CN114074951B - Method for preparing rare earth fluoride by using fluorinated ionic liquid - Google Patents
Method for preparing rare earth fluoride by using fluorinated ionic liquid Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
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- C01F17/265—Fluorides
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention discloses a method for preparing rare earth fluoride by using fluorinated ionic liquid. Rare earth fluoride in the chemical formula REF 3 And (c) represents at least one element selected from La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, Y and Sc. The ionic fluoride liquid and the rare earth oxide are used as raw materials, the rare earth oxide is directly converted into the rare earth fluoride by a solvothermal method, and the reaction can be carried out under the condition of relatively low temperature, so that certain dangers caused by fluorine gas generated at high temperature are avoided; meanwhile, the preparation method of the rare earth fluoride provided by the invention has mild reaction conditions, and the rare earth fluoride can be obtained without adding any surfactant, catalyst or template, so that the purity and yield of the rare earth fluoride are greatly improved. The rare earth fluoride prepared by the invention has the oxygen content lower than 100ppm, and can be widely used for preparing rare earth fluoride monocrystal, low-oxygen metal gadolinium and fluorescent matrix materials.
Description
Technical Field
The invention belongs to the field of rare earth fluoride powder materials with special physical properties and preparation thereof, and particularly relates to a method for preparing rare earth fluoride by using fluorinated ionic liquid.
Background
The rare earth compound has a unique 4f electronic layer structure, and the electronic, optical and chemical characteristics generated by electronic transition in the shell can provide a proper and effective crystal field for the central luminescent ion and promote the excitation and luminescence of the central luminescent ion, so that the rare earth compound is widely applied to the fields of optics, photoelectrons, diagnosis, biological markers, catalysis and the like. Rare earth fluorides (i.e., rare earth fluorides) have lower vibrational energy, wide band gap, high refractive index, and minimal quenching of the excited states of the rare earth ions than oxygen-based systems, making fluorinated rare earth-based luminescent materials the most promising photoinduced nonlinear optical host materials.
The above characteristics of rare earth fluoride can not only enhance the radiation relaxation rate of the material but also prolong the metastable energy level life of rare earth luminescent ions, thereby greatly improving the luminous efficiency. Therefore, in rare earth luminescent materials, the photon yield is much higher when fluoride is used as luminescent matrix than the prior luminescent matrix with most oxides and inorganic substances. In addition, compared with the traditional biological probe, the rare earth fluoride nanocrystalline has the advantages of good biocompatibility, strong tissue penetration depth, low biological toxicity, extremely strong chemical property stability, easy grafting and the like in the fields of biological imaging, pathological detection, tumor treatment and the like.
The existing methods for preparing the rare earth fluoride mainly comprise three methods: hydrothermal (solvothermal) method, thermal decomposition method and high-temperature coprecipitation method. The three methods are mature, but the current research shows that most of the preparation of the rare earth fluoride needs to be carried out under the condition of higher temperature, fluorine gas is easy to generate under the condition of high temperature, a certain danger exists, and meanwhile, the methods are relatively complex, consume energy and are also unfavorable for the environment. Therefore, developing a simple, green, general method for preparing rare earth fluoride without adding any surfactant, catalyst or template under mild conditions becomes a technical problem to be solved.
Ionic Liquids (ILs) have good stability, extremely low vapor pressure and difficult volatility and are considered to be very safe solvents. The room temperature molten salts have proved that they have potential application values in metal extraction, crystal engineering, dissolution of metal oxides and the like. For example, the addition of nitric acid or an HF-based ionic liquid in the presence of ILs having complexing chemistry (e.g., -COOH) can promote dissolution of uranium oxide. ILs, on the other hand, may also be used as a source of fluorine and as a solvent for precipitating fluoride. Therefore, the ionic liquid is used as a novel environment-friendly reaction medium and has been successfully applied to the preparation of inorganic materials. The ionic liquid is used as a solvent or a template for preparing the nano-structure material, so that the synthesis of the inorganic material with new morphology or improvement is possible.
Disclosure of Invention
In order to improve the technical problems, the invention provides a preparation method of rare earth fluoride, which comprises the following steps: carrying out solvothermal reaction on the rare earth oxide and the fluorinated ionic liquid to prepare rare earth fluoride;
the rare earth fluoride is represented by formula REF 3 A representation; wherein RE represents a rare earth element selected from at least one of La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, Y and Sc; preferably at least one selected from La, ce, pr, nd and Sm.
According to an embodiment of the invention, the rare earth oxide is selected from the oxides of the above rare earth elements RE, for example from Nd 2 O 3 、La 2 O 3 、Ce 2 O 3 At least one of them.
