CN114806566B - Preparation method and application of micro rare earth molybdate up-conversion luminescent material - Google Patents
Preparation method and application of micro rare earth molybdate up-conversion luminescent material Download PDFInfo
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Abstract
The invention belongs to the technical field of up-conversion luminescent materials, and particularly relates to a preparation method and application of a micro rare earth molybdate up-conversion luminescent materialThe application is. The rare earth molybdate up-conversion luminescent material adopts Ln 2 Mo 4 O 15 (Ln = Y, gd, la, lu) as a host, and rare earth ions as an activator and a sensitizer are doped into the host. Firstly, preparing rare earth doped monodisperse, spherical and superfine rare earth oxide by adopting a uniform precipitation method, then fully mixing the rare earth doped monodisperse, spherical and superfine rare earth oxide with ammonium molybdate, and calcining the mixture at 700-800 ℃ for 1-5h to obtain a target product. The method of the invention can prepare fine Ln 2 Mo 4 O 15 The upconversion particles have the average particle size of not more than 1.5 mu m, are spherical and have good dispersibility, and can be applied to the fields of high-resolution display, in-vitro biological imaging and the like.
Description
Technical Field
The invention belongs to the technical field of up-conversion luminescent materials, and particularly relates to a preparation method and application of a micro rare earth molybdate up-conversion luminescent material.
Background
The up-conversion luminescent material can emit visible light under the excitation of infrared laser, and has special properties, so that the up-conversion luminescent material has wide application prospects in the fields of optical fiber communication, infrared detection, biological marking, anti-counterfeiting, display and the like. The choice of the host material is particularly critical for practical applications of the up-converting luminescent material. Research shows that the matrix with lower phonon energy has higher up-conversion luminous efficiency. According to the report, halides and sulfides have lower phonon energy, and the current efficient up-conversion materials mostly use halides and sulfides as substrates. However, the chemical stability and machinability of halides and sulfides are poor and the pollution during the production process is severe. In contrast, oxides are mostly non-toxic and chemically very stable, and are ideal choices for upconverting matrix materials. Wherein, rare earth molybdate Ln 2 Mo 4 O 15 (Ln = Y, gd, la, lu) has been receiving more and more attention in recent years because of its moderate phonon energy and high luminous efficiency in oxide.
At present, the preparation of rare earth doped Ln is related to the preparation at home and abroad 2 Mo 4 O 15 The reports (Journal of Alloys and Compounds,2022,895,162516, journal of Alloys and Compounds,2020,814,152237, RSC Advances,2016,6, 109278) but all of these materials were prepared by conventional high temperature solid phase methods, with larger particle sizes (see FIGS. (R))>5 μm) cannot meet the application requirements of special fields such as higher and higher display resolution and biological detection. Although some new preparation methods (Materials Research Express,2018,5,066204, journal of Nanoscience and nanotechnology,2016,16, 4003) have emerged in recent years, the Materials prepared by these methods are not good in particle morphology and dispersibility, are not suitable for practical use, and are not suitable for mass production.
Disclosure of Invention
In view of the above situation, the present invention aims to provide a method for preparing a rare earth ion doped molybdate substrate up-conversion luminescent material with small size, regular morphology and good dispersibility.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a micro rare earth molybdate up-conversion luminescent material, which is prepared from Ln 2 Mo 4 O 15 (Ln = Y, gd, la and Lu) is taken as a matrix, one or two of Yb and Nd is taken as a sensitizing agent, and one or two of Er, tm, ho, pr and Sm is taken as an activating agent; the mol doping amount of the activator rare earth ions is 0.1-10%, and the mol doping amount of the sensitizer rare earth ions is 10-50%.
Furthermore, the luminescent material is spherical-like, and the particle size is less than or equal to 1.5 mu m.
In another aspect, the present invention provides a method for preparing the above luminescent material, including the following steps:
1) Weighing matrix rare earth nitrate, activator rare earth nitrate and sensitizer rare earth nitrate according to the doping proportion, and dissolving in water to form a solution A;
2) Weighing urea, and dissolving the urea in water to form a solution B;
3) Pre-heating the solution A to 60-80 ℃ through a water bath, then pouring the solution B into the solution A to form a mixed solution C, heating the mixed solution C to 80-95 ℃, and continuing curing for 30-90min when the mixed solution is observed to be light blue turbid;
4) After the ripening is finished, centrifugally separating out the precipitate, washing with purified water for three times and washing with ethanol for one time, drying at 40 ℃ for 12 hours, and calcining the dried precipitate at 600-800 ℃ for 1 hour to obtain a rare earth oxide precursor;
5) According to the formula Ln of molybdate 2 Mo 4 O 15 Weighing rare earth oxide precursors and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 And O, pouring the mixture into a mortar, fully grinding and mixing, and calcining the ground mixture at 700-800 ℃ for 1-5h to obtain a target sample.
