CN102153576A - Rare earth complex coated with silicon dioxide and preparation method of rare earth complex - Google Patents
Rare earth complex coated with silicon dioxide and preparation method of rare earth complex Download PDFInfo
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- CN102153576A CN102153576A CN2011100322406A CN201110032240A CN102153576A CN 102153576 A CN102153576 A CN 102153576A CN 2011100322406 A CN2011100322406 A CN 2011100322406A CN 201110032240 A CN201110032240 A CN 201110032240A CN 102153576 A CN102153576 A CN 102153576A
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Abstract
The invention provides a rare earth complex coated with silicon dioxide and a preparation method of the rare earth complex, wherein the rare earth complex is a particle product formed by using the rare earth complex as a nuclear body and using the silicon dioxide generated after a silicon dioxide precursor is hydrolyzed as a surface coating object. A fluorescence test shows that the fluorescence intensity of the coated rare earth complex is obviously strengthened. Meanwhile, the obtained rare earth complex has the characteristic that the rare earth complex coated with the silicon dioxide is insoluble in an organic solvent. By adopting the method, the cost of rare earth can be reduced to the great extent.
Description
Technical field
The invention provides a kind of rare earth compounding of coated with silica, be with rare earth compounding as nucleome, with the silicon-dioxide that generates after the silica precursor hydrolysis as the formed saccharoid of surperficial coating, with and preparation method thereof.Fluorometric investigation shows that the fluorescence intensity of the rare earth compounding after the coating has obtained enhancing.Resulting rare earth compounding has the characteristics that are insoluble to organic solvent simultaneously.
Background technology
China has abundant rare earth resources, and the new function material that rare earth resources is carried out deep processing production high added value has important scientific value and realistic meaning.Rare earth compounding has unique advantage as luminescent material, and for example internal quantum efficiency is very high, about emission peak halfwidth 10nm, have very high color purity.Rare earth compounding has special application at aspects such as false proof, fluorescent probe, luminous demonstrations.
The fluorescence property that improves rare earth compounding comprises that fluorescence intensity and stability have very important significance for its practical application.Main method is the kind and the structure of the part of improvement and rare-earth ion coordination at present.The scientific research personnel of some rare earth aspects has studied inorganic and the organic rare-earth ligand hybrid luminescent materials.Rare earth compounding is incorporated in the inorganic network structure, have advantage organic, inorganic materials concurrently in the hope of the luminescent material that obtains, the work of this respect is for example referring to Hench L L, West J K.The sol-gel process.Chem.Rev., 1990,90 (1): 33-72; Xu Q H, Fu L S, Li L S, et al.J.Mater.Chem., 2000,10 (11), 2532-2536; Bekiari V, Lianos P.Adv.Mater., 1998,10 (17): 1455-1458; Carlos L D, Sa Ferreira R A, Rainho J P, et al.Adv.Func.Mater., 2002,12:819-823; Embert F, Mehdi A, Reye C, et al.Chem.Mater., 2001,13:4542-4549; Dong D W, Jiang S C, Men Y F, et al.Adv.Mater., 2000,12 (9): 646-649; Henandez R, Franville A C, Minoofar P, et al.J.Am.Chem.Soc., 2001,123:1248-1249; Minoofar P N, Hemandez R, Chia S, et al.J.Am.Chem.Soc., 2002,124:14388-14396.
Following document also relates to the matrix material of rare earth compounding and many achievements of electroluminescent aspect thereof: Zhao Ying, Yang Li-min, Zhang Li, et al. (Zhao Ying, Yang Limin, Zhang Li etc.), Acta Polymerica Sinica (polymer journal), 2000,4:393-396; Guo Dong, Liang Chun-jun, Lin Peng, et al. (Guo Dong, Liang Chunjun, Lin Peng etc.), Journal of The Chinese Rare Earth Society (Chinese rare-earth journal), 2004,22 (6): 879-882; Zhang Li, Yang Zhan-lan, Sun Ying, et al. (Zhang Li, Yang Zhanlan, Sun Ying etc.), Spectroscopy and Spectral Analysis (spectroscopy and spectroscopic analysis), 2000,20 (5): 661-662; Tao Dong-liang, Zhang Ting, Xu Yi-zhuang, et al. (Tao Dongliang, Zhang Ting, Xu Yizhuan etc.), Journal of The Chinese Rare Earth Society (Chinese rare-earth journal), 2001,19 (6): 543-547; Tao D L, Xu Y Z, ZhouF S, et al.Thin Solid Films, 2003,436:281-285; Tao D L, Xu Y Z, Feng J, et al.Journal of Materials Chemistry, 2004,14:1252-1256; Pan Y F, Zheng A N, Hu FZ, et al.Journal of Applied Polymer Science, 2006,100:1506-1510.
