CN111187424A - Lanthanide rare earth-organic polymer precursor, lanthanide rare earth oxide fiber, and preparation method and application thereof - Google Patents
Lanthanide rare earth-organic polymer precursor, lanthanide rare earth oxide fiber, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a lanthanide rare earth-organic polymer precursor, a lanthanide rare earth oxide fiber, a preparation method and application thereof, wherein the preparation process comprises the following steps: 1) preparing a lanthanide series rare earth-organic polymer precursor; 2) preparing precursor fiber by electrostatic spinning: dissolving a rare earth-organic polymer precursor serving as a raw material by using an organic solvent, adding a spinning auxiliary agent to obtain a precursor spinning solution, and performing electrostatic spinning on the spinning solution at a voltage of 5-20 kV to obtain precursor fibers; 3) and (3) carrying out heat treatment on the precursor fiber in air to obtain the lanthanide rare earth oxide fiber. The fiber has the advantages of high purity, high strength, uniform and adjustable diameter, good flexibility, compact structure, no defects such as air holes and cracks and the like, and has wide application prospect in the fields of catalysis, illumination, nuclear industry, laser, storage, sensing, display, biological marking, ceramic materials, refractory materials and the like.
Description
The technical field is as follows:
the invention relates to a lanthanide rare earth-organic polymer precursor, a lanthanide rare earth oxide fiber and a preparation method thereof, in particular to a method for preparing a corresponding oxide fiber from the lanthanide rare earth-organic polymer precursor with a linear polymerization structure, belonging to the technical field of new materials.
Background art:
the lanthanide rare earth oxide refers to an oxide of 15 elements from lanthanum to lutetium in group IIIB of the periodic Table of elements. The rare earth element has the characteristics of high electrovalence, large radius, rich electronic energy level, easy polarization, positive correlation between refractive index and polarization strength, good thermal stability of rare earth oxide and the like, and has wide application prospects in the fields of catalysis, illumination, nuclear industry, laser, storage, sensing, display, biological marking, ceramic materials, refractory materials and the like. At present, the research on rare earth oxides mainly focuses on the aspects of powder, ceramic blocks, single crystals and the like. The preparation method of the rare earth oxide fiber comprises hydrothermal, solvothermal, electrostatic spinning and the like, wherein the fiber prepared by the hydrothermal and solvothermal methods is short in length, large in brittleness and limited in use; electrospinning has recently received considerable attention from researchers as an effective method for producing fibers. However, flexibility and purity are currently major issues that limit their practical applications for rare earth oxide fibers.
Chinese patent document CN101912582A discloses a La2O3:Tb3+Dissolving lanthanum acetate and terbium acetate in water, adding polyoxyethylene with the mass being 1-1.2 times of the total amount of acetate, stirring for 4 hours to obtain a spinning solution, and performing electrostatic spinning and subsequent heat treatment to obtain La2O3:Tb3+The fiber has larger diameter distribution dispersion, and because the content of the oxide in the precursor is lower, a large amount of organic matters are decomposed to cause more defects on the surface of the fiber, which influences the flexibility of the fiber. R. Thangappan et al prepared Gd using PVA as structural template and gadolinium nitrate as metal source2O3Nanofiber (see Applied Surface Science 261(2012)770-773), which has good optical properties but has more Surface pores, shorter length and higher strengthAnd (4) poor. Chinese patent document CN104153124A discloses a method for preparing a flexible rare earth oxide nanofiber membrane, which obtains a rare earth nanofiber membrane with good flexibility, but needs to add a non-rare earth stabilizer and a silane coupling agent in the preparation process, thereby greatly reducing the purity of the rare earth oxide nanofiber membrane.
The invention content is as follows:
aiming at the defects of the existing rare earth oxide fiber preparation technology, the invention provides a lanthanide rare earth-organic polymer precursor, a lanthanide rare earth oxide fiber, a preparation method and application thereof. The prepared lanthanide rare earth oxide fiber material has high purity and good flexibility.
The technical scheme of the invention is as follows:
the preparation method of the lanthanide series rare earth-organic polymer precursor comprises the following steps:
dissolving a rare earth metal source in anhydrous methanol, and mixing the metal source: adding the ligand at a ligand molar ratio of 1: 0.5-2, stirring for 30-200 minutes, and adding the metal source: dropwise adding triethylamine at a molar ratio of 1: 1-4, continuously stirring, and then drying under reduced pressure at 25-40 ℃; and soaking the product in an extracting agent, standing for 24-144 hours, filtering, removing filter residues, and drying the filtrate at the temperature of 25-40 ℃ under reduced pressure to obtain the rare earth-organic polymer precursor. The precursor has stable property and certain spinnability.