According to an embodiment of the present invention, the fluorinated ionic liquid may be selected from [ Bmim ]][PF 6 ](1-butyl-3-methylimidazole hexafluorophosphate) and [ Bmim][BF 4 ]At least one of (1-butyl-3-methylimidazole tetrafluoroborate); preferably [ Bmim ]][PF 6 ]。
According to an embodiment of the invention, the fluorinated ionic liquid to rare earth oxide molar mass ratio (mL/mmol) is 1 (0.04-0.5), for example 1 (0.05-0.4), exemplified by 1:0.09, 1:0.12, 1:0.19, 1:0.2, 1:0.3.
According to an embodiment of the invention, the solvothermal reaction is carried out in a temperature and pressure resistant vessel, for example a polytetrafluoroethylene liner. Preferably, the mixture of fluorinated ionic liquid and rare earth oxide has a filling degree in the polytetrafluoroethylene lining of 30-50%, for example 35-45%.
According to an embodiment of the invention, the solvothermal reaction has a temperature of 150-200 ℃, for example 160-180 ℃, exemplary 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃.
According to an embodiment of the invention, the solvothermal reaction time is 24-96h, for example 36-72h, exemplary 24h, 36h, 48h, 60h, 72h, 84h, 96h.
According to the embodiment of the invention, the preparation method further comprises the process of carrying out solid-liquid separation on the reaction system after the reaction is finished to obtain a reaction product. For example, the solid-liquid separation may employ means known in the art, such as centrifugation. Preferably, the rotational speed of the centrifugation is 6000-10000rpm, for example 7000-9000rpm, exemplary 6000rpm, 7000rpm, 8000rpm, 9000rpm, 10000rpm. Further, the centrifugation time is 3-10min, such as 5-8min, and exemplary is 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min.
According to an embodiment of the present invention, the preparation method further comprises washing the reaction product obtained by the solid-liquid separation. For example, the reaction product is washed with a solvent capable of dissolving the fluorinated ionic liquid. Preferably, the solvent may be absolute ethanol. As another example, the number of times of washing may be one, two or more times, preferably three times.
According to an embodiment of the invention, the preparation method further comprises drying the washed reaction product. For example, the drying temperature is 60 to 90 ℃, preferably 70 to 80 ℃, and exemplary 60 ℃, 70 ℃, 80 ℃, 90 ℃. Further, the drying time is 12 to 24 hours, preferably 15 to 20 hours, and exemplified by 12 hours, 15 hours, 18 hours, 20 hours, 21 hours, 24 hours.
According to an embodiment of the invention, the preparation method comprises the steps of:
placing rare earth oxide and fluorinated ionic liquid in a temperature-resistant pressure-resistant reaction vessel, and performing solvothermal reaction; after the reaction is completed, carrying out solid-liquid separation, and washing and drying the obtained reaction product to obtain the rare earth fluoride.
The invention also provides rare earth fluoride prepared by the preparation method, which is shown as a chemical formula REF 3 A representation; wherein RE represents a rare earth element selected from at least one of La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, Y and Sc; preferably at least one selected from La, ce, pr, nd and Sm.
According to an embodiment of the invention, the oxygen content of the rare earth fluoride is lower than 100ppm, for example lower than 95ppm, exemplary 80ppm, 85ppm, 89ppm, 90ppm, 95ppm.
The invention has the beneficial effects that:
(1) The invention takes fluorinated ionic liquid and rare earth oxide as raw materials, and realizes the process of preparing solid rare earth fluoride from solid rare earth oxide under the high-temperature and high-pressure environment created by ionic liquid without dissolving solid rare earth oxide through solvothermal reaction. The method can be used for reaction at relatively low temperature, and avoids certain dangers caused by fluorine gas generated at high temperature.
(2) The preparation method of the rare earth fluoride provided by the invention has mild reaction conditions, and the rare earth fluoride can be obtained without adding any surfactant, catalyst or template, so that the purity of the rare earth fluoride is greatly improved.
(3) The oxygen content of the rare earth fluoride prepared by the method is lower than 100ppm, and the rare earth fluoride single crystal, low-oxygen metal gadolinium, fluorescent matrix materials and the like are prepared by the method.
Drawings
FIG. 1 is a process flow diagram of the solvothermal method of the invention for preparing rare earth fluoride.
FIG. 2 shows NdF synthesized in example 1 of the present invention 3 Is a XRD pattern of (C).
FIG. 3 shows the LaF synthesized in example 2 of the present invention 3 Is a XRD pattern of (C).
FIG. 4 shows a CeF synthesized in example 3 of the present invention 3 Is a XRD pattern of (C).