Though rare earth compounding has many advantages, comprise purity of color and resolvability etc., as inorganic organic coordination bonded hybrid material, aspect fluorescence stable, be weaker than the inorganic rare earth luminescent material always.In order to solve this difficult problem, Zhao Ying etc. are (referring to Acta Polymerica Sinica (polymer journal), 2000,4:393-396) disclose a kind of method that adopts polyphosphazene polymer methyl methacrylate compound rare-earth title complex, and studied the luminescent properties of prepared material.This method has been improved the stability of rare earth compounding to a certain extent.(Journal of Applied Polymer Science such as Pan Yuanfeng, 2006,100:1506-1510) adopt the reaction of high polymer monomer vinylformic acid and rare earth ion to form rare earth compounding, and then prepared novel macromolecule rare-earth complexe, thereby realized rare earth compounding is introduced in the macromolecular chain with styrene copolymerized.But this method need be selected suitable part, because Acrylic Acid Monomer has determined its space structure must select suitable part could form title complex.In general, the part that molecular weight ratio is bigger is difficult to form jointly with it rare earth compounding, and this has just influenced the fluorescence property of final rare earth compounding to a certain extent.
Therefore, demand the rare earth compounding that need provide a kind of novel structure, excellent performance and preparation method thereof urgently.
Summary of the invention
Therefore, one of purpose of the present invention is to provide a kind of rare earth compounding of coated with silica; Another purpose of the present invention is to provide a kind of method for preparing the rare earth compounding of this coated with silica.
The inventor is through discovering with keen determination, if with rare earth compounding with fluorescence property as nuclear, as surperficial coating, just can self-assembly form a kind of rare earth compounding of coated with silica with the silicon-dioxide that generates after the silica precursor hydrolysis.Rare earth compounding before not coating is dissolved in organic solvent, and the rare earth compounding that makes according to the present invention is insoluble to organic solvent, and this shows that surface coated effect is very remarkable; The fluorometric investigation result shows that the fluorescence intensity of the rare earth compounding after the coating obviously strengthens.Thereby finished the present invention.
The following specifically describes the present invention.
In one embodiment of the invention, a kind of rare earth compounding of coated with silica is provided, be as nucleome with rare earth compounding, with the silicon-dioxide that generates after the silica precursor hydrolysis as the formed saccharoid of surperficial coating, described rare earth compounding be can emitting fluorescence rare earth compounding, the multicomponent complex that preferred europium, terbium, dysprosium and organic molecule as part form, described silica precursor is the silica-base material that can generate silicon-dioxide by hydrolysis.
In another embodiment, described rare earth compounding is Eu (TTA)
3Phen, Tb (aspirin)
3Phen, Dy (TTA)
3Phen, preferred Eu (TTA)
3Phen, wherein phen is adjacent luxuriant and rich with fragrance sound of vomiting quinoline, and TTA is a 2-thiophene trifluoromethyl methyl ethyl diketone, and aspirin is an acetylsalicylic acid.Described silica precursor is tetraethoxy (TEOS).These rare earth compoundings are known, and its preparation method and structural characterization all have related in lot of documents, as the document of mentioning in the background technology.The present invention can directly use these rare earth compoundings, also can at first prepare them according to the method for describing in these documents, and then it is coated.
In another embodiment, the rare earth compounding of described coated with silica is SiO
2/ Eu (TTA)
3Phen, it has sharp-pointed emission peak at 617.4nm.
The rare earth compounding of the coated with silica of mentioning in the above embodiment is to make by being prepared as follows the method described in the embodiment.
In a preparation of the present invention embodiment, a kind of method for preparing the rare earth compounding of coated with silica is provided, be as the nucleome material with rare earth compounding, it is scattered in the organic solvent, the silicon-dioxide that silica precursor generates after hydrolysis forms the surperficial coating of nucleome material, thereby form the rare earth compounding of granulous coated with silica, the rare earth compounding that is adopted be can emitting fluorescence rare earth compounding, preferred europium, terbium, dysprosium and the multicomponent complex that forms as the organic molecule of part, the silica precursor that is adopted is for generating the silica-base material of silicon-dioxide by hydrolysis.