Further, the ratio of the sum of the mole numbers of the matrix rare earth nitrate, the activator rare earth nitrate and the sensitizer rare earth nitrate to the mole number of the urea is 1.
Further, the total concentration of the rare earth cations in the mixed solution C is 0.001-1mol/L.
Further, the matrix rare earth nitrate comprises yttrium nitrate, gadolinium nitrate, lanthanum nitrate, lutetium nitrate; the sensitizer rare earth nitrate comprises one or two of ytterbium nitrate and neodymium nitrate; the activator rare earth nitrate comprises one or more of erbium nitrate, holmium nitrate, thulium nitrate, praseodymium nitrate and samarium nitrate.
The invention further provides an application of the luminescent material, which can be applied to the field of in vitro biological imaging.
The invention has the beneficial effects that:
the method can prepare the fine rare earth doped Ln 2 Mo 4 O 15 Upconverting particles, the average particle size of which does not exceed 1.5 μm, much smaller than the methods reported in the literature; the particles are spherical and have good dispersibility, and can be used for high resolution display and in vitro biologyImaging and the like; the method disclosed by the invention is simple to operate, low in cost, pollution-free in preparation process and very suitable for large-scale production.
Drawings
FIG. 1 shows Yb prepared in example 1 3+ 、Er 3+ Co-doped Y 2 O 3 SEM pictures of the samples;
FIG. 2 shows the target samples 1 and Y prepared in example 1 2 Mo 4 O 15 (PDF # 53-0358) standard card X-ray diffraction data;
FIG. 3 is an SEM photograph of a target sample 1 prepared in example 1;
FIG. 4 is an emission spectrum of a target sample 1 prepared in example 1 under excitation of a 980nm laser;
FIG. 5 is an SEM picture of a target sample 2 prepared in example 2;
FIG. 6 is an emission spectrum of a target sample 2 prepared in example 2 under excitation by a 980nm laser;
FIG. 7 is the emission spectra of different samples of example 3 under excitation by a 980nm laser;
FIG. 8 is an emission spectrum of a target sample 4 prepared in example 4 under excitation of a 980nm laser;
FIG. 9 shows the emission spectra of different samples of example 5 under excitation by a 980nm laser.
Detailed Description
The following examples are provided to clearly and specifically describe the technical solutions of the present invention, but the present invention is not limited in any way by the examples.
Example 1
Y 2 Mo 4 O 15 :18％Yb 3+ ,1％Er 3+ The preparation method comprises the following steps:
1) Weighing yttrium nitrate, ytterbium nitrate and erbium nitrate according to a stoichiometric ratio to enable the total amount of rare earth cations to reach 0.016mol, and preparing 800ml of aqueous solution with a proper amount of purified water, wherein the aqueous solution is marked as solution A;
2) Weighing 96g of urea, dissolving the urea in 320ml of purified water, marking as a solution B, and filtering the solution A and the solution B through filter paper to remove impurities in the solution;
3) Heating the solution A to 60 ℃ in advance through water bath, then pouring the solution B and a proper amount of purified water filtered by filter paper into the solution A to prepare a mixed solution with the total volume of 1.6L, heating the mixed solution to 82 ℃, and continuously curing for 45min when the mixed solution is observed to be light blue turbid;
4) After the aging is finished, taking out the beaker containing the mixed solution from the water bath, placing the beaker in cold water for cooling, then carrying out centrifugal separation (4500 rmp multiplied by 5 min) on the solution, washing the precipitate with purified water for three times, washing the precipitate with isopropanol for one time, drying the precipitate at 40 ℃ for 12h to obtain white powder, and calcining the white powder at 700 ℃ for 1h to obtain white Yb 3+ 、Er 3+ Co-doped Y 2 O 3 A precursor;
5) Weighing the rare earth oxide precursor and (NH) according to the stoichiometric ratio 4 ) 6 Mo 7 O 24 ·4H 2 And O, then mixing them, pouring them into a mortar, sufficiently grinding and mixing them, and calcining the ground mixture at 750 ℃ for 2 hours to obtain the objective sample 1.
FIG. 1 is Y 2 O 3 SEM photograph of the precursor, from which it can be seen that Y was prepared 2 O 3 The precursor is in a perfect spherical shape, the particle size is very uniform, the average particle size is small and is about 80nm, and the precursor is taken as a raw material, so that the small-size molybdate up-conversion material with uniform particle size is formed.