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Referring to FIG. 1, fluorinated ionic liquids [ Bmim ] are utilized][PF 6 ]Direct preparation of rare earth fluoride NdF 3 Comprises the following steps:
(1) Weigh 1.12mmol Nd 2 O 3 Solid powder and 6mL fluorinated ionic liquid [ Bmim][PF 6 ]Placing the polytetrafluoroethylene lining in a stainless steel reaction kettle after placing the polytetrafluoroethylene lining in 20mL of polytetrafluoroethylene lining;
(2) Putting a stainless steel reaction kettle into an oven for solvothermal reaction, controlling the reaction temperature to be 180 ℃ and the reaction time to be 48 hours, and utilizing the ion heat of the ionic liquid to carry out solid Nd 2 O 3 Conversion to solid NdF at high temperature and high pressure 3 The method comprises the steps of carrying out a first treatment on the surface of the After the reaction is finished, taking out the reaction product, centrifuging, controlling the centrifugal speed to 8000rpm, and centrifuging for 5min to realize solid-liquid separation;
(3) Washing the precipitate with absolute ethyl alcohol for three times, and removing residual ionic liquid;
(4) Drying the precipitate at 80deg.C for 12 hr to obtain NdF 3 And (3) powder.
NdF prepared in this example 3 The XRD pattern of the powder is shown in figure 2, and the XRD pattern of the product is shown as NdF 3 The characteristic peaks of the (PDF # 78-1859) standard card are consistent, indicating that the product prepared by this method is NdF 3 And (3) powder. Meanwhile, the oxygen content in the rare earth fluoride is calculated by adopting an elemental analyzer (Elementar Vari EL Cube), and the oxygen content of the rare earth fluoride is 89ppm, thereby indicating Nd 2 O 3 To NdF 3 The conversion rate of (C) is higher, and NdF with high purity can be prepared by the method of the embodiment 3 。
Example 2
By means of fluorinated ionic liquids [ Bmim][PF 6 ]Direct preparation of rare earth fluoride LaF 3 Comprises the following steps:
(1) Weigh 0.56mmol La 2 O 3 Solid powder and 6mL fluorinated ionic liquid [ Bmim][PF 6 ]Placing the polytetrafluoroethylene lining in a stainless steel reaction kettle after placing the polytetrafluoroethylene lining in 20mL of polytetrafluoroethylene lining;
(2) Putting the stainless steel reaction kettle into a baking oven for solvothermal reaction, controlling the reaction temperature to 160 ℃ and the reaction time to 96hIon heating of ionic liquid to obtain solid La 2 O 3 Conversion to solid LaF at high temperature and high pressure 3 The method comprises the steps of carrying out a first treatment on the surface of the After the reaction is finished, taking out the reaction product, centrifuging, controlling the centrifugal speed to 6000rpm, and centrifuging for 10min to realize solid-liquid separation;
(3) Washing the precipitate with absolute ethyl alcohol for three times, and removing residual ionic liquid;
(4) Drying the precipitate at 80deg.C for 18 hr to obtain LaF 3 And (3) powder.
LaF prepared in this example 3 The XRD pattern of the powder is shown in figure 3, and the XRD curve of the product is shown as LaF 3 The characteristic peaks of the (PDF#76-0510) standard card are consistent, which shows that the product prepared by the method is LaF 3 And (3) powder. Meanwhile, the oxygen content in the rare earth fluoride is calculated by adopting an elemental analyzer (Elementar Vari EL Cube) to obtain that the oxygen content of the rare earth fluoride is 80ppm, thereby indicating La 2 O 3 To LaF 3 The conversion rate of (C) is higher, and NdF with high purity can be prepared by the method of the embodiment 3 。
Example 3
By means of fluorinated ionic liquids [ Bmim][PF 6 ]Direct preparation of rare earth fluoride CeF 3 Comprises the following steps:
(1) Weigh 1.12mmol Ce 2 O 3 Solid powder and 9mL fluorinated ionic liquid [ Bmim][PF 6 ]Placing the polytetrafluoroethylene lining in a stainless steel reaction kettle after placing the polytetrafluoroethylene lining in 20mL of polytetrafluoroethylene lining;
(2) Putting a stainless steel reaction kettle into an oven for solvothermal reaction, controlling the reaction temperature to be 200 ℃ and the reaction time to be 24 hours, and utilizing the ion heat of the ionic liquid to carry out solid Ce 2 O 3 Conversion to solid CeF at high temperature and high pressure 3 The method comprises the steps of carrying out a first treatment on the surface of the After the reaction is finished, taking out the reaction product, centrifuging, controlling the centrifugal speed to 10000rpm, and centrifuging for 3min to realize solid-liquid separation;
(3) Washing the precipitate with absolute ethyl alcohol for 4 times, and removing residual ionic liquid;
(4) Drying the precipitate at 90deg.C for 12 hr to obtain CeF 3 And (3) powder.