In another preparation embodiment, the rare earth compounding that is adopted is Eu (TTA)
3Phen, Te (aspirin)
3Phen, Dy (TTA)
3Phen, preferred Eu (TTA)
3Phen.The silica precursor that is adopted is tetraethoxy (TEOS).
In another preparation embodiment, described organic solvent be for disperseing any solvent of rare earth compounding, for example alcohols, ketone and halogenated alkane etc., preferred alcohols kind solvent, for example methyl alcohol, ethanol or Virahol.
In another preparation embodiment, the rare earth compounding of formed coated with silica is SiO
2/ Eu (TTA)
3Phen, it has sharp-pointed emission peak at 617.4nm.
In another preparation embodiment, rare earth compounding and silica precursor are scattered in organic solvent such as methyl alcohol, ethanol or the Virahol, dispersion liquid is carried out supersound process, stir then.Ammoniacal liquor, deionized water and methyl alcohol, ethanol or isopropanol mixture are added in the dispersion liquid, continue to stir the back separated product also with organic solvent such as methyl alcohol, ethanol or washed with isopropyl alcohol.Product obtains the finished product after drying.
In another preparation embodiment, with Eu (TTA)
3Phen and TEOS are scattered in the Virahol.Dispersion liquid is carried out ultrasonic, stir then, ammoniacal liquor (28%), deionized water and isopropanol mixture are added in the dispersion liquid, continue to stir the back separated product and also use washed with isopropyl alcohol.Product is at 70-100 ℃, and drying obtains the finished product under the preferred 80-90 ℃ of temperature.
The present invention discovers that rare earth compounding is through after the coated with silica, and its chemical constitution and structure do not change.Yet wide variation have but taken place in its fluorescence intensity, for example, and Eu (TTA)
3Phen is through after the coated with silica, and the intensity of fluorescence emission peak has improved more than 2 times, sharp-pointed emission peak occurred at 617.4nm simultaneously.Though be not bound by any theory, but these results can be interpreted as: after coated with silica, rare earth compounding is fettered to a certain extent, make between its molecule compact more and the rigidization more that becomes, the molecular heat vibration weakening, because the energy that thermal vibration is lost reduces, thereby has strengthened its fluorescence intensity.
The rare earth compounding of coated with silica of the present invention or this cladded type rare earth compounding prepared according to the methods of the invention are a kind of novel rare-earth luminescent materials, the advantage that performance makes new advances, for uncoated existing rare earth compounding, its solvent resistance improves, and cost performance is able to obvious raising.
As a kind of new type functional rare earth compounding, this cladded type rare earth compounding of the present invention has the characteristics of inorganic-organic hybrid material, not only can save rare earth resources, and improved the stability of rare earth compounding, not only there is being important use to be worth aspect anti-counterfeiting mark, the fluorescent probe, and can be used on the electroluminescent device.The granular size of the rare earth compounding by controlling this coated with silica, as the luminescent layer of electroluminescent device, then the stability of device can improve then.
Therefore, coated with silica rare earth compounding of the present invention has not only solved the problem of rare earth compounding stability itself, and the novel fluorescence that has also prepared a kind of high added value simultaneously first strengthens rare earth luminescent material.
Description of drawings
Fig. 1 is rare earth compounding Eu (TTA)
3The rare earth compounding SiO of phen and coated with silica
2/ Eu (TTA)
3The emmission spectrum figure of phen, excitation wavelength is 383nm; Wherein, dotted line is represented the spectrogram of rare earth compounding, and solid line is represented the spectrogram of the rare earth compounding of coated with silica;
Fig. 2 is rare earth compounding Eu (TTA)
3The rare earth compounding SiO of phen and coated with silica
2/ Eu (TTA)
3The exciting light spectrogram of phen, the detection wavelength is 611nm; Wherein, dotted line is represented the spectrogram of rare earth compounding, and solid line is represented the spectrogram of the rare earth compounding of coated with silica;
Fig. 3 is rare earth compounding Eu (TTA)
3The fluorescence decay curve of phen, wherein, level and smooth relatively curve is the match extinction curve among the last figure, the curve of another indentation is the actual attenuation curve; In figure below, the jagged curve of the curve that is is a residual error;
Fig. 4 is the rare earth compounding SiO of coated with silica
2/ Eu (TTA)
3The fluorescence decay curve of phen, wherein, level and smooth relatively curve is the match extinction curve among the last figure, the curve of another indentation is the actual attenuation curve; In figure below, the jagged curve of the curve that is is a residual error;
Fig. 5 is the rare earth compounding SiO of coated with silica
2/ Eu (TTA)
3The electromicroscopic photograph of phen, as seen its pattern is a saccharoid.