FIG. 2 is an X-ray diffraction pattern (XRD) of the target sample 1, from which XRD diffraction peaks and Y of the sample can be seen 2 Mo 4 O 15 (PDF # 53-0358) the standard cards matched well. Furthermore, all diffraction peaks are shifted to a large angle direction compared to the standard card (PDF # 53-0358). This is due to the small radius of Yb 3+ And Er 3+ Ion doping replaces Y 3+ The shrinkage of the host lattice by the ions indicates the successful doping of the rare earth ions into Y 2 Mo 4 O 15 In a matrix.
Fig. 3 is an SEM picture of the target sample 1, and it can be seen from the figure that the average particle size of the prepared rare earth doped yttrium molybdate is about 1.5 μm, and the particles have regular morphology, are spheroidal, have good dispersibility, and are very beneficial to practical application.
Fig. 4 is an emission spectrum of the target sample 1 prepared in example 1 under excitation of a 980nm laser, and it can be seen that the sample mainly exhibits green emission at 510-575nm and green color purity is high.
Example 2
Gd 2 Mo 4 O 15 :40％Yb 3+ ,0.5％Tm 3+ The preparation method comprises the following steps:
1) Weighing gadolinium nitrate, ytterbium nitrate and thulium nitrate according to a stoichiometric ratio to enable the total amount of rare earth cations to reach 0.016mol, and preparing 800ml of aqueous solution with a proper amount of purified water, wherein the aqueous solution is marked as solution A;
2) Weighing 96g of urea, dissolving the urea in 320ml of purified water, marking as a solution B, and filtering the solution A and the solution B through filter paper to remove impurities in the solution;
3) The solution A is preheated to 60 ℃ through a water bath, then the solution B and a proper amount of purified water filtered by filter paper are poured into the solution A to prepare a mixed solution with the total volume of 1.6L, and the temperature of the mixed solution is raised to 82 ℃. When light blue turbidity is observed in the mixed solution, continuously curing for 30min;
4) And after the aging is finished, taking the beaker filled with the mixed solution out of the water bath, and placing the beaker in cold water for cooling. Subsequently, the solution was centrifuged (4500 rmp × 5 min), and the precipitate was washed with purified water three times and once with isopropanol, then dried at 40 ℃ for 12h to give a white powder, which was calcined at 600 ℃ for 1h to give white Yb 3+ 、Tm 3+ Co-doped Gd 2 O 3 A precursor;
5) Weighing the rare earth oxide precursor and (NH) according to the stoichiometric ratio 4 ) 6 Mo 7 O 24 ·4H 2 And O, then mixing them, pouring them into a mortar, sufficiently grinding and mixing them, and calcining the ground mixture at 700 ℃ for 2 hours to obtain the target sample 2.
Fig. 5 is an SEM picture of the target sample 2, and it can be seen from the figure that the average particle size of the prepared rare earth doped gadolinium molybdate is about 1.3 μm, and the particles are spherical-like and have good dispersibility.
FIG. 6 is an emission spectrum of the target sample 2 prepared in example 2 under excitation by a 980nm laser. It can be seen that the emission spectrum of target sample 2 at 980nm excitation exhibits blue light at 450-510nm, red light at 620-670nm and near infrared emission at 760-840nm, respectively.
Example 3
Gd 2 Mo 4 O 15 :x％Yb 3+ ,0.5％Tm 3+ The target samples 3 (a) to 3 (e) were obtained by changing the amount of ytterbium nitrate added and the other conditions and steps were the same as those of the preparation method of the target sample 2 in example 2, and the influence of different doping concentrations on the emission intensity was examined.
TABLE 1
FIG. 7 shows the emission spectra of different samples of example 3 under excitation by a 980nm laser. As can be seen from the figure, with Yb 3+ The luminous intensity of the sample is firstly enhanced and then weakened by increasing the ion concentration, and the luminous intensity reaches the maximum when the doping concentration is 40%.
Example 4
Gd 2 Mo 4 O 15 :40％Yb 3+ ,0.5％Er 3+ ,0.5％Tm 3+ The preparation method comprises the following steps:
1) Weighing gadolinium nitrate, ytterbium nitrate, erbium nitrate and thulium nitrate according to a stoichiometric ratio to enable the total amount of rare earth cations to reach 0.016mol, and preparing 800ml of aqueous solution with a proper amount of purified water, wherein the solution is marked as solution A;
2) Weighing 96g of urea, dissolving the urea in 320ml of purified water, marking as a solution B, and filtering the solution A and the solution B through filter paper to remove impurities in the solution;
3) Heating the solution A to 60 ℃ in advance through water bath, then pouring the solution B and a proper amount of purified water filtered by filter paper into the solution A to prepare a mixed solution with the total volume of 1.6L, heating the mixed solution to 82 ℃, and continuously curing for 30min when the mixed solution is observed to be light blue turbid;
4) And after the aging is finished, taking the beaker filled with the mixed solution out of the water bath, and placing the beaker in cold water for cooling. Subsequently, the solution was centrifuged (4500 rmp × 5 min), and the precipitate was washed with purified water three times and once with isopropanol, then dried at 40 ℃ for 12h to give a white powder, which was calcined at 600 ℃ for 1h to give white Yb 3+ 、Er 3+ 、Tm 3+ Co-doped Gd 2 O 3 A precursor;
5) Weighing the rare earth oxide precursor and (NH) according to the stoichiometric ratio 4 ) 6 Mo 7 O 24 ·4H 2 And O, then mixing them, pouring them into a mortar, sufficiently grinding and mixing them, and calcining the ground mixture at 700 ℃ for 2 hours to obtain a target sample 4.