According to the invention, it is preferred that the metal source: ligand: the molar ratio of triethylamine is 1: 0.5-1.2: 1.5-4, and the mass of anhydrous methanol added in each 100 g of metal source is 300-600 g;
preferably, the reduced pressure drying temperature after adding triethylamine is 30-40 ℃;
preferably, the addition amount of the extracting agent is 2000-3000 ml per mol of the metal source, and the standing time is 48-96 hours.
According to the present invention, preferably, the metal source is one or more of a lanthanum source, a cerium source, a spectrum source, a neodymium source, a samarium source, a europium source, a gadolinium source, a terbium source, a dysprosium source, a holmium source, an erbium source, a thulium source, a ytterbium source, or a lutetium source;
further preferably, the lanthanum source is one or a mixture of crystalline lanthanum chloride and anhydrous lanthanum chloride;
the cerium source is one or a mixture of crystallized cerium chloride and anhydrous cerium chloride;
the spectrum source is one or a mixture of crystalline praseodymium chloride and anhydrous praseodymium chloride;
the neodymium source is one or a mixture of crystalline neodymium chloride and anhydrous neodymium chloride;
the samarium source is one or a mixture of crystalline samarium chloride and anhydrous samarium chloride;
the europium source is one or a mixture of crystal europium chloride and anhydrous europium chloride;
the gadolinium source is one or a mixture of crystalline gadolinium chloride and anhydrous gadolinium chloride;
the terbium source is one or a mixture of crystal terbium chloride and anhydrous terbium chloride;
the dysprosium source is one or a mixture of crystalline dysprosium chloride and anhydrous dysprosium chloride;
the holmium source is one or a mixture of crystalline holmium chloride and anhydrous holmium chloride;
the erbium source is one or a mixture of crystal erbium chloride and anhydrous erbium chloride;
the thulium source is one or a mixture of crystal thulium chloride and anhydrous thulium chloride;
the ytterbium source is one or a mixture of crystal ytterbium chloride and anhydrous ytterbium chloride;
the lutetium source is one or a mixture of crystalline lutetium chloride and anhydrous lutetium chloride.
According to the invention, preferably, the ligand is one or more of β -diketone such as acetylacetone, ethyl acetoacetate, methyl acetoacetate and the like;
preferably, the extracting agent is one or a mixture of acetone and tetrahydrofuran.
According to the invention, the lanthanide rare earth-organic polymer precursor prepared as described above is also provided.
According to the invention, the preparation method of the lanthanide rare earth oxide fiber comprises the following steps:
adding a lanthanide rare earth-organic polymer precursor into a spinning auxiliary agent, preparing a spinning solution in an organic solvent, carrying out electrostatic spinning on the spinning solution to obtain precursor fiber, and then carrying out heat treatment to obtain the lanthanide rare earth oxide fiber.
According to the present invention, preferably, the mass ratio of the rare earth-organic polymer precursor, the spinning auxiliary agent and the organic solvent is: 50-150: 1: 100-800.
According to the invention, preferably, the organic solvent is one or more of absolute methanol, absolute ethanol and N, N-Dimethylformamide (DMF);
preferably, the spinning auxiliary agent is one or a mixture of polyvinylpyrrolidone (PVP) and polyethylene oxide (PEO).
According to the present invention, it is preferred that the electrospinning conditions are: spinning voltage is 5-20 kV, the distance between a spinning nozzle and a receiving device is 10-30 cm, the advancing speed of a spinning solution is 0.5-4 ml/h, the ambient temperature is 5-45 ℃, and the humidity is 20-75%. Multiple forms of precursor fibers can be obtained by different receiving devices.
According to the present invention, it is preferred that the electrospinning conditions are: the spinning voltage is 6-18 kV, the propelling speed of the injection pump is 0.8-3 ml/h, the spinning environment temperature is 15-40 ℃, and the spinning environment humidity is 20-55%.
According to the present invention, preferably, the heat treatment process is performed in an air environment;
preferably, the heat treatment temperature is 600-1200 ℃.
According to the present invention, preferably, the heat treatment process is: heating to the heat treatment temperature at the speed of 0.5-5 ℃/min, preserving the heat for 10-240 minutes at the highest temperature, and then cooling along with the furnace.