Embodiment
Below with preferred embodiment and further specify the present invention in conjunction with the accompanying drawings.Characteristics of the present invention and advantage will become more clear along with these explanations.But, these embodiments only are illustrative, and it is to protection scope of the present invention and do not constitute any limitation.It will be appreciated by those skilled in the art that under the situation that does not exceed or depart from protection domain of the present invention, technical solutions and their implementation methods of the present invention have multiple modification, improvement or Equivalent, these all should fall within the scope of protection of the present invention.
Below with rare earth compounding Eu (TTA)
3Phen is an example, and (TEOS) is silica precursor with tetraethoxy, the rare earth compounding SiO of preparation coated with silica after hydrolysis
2/ Eu (TTA)
3Phen.
Obviously it will be understood by those skilled in the art that with rare earth compounding Eu (TTA)
3Phen is other rare earth compoundings such as Tb (aspirin) similarly
3Phen and Dy (TTA)
3Phen etc., the rare earth compounding that can make corresponding coated with silica by the mode described in following examples and method equally, the rare earth compounding SiO of its SPECTROSCOPIC CHARACTERIZATION and coated with silica
2/ Eu (TTA)
3Phen is also similar, repeats no more in the literary composition.
Embodiment 1
Rare earth compounding Eu (TTA)
3The preparation of phen
With Eu
2O
3(purity 99.99%) is dissolved in the dilute hydrochloric acid, slowly evaporates postcooling, separates out white crystals EuCl
36H
2O puts into the moisture eliminator drying for standby after the filtration.EuCl with 1mmol
3.6H
22 of O and 3mmol.Thiophene trifluoroacetylacetone (TTA) is dissolved in the 20mL dehydrated alcohol.Then, the triethylamine (0.42mL) that adds 3mmol.Add the adjacent luxuriant and rich with fragrance sound of vomiting quinoline (phen) of 1mmol at last, the adularescent precipitation generates, stir will precipitate suction filtration behind the 0.5h and come out, with behind the absolute ethanol washing several once more suction filtration come out, put into the moisture eliminator drying for standby.
2 minor element analytical resultss of sample are as shown in table 1, with Eu (TTA)
3The theoretical value that phen calculates meets; Its excitation wavelength be under the 383nm emmission spectrum figure as shown in Figure 1, detect wavelength be under the 611nm the exciting light spectrogram as shown in Figure 2, with the Eu (TTA) of bibliographical information
3The spectrogram of phen coincide.
Table 1: the results of elemental analyses of rare earth compounding
| Sample | C | H | N |
| Eu(TTA) 3phen | 43.58％ | 2.29％ | 3.02％ |
| Eu(TTA) 3phen | 43.56％ | 2.27％ | 2.98％ |
Embodiment 2
Coated with silica rare earth compounding SiO
2/ Eu (TTA)
3The preparation of phen
Eu (TTA) with 0.2g
3The TEOS of phen and 2mL is scattered in the Virahol of 20mL.Solution is put into ultrasonic apparatus carry out supersound process 1h, then, solution transferred to carry out electronic stirring in the flask, stir speed (S.S.) remains on 3000n/min.In the disposable adding flask of isopropanol mixture with ammoniacal liquor (28%), 1mL deionized water and the 5mL of 1mL, continue to stir behind the 20h centrifugation product and for several times with washed with isopropyl alcohol.Product dry 12h under 80 ℃ of temperature obtains the finished product.
The quality of weighing the finished product is 0.3g.This explanation have about 0.1g be since coated with silica at Eu (TTA)
3The result on phen surface.
2 minor element analytical resultss of these the finished product are as shown in table 2, and its C, H, N constituent content are than Eu (TTA)
3Respective value among the phen decreases.