CeF prepared in this example 3 The XRD pattern of the powder is shown in figure 4, and the XRD pattern of the product is shown as CeF 3 The characteristic peaks of the (PDF # 89-1933) standard card are consistent, which shows that the product prepared by the method is CeF 3 And (3) powder. Meanwhile, the oxygen content in the rare earth fluoride is calculated by adopting an elemental analyzer (Elementar Vari EL Cube) to obtain that the oxygen content of the rare earth fluoride is 95ppm, thereby indicating Ce 2 O 3 To CeF 3 The conversion rate of (C) is higher, and the high-purity CeF can be prepared by the method of the embodiment 3 。
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (19)
1. The preparation method of the rare earth fluoride is characterized by comprising the following steps: carrying out solvothermal reaction on the rare earth oxide and the fluorinated ionic liquid to prepare rare earth fluoride;
the rare earth fluoride is represented by formula REF 3 A representation; wherein RE represents a rare earth element selected from at least one of La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, Y and Sc;
the fluorinated ionic liquid is selected from [ Bmim ]][PF 6 ]、[Bmim][BF 4 ]At least one of (a) and (b).
2. The method of claim 1, wherein the rare earth oxide is selected from the group consisting of oxides of rare earth elements RE.
3. The method of claim 2, wherein the rare earth oxide is selected from Nd 2 O 3 、La 2 O 3 、Ce 2 O 3 At least one of them.
4. The method of claim 1, whereinThe fluorinated ionic liquid is [ Bmim ]][PF 6 ]。
5. The method of claim 1, wherein the fluorinated ionic liquid is present in a ratio of volume molar mass (mL/mmol) to rare earth oxide of 1 (0.04-0.5).
6. The method of claim 5, wherein the ratio of the fluorinated ionic liquid to the rare earth oxide by volume molar mass (mL/mmol) is 1 (0.05-0.4).
7. The method of claim 1, wherein the solvothermal reaction is performed in a temperature and pressure resistant vessel.
8. The method of claim 7, wherein the temperature and pressure resistant vessel is a polytetrafluoroethylene liner;
the filling degree of the mixture of the fluorinated ionic liquid and the rare earth oxide in the polytetrafluoroethylene lining is 30-50%.
9. The method of claim 1, wherein the solvothermal reaction temperature is 150-200 ℃.
10. The method of claim 9, wherein the solvothermal reaction is at a temperature of 160-180 ℃.
11. The method of claim 1, wherein the solvothermal reaction time is 24-96 hours.
12. The method of claim 11, wherein the solvothermal reaction time is from 36 to 72 hours.
13. The method according to any one of claims 1 to 12, further comprising a step of subjecting the reaction system to solid-liquid separation after the completion of the reaction to obtain a reaction product.
14. The method of claim 13, further comprising washing the reaction product obtained by the solid-liquid separation.
15. The method of claim 14, further comprising drying the washed reaction product at a temperature of 60 to 90 ℃ for a time of 12 to 24 hours.
16. The preparation method according to any one of claims 1 to 12, characterized in that the preparation method comprises the steps of:
placing rare earth oxide and fluorinated ionic liquid in a temperature-resistant pressure-resistant reaction vessel, and performing solvothermal reaction; after the reaction is completed, carrying out solid-liquid separation, and washing and drying the obtained reaction product to obtain the rare earth fluoride.
17. The rare earth fluoride produced by the process of any one of claims 1-16, wherein the rare earth fluoride is of formula REF 3 A representation; wherein RE represents a rare earth element selected from at least one of La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, Y and Sc.
18. The rare earth fluoride of claim 17, wherein RE is selected from at least one of La, ce, pr, nd and Sm.
19. Rare earth fluoride according to claim 17, wherein the oxygen content of the rare earth fluoride is less than 100ppm.
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| CN115092952B (en) * | 2022-07-05 | 2023-10-03 | 冕宁县新盛源新材料科技有限公司 | Production process of rare earth fluoride |
| CN115181868B (en) * | 2022-07-18 | 2023-07-21 | 乐山盛和稀土有限公司 | Preparation method of rare earth fluoride |
| CN115321585B (en) * | 2022-08-09 | 2023-08-11 | 先导薄膜材料(安徽)有限公司 | Indium hydroxide washing process |
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