The lanthanide rare earth oxide fiber material prepared by the preparation method has the excellent characteristics of high purity, high strength, good flexibility, uniform and adjustable diameter and the like, various material application forms can be obtained by adopting different collection modes, and the obtained fiber has uniform internal crystal grain size, compact arrangement and no defects of pores, cracks and the like on the surface of the fiber.
According to the invention, the lanthanide rare earth oxide fiber material is applied to the fields of catalysis, illumination, nuclear industry, laser, storage, sensing, display, biological marking, ceramic materials and refractory materials.
The invention has the technical characteristics and excellent effects that:
1. the invention firstly provides a lanthanide rare earth-organic polymer precursor and a universal preparation method of oxide fibers thereof, the oxide content in the prepared rare earth-organic polymer precursor is more than 60%, the content of lanthanide rare earth oxide in the precursor is greatly improved, the improvement of the density of the oxide fibers in the subsequent heat treatment process is facilitated, and the excellent flexibility and the higher strength of the oxide fibers are ensured.
2. The rare earth-organic polymer precursor prepared by the invention has stable property, does not deteriorate after being stored at room temperature for one year, and the spinning solution prepared by the rare earth-organic polymer precursor is clear and transparent, and can be stored at room temperature for one year without precipitation, turbidity and other phenomena.
3. The invention can obtain various lanthanide series rare earth oxide fiber material application forms by adopting different collection modes.
4. The lanthanide series rare earth oxide fiber prepared by the method has the advantages of high purity, high strength, uniform and adjustable diameter, good flexibility, compact structure, no defects such as air holes and cracks and the like. The invention does not need complex heat treatment and atmosphere protection, has simple preparation process and is easy for industrialized production.
Drawings
FIG. 1 is a photograph of a lutetium-organic polymer precursor prepared in example 2.
Fig. 2 is a plot of the lutetium-organic polymer precursor TG prepared in example 2.
FIG. 3 is an optical photograph of the lutetium oxide fiber prepared in example 2.
FIG. 4 is an X-ray diffraction (XRD) pattern of the lutetium oxide fiber prepared in example 2.
FIG. 5 is an SEM photograph of lutetium oxide fibers prepared in example 2.
The specific implementation mode is as follows:
the invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. At the same time, it should be noted that: it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the invention, and these modifications and improvements should be considered within the scope of the invention.
The raw materials used in the examples are all conventional commercial products.
Example 1:
a preparation method of a lanthanum-organic polymer precursor and lanthanum oxide fiber comprises the following steps:
(1) dissolving 100 g of anhydrous lanthanum chloride in 600 g of anhydrous methanol, adding 41 g of acetylacetone into the solution after the lanthanum chloride is completely dissolved, stirring for 2 hours, dropwise adding 100 g of triethylamine, and continuously stirring for 2 hours after the dropwise addition is finished to obtain a clear triethylamine precursor solution;
(2) transferring the clear solution prepared in the step (1) into a round-bottom flask, concentrating the clear solution into dry powder at 38 ℃ under reduced pressure, adding 850 g of acetone into the round-bottom flask, sealing the opening, and standing for 72 hours;
(3) filtering triethylamine hydrochloride insoluble in the round-bottom flask in the step (2) to obtain a lanthanum-acetylacetone polymer precursor solution, transferring the lanthanum-acetylacetone polymer precursor solution into another round-bottom flask, and drying the lanthanum-acetylacetone polymer precursor solution at 32 ℃ under reduced pressure to obtain lanthanum-acetylacetone polymer precursor powder;
(4) dissolving 0.10 g of PEO in 20 g of anhydrous methanol, adding 6 g of lanthanum-acetylacetone polymer precursor, stirring to obtain a clear and transparent precursor spinning solution, and performing electrostatic spinning on the precursor spinning solution to obtain precursor fibers, wherein the spinning voltage is 7kV, the propelling speed of an injection pump is 2ml/h, the environmental humidity is 40%, and the spinning process is performed at room temperature;
(5) and (3) heating the precursor fiber prepared in the step (4) to 800 ℃ at the speed of 1 ℃/min in a heat treatment furnace, preserving the temperature for 1 hour at the temperature of 800 ℃, and cooling along with the furnace.
The obtained flexible lanthanum oxide fiber has compact and smooth surface, purity up to 99.9%, uniform diameter of about 600 nm.