The finished product excitation wavelength be under the 383nm emmission spectrum figure as shown in Figure 1, SiO
2/ Eu (TTA)
3Phen tangible spike occurred at 617.4nm.Detect wavelength be under the 611nm the exciting light spectrogram as shown in Figure 2.
Table 2: the results of elemental analyses of coated with silica rare earth compounding
| Sample | C | H | N |
| SiO 2-Eu(TTA) 3phen | 37.91％ | 2.05％ | 2.42％ |
| SiO 2-Eu(TTA) 3phen | 37.79％ | 2.04％ | 2.39％ |
Test implementation example 3
SiO
2/ Eu (TTA)
3The fluorescence spectrometry of phen
Fluorescence spectrum is measured on the F-4500 spectrophotofluorometer.Exciting slit and emission slit all is 1nm.In order to compare fluorescence intensity, sample section is at one time measured its fluorescence spectrum.
Fig. 1 is rare earth compounding Eu (TTA)
3Phen and coated with silica rare earth compounding SiO
2/ Eu (TTA)
3The emmission spectrum figure of phen, excitation wavelength is 383nm.The two is all very sharp-pointed at the main emission peak of 611.6nm as we can see from the figure, and emission peak positions is without any variation.This explanation coated with silica does not exert an influence to the energy level of rare earth ion.But, SiO
2/ Eu (TTA)
3Phen tangible spike but occurred at 617.4nm, and Eu (TTA)
3Phen can't see tangible peak shape in this position, can only tell the peak by fitting of a curve.
According to rare earth Eu
3+Level scheme, the emission peak of rare earth Eu title complex should have seven emission peaks, at SiO
2/ Eu (TTA)
3All can be clear that in the emmission spectrum of phen, be positioned at 579.6nm, 590.2nm, 596.6nm, 611.6nm, 625.2nm, 617.4nm and 652.0nm, corresponding Eu respectively
3+Energy level transition be
5D
0-
7F
0,
5D
0-
7F
1,
5D
0-
7F
2,
5D
0-
7F
3,
5D
0-
7F
4,
5D
0-
7F
5And
5D
0-
7F
6It should be noted that most that the intensity of fluorescence emission peak has obtained increasing substantially, and has improved more than 2 times through after the coated with silica.
Fig. 2 is Eu (TTA)
3Phen and SiO
2/ Eu (TTA)
3The exciting light spectrogram of phen, the detection wavelength is 611nm.As can be seen from the figure the excitation spectrum peak shape of the two is similar, and this shows that coated with silica is to Eu (TTA)
3The molecular composition of phen is influence not, because the excitation spectrum of rare earth compounding and molecular composition have close getting in touch.Silicon-dioxide only is the surface that physical package overlays on rare earth compounding, and chemical reaction does not take place with it.
Can see that rare earth compounding is through after the coated with silica, its chemical constitution and structure do not change.Yet wide variation have but taken place in its fluorescence intensity, sharp-pointed emission peak occurred at 617.4nm simultaneously.These results show, after the coated with silica, and Eu (TTA)
3The compact more and rigidization more that becomes between the phen molecule, molecular heat vibration weakening, the energy that is lost reduce, thereby have strengthened its fluorescence intensity.
Test implementation example 4
Eu (TTA)
3Phen and SiO
2/ Eu (TTA)
3The mensuration of the fluorescence decay curve of phen
What the mensuration of time lifetime was used is the stable state transient time to differentiate fluorescence spectrophotometer (Britain Edinburgh Instruments Ltd.).Used medicine all is an analytical reagent.
Fig. 3 and Fig. 4 are Eu (TTA)
3Phen and SiO
2/ Eu (TTA)
3The fluorescence decay curve of phen.By the single index match as can be seen, Eu (TTA)
3The fluorescence lifetime of phen is 810.65 microseconds, and SiO
2/ Eu (TTA)
3The fluorescence lifetime of phen is 764.71 microseconds.
Presentation of results, after the coated with silica, the fluorescence lifetime of rare earth compounding has shortened, and this result has shown that also the fluorescence intensity of rare earth compounding is not to be directly proportional with its fluorescence lifetime.Fluorescence lifetime is represented particle in the mean time that excited state exists, and fluorescence intensity gives the number of photons of being launched behind the rare earth ion relevant with part absorption transmission ofenergy.Behind the coated with silica rare earth compounding, make Eu (TTA)
3The phen molecular structure is rigidization more, and part will transmit energy to rare earth ion with faster rate after absorbing energy, has strengthened fluorescence intensity then, has also reduced fluorescence lifetime simultaneously.