FIG. 8 is an emission spectrum of the target sample 4 prepared in example 4 under excitation of a 980nm laser. As can be seen from the figure, the emission spectrum of the target sample 4 under 980nm excitation exhibits blue light at 450-510nm, green light at 515-575nm, red light at 620-670nm and near infrared emission at 760-840nm, respectively.
Example 5
Gd 2 Mo 4 O 15 :40％Yb 3+ ,y％Er 3+ ,0.5％Tm 3+ The target samples 5 (a) and 5 (b) were obtained by changing the amount of erbium nitrate added and the other conditions and steps were the same as those of the preparation of the target sample 4 in example 4, and the influence of different doping concentrations on the emission intensity was examined.
TABLE 2
| Sample (I) | Sample structural formula |
| Target sample 4 | Gd 2 Mo 4 O 15 :40％Yb 3+ ,0.5％Er 3+ ,0.5％Tm 3+ |
| Target sample 5 (a) | Gd 2 Mo 4 O 15 :40％Yb 3+ ,1.5％Er 3+ ,0.5％Tm 3+ |
| Target sample 5 (b) | Gd 2 Mo 4 O 15 :40％Yb 3+ ,3.0％Er 3+ ,0.5％Tm 3+ |
FIG. 9 shows the emission spectra of different samples of example 5 under excitation by a 980nm laser. As can be seen from the figure, with Er 3+ The emission of the sample shows a trend of gradually weakening blue, red and near infrared emission and gradually increasing green emission by increasing the ion concentration.
Claims (5)
1. A preparation method of a micro rare earth molybdate up-conversion luminescent material is characterized by comprising the following steps: by Ln 2 Mo 4 O 15 Is taken as a substrate, ln is one of Y, gd, la and Lu, yb is a sensitizing agent, and one or more of Er, tm and Ho are activating agents; the mol doping amount of the activator rare earth ions is 0.1-10%, and the mol doping amount of the sensitizer rare earth ions is 10-50%;
the preparation method of the luminescent material comprises the following steps:
weighing matrix rare earth nitrate, activator rare earth nitrate and sensitizer rare earth nitrate according to the doping proportion, and dissolving in water to form a solution A;
weighing urea, and dissolving the urea in water to form a solution B;
3) Pre-heating the solution A to 60-80 ℃ through a water bath, then pouring the solution B into the solution A to form a mixed solution C, heating the mixed solution C to 80-95 ℃, and continuing curing for 30-90min when the mixed solution is observed to be light blue turbid;
4) After the aging is finished, centrifugally separating out precipitate, washing with purified water for three times and washing with ethanol for one time, drying at 40 ℃ for 12 hours, and calcining the dried precipitate at 600-800 ℃ for 1 hour to obtain a rare earth oxide precursor;
5) According to the formula Ln of molybdate 2 Mo 4 O 15 Weighing rare earth oxide precursors and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 And O, pouring the mixture into a mortar, fully grinding and mixing, and calcining the ground mixture at 700-800 ℃ for 1-5h to obtain a target sample.
2. The method of claim 1, wherein: the luminescent material is in a sphere-like shape, and the particle size is less than or equal to 1.5 mu m.
3. The method of claim 1, wherein: the ratio of the sum of the mole numbers of the matrix rare earth nitrate, the activator rare earth nitrate and the sensitizer rare earth nitrate to the mole number of the urea is 1.
4. The method of claim 1, wherein: in the mixed solution C, the total concentration of rare earth cations is 0.001-1mol/L.
5. The method of claim 1, wherein: the matrix rare earth nitrate is one of yttrium nitrate, gadolinium nitrate, lanthanum nitrate and lutetium nitrate; the sensitizer rare earth nitrate is ytterbium nitrate; the activator rare earth nitrate is one or more of erbium nitrate, holmium nitrate and thulium nitrate.
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