume ratio of 1:4;
or, in S4, the alkali solution is a methanol solution in which a metal hydroxide and ammonium fluoride are dissolved;
the concentration of the metal hydroxide in the methanol solution dissolved with the metal hydroxide and the ammonium fluoride is 0.05-1M, and the concentration of the ammonium fluoride is 0.15-0.4M.
6. The method according to any one of claims 2-5, wherein: in the S6, the reaction temperature ranges from 20 ℃ to 60 ℃, preferably 50 ℃, and the reaction time ranges from 30min to 24h, preferably 30min;
or in the S7, the reaction temperature ranges from 290 ℃ to 310 ℃, preferably 290 ℃, and the reaction time ranges from 45 min to 90min, preferably 60min.
7. The method according to any one of claims 2-6, wherein: in the method S3, the temperature for heating and dehydrating is 120-150 ℃;
in S5, the cooling temperature is 20-60 ℃.
8. The method according to any one of claims 2-7, wherein: in the method S3, rare earth nanoparticles are also added, so that the finally obtained lanthanum-based rare earth luminescent nano material is a core/shell type nano crystal.
9. The lanthanum-based rare earth luminescent nanomaterial prepared by the method of any one of claims 1 to 8.
10. The lanthanum-based rare earth luminescent nanomaterial of claim 9 for biomedical applications, in particular for the field of near-infrared two-zone imaging.
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