Abovely describe the present invention in conjunction with specific embodiments.But, these embodiments only are illustrative, and it is to protection scope of the present invention and do not constitute any limitation.It will be appreciated by those skilled in the art that under the situation that does not exceed or depart from protection domain of the present invention, technical solutions and their implementation methods of the present invention have multiple modification, improvement or Equivalent, these all should fall within the scope of protection of the present invention.
Claims (10)
1. the rare earth compounding of a coated with silica, be as nucleome with rare earth compounding, with the silicon-dioxide that generates after the silica precursor hydrolysis as the formed saccharoid of surperficial coating, described rare earth compounding be can emitting fluorescence rare earth compounding, the multicomponent complex that preferred europium, terbium, dysprosium and organic molecule as part form, described silica precursor is the silica-base material that can generate silicon-dioxide by hydrolysis.
2. the rare earth compounding of coated with silica according to claim 1 is characterized in that, described rare earth compounding is Eu (TTA)
3Phen, Tb (aspirin)
3Phen, Dy (TTA)
3Phen, preferred Eu (TTA)
3Phen, phen are adjacent luxuriant and rich with fragrance sound of vomiting quinolines, and TTA is a 2-thiophene trifluoromethyl methyl ethyl diketone, and aspirin is an acetylsalicylic acid, and described silica precursor is tetraethoxy (TEOS).
3. the rare earth compounding of coated with silica according to claim 1 and 2 is characterized in that, the rare earth compounding of described coated with silica is SiO
2/ Eu (TTA)
3Phen, it has sharp-pointed emission peak at 617.4nm.
4. method for preparing the rare earth compounding of coated with silica, be as the nucleome material with rare earth compounding, it is scattered in the organic solvent, the silicon-dioxide that silica precursor generates after hydrolysis forms the surperficial coating of nucleome material, thereby form the rare earth compounding of granulous coated with silica, the rare earth compounding that is adopted be can emitting fluorescence rare earth compounding, the multicomponent complex that preferred europium, terbium, dysprosium and organic molecule as part form, the silica precursor that is adopted is the silica-base material that can generate silicon-dioxide by hydrolysis.
5. according to the method for claim 4, it is characterized in that the rare earth compounding that is adopted is Eu (TTA)
3Phen, Te (aspirin)
3Phen, Dy (TTA)
3Phen, preferred Eu (TTA)
3Phen, phen are adjacent luxuriant and rich with fragrance sound of vomiting quinolines, and TTA is a 2-thiophene trifluoromethyl methyl ethyl diketone, and aspirin is an acetylsalicylic acid, and the silica precursor that is adopted is tetraethoxy (TEOS).
6. according to claim 4 or 5 described methods, it is characterized in that described organic solvent be for disperseing the solvent of rare earth compounding, for example alcohols, ketone and halogenated alkane etc., preferred alcohols kind solvent, for example methyl alcohol, ethanol or Virahol.
7. according to the method for one of claim 4 to 6, it is characterized in that the rare earth compounding of formed coated with silica is SiO
2/ Eu (TTA) 3phen, it has sharp-pointed emission peak at 617.4nm.
8. according to the method for one of claim 4 to 7, it is characterized in that, rare earth compounding and silica precursor are scattered in organic solvent such as methyl alcohol, ethanol or the Virahol, dispersion liquid is carried out supersound process, stir then, the mixture of ammoniacal liquor, deionized water and methyl alcohol, ethanol or Virahol is added in the dispersion liquid, continue to stir the back separated product also with organic solvent such as methyl alcohol, ethanol or washed with isopropyl alcohol, product obtains the finished product after drying.
9. according to the method for one of claim 4 to 8, it is characterized in that, Eu (TTA)
3Phen and TEO S are scattered in the Virahol, carry out dispersion liquid ultrasonic, stir then, ammoniacal liquor (28%), deionized water and isopropanol mixture are added in the dispersion liquid, continue to stir the back separated product and use washed with isopropyl alcohol, product is at 70-100 ℃, and drying obtains the finished product under preferred 80 ℃ of-90 ℃ of temperature.
10. according to the rare earth compounding of the described coated with silica of one of claim 1 to 3, it is characterized in that it is to be made by the method according to one of claim 4 to 9.
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