Example 2:
a preparation method of a lutetium-organic polymer precursor and lutetium oxide fiber comprises the following steps:
(1) dissolving 100 g of crystalline lutetium chloride in 300 g of anhydrous methanol, adding 38 g of acetylacetone into the solution after complete dissolution, stirring for 2 hours, dropwise adding 77 g of triethylamine, and continuously stirring for 2 hours after dropwise addition to obtain a clear triethylamine precursor solution;
(2) transferring the clear solution prepared in the step (1) into a round-bottom flask, concentrating the clear solution into dry powder at 38 ℃ under reduced pressure, adding 750 grams of tetrahydrofuran into the round-bottom flask, sealing the opening, and standing for 72 hours;
(3) filtering triethylamine hydrochloride insoluble in the round-bottom flask obtained in the step (2) to obtain a lutetium-acetylacetone polymer precursor solution, transferring the lutetium-acetylacetone polymer precursor solution into another round-bottom flask, and drying the lutetium-acetylacetone polymer precursor solution at 32 ℃ under reduced pressure to obtain lutetium-acetylacetone polymer precursor powder; a photograph of the lutetium-organic polymer precursor is shown in FIG. 1, and a TG curve of the lutetium-organic polymer is shown in FIG. 2.
(4) Dissolving 0.06 g of PEO in 20 g of absolute ethyl alcohol, adding 10 g of lutetium-acetylacetone polymer precursor, stirring to obtain a clear and transparent precursor spinning solution, and performing electrostatic spinning on the precursor spinning solution to obtain precursor fibers, wherein the spinning voltage is 10kV, the propelling speed of an injection pump is 2.5ml/h, the environmental humidity is 55%, and the spinning process is performed at room temperature;
(5) and (3) heating the precursor fiber prepared in the step (4) to 900 ℃ at the speed of 1 ℃/min in a heat treatment furnace, preserving the heat at the temperature of 900 ℃ for 1 hour, and cooling along with the furnace.
An optical photograph of the lutetium oxide fiber prepared in this example is shown in FIG. 3, an X-ray diffraction (XRD) pattern of the lutetium oxide fiber is shown in FIG. 4, and an SEM photograph of the lutetium oxide fiber is shown in FIG. 5. Therefore, the obtained lutetium oxide fiber has compact and smooth surface, good flexibility, purity of 99.95 percent, uniform diameter of about 450 nanometers.
Examples 3 to 17
Examples 3-17 the procedure is the same as in example 1, wherein the parameters for preparing the rare earth-organic polymer precursor, the parameters for preparing the spinning solution, and the diameter and purity of the flexible rare earth oxide fiber are shown in tables 1-3.
Note: stirring time 1-stirring time after adding ligand; stirring time is 2-stirring time after triethylamine is added;
drying temperature is 1-the drying temperature of the precursor solution containing triethylamine hydrochloride;
drying temperature 2-drying temperature of the filtered precursor solution after extraction with the extractant.
TABLE 1
TABLE 2
TABLE 3
Comparative example 1
As described in step (1) of example 2, 100 g of crystalline lutetium chloride was dissolved in 300 g of anhydrous methanol, 20 g of acetylacetone was added to the solution after complete dissolution, and after stirring for 2 hours, 77 g of triethylamine was added dropwise, and after the addition was completed, stirring was continued for 2 hours, and the resulting solution was milky white. Indicating that lower amounts of ligand lead to hydrolysis of the precursor.
Comparative example 2
And (3) raising the temperature of the precursor fiber prepared in the step (4) to 900 ℃ at 200 ℃/min in a heat treatment furnace, preserving the temperature at 900 ℃ for 1 hour, and cooling along with the furnace, as described in the step (5) of the example 2.
The obtained lutetium oxide fiber has more pores. During the heat treatment process, the porosity of the fibers is increased easily and the strength and the toughness are reduced easily due to the excessively high temperature rise rate.
Claims (10)
1. The preparation method of the lanthanide series rare earth-organic polymer precursor comprises the following steps:
dissolving a rare earth metal source in anhydrous methanol, and mixing the metal source: adding the ligand at a ligand molar ratio of 1: 0.5-2, stirring for 30-200 minutes, and adding the metal source: dropwise adding triethylamine at a molar ratio of 1: 1-4, continuously stirring, and then drying under reduced pressure at 25-40 ℃; and soaking the product in an extracting agent, standing for 24-144 hours, filtering, removing filter residues, and drying the filtrate at the temperature of 25-40 ℃ under reduced pressure to obtain the rare earth-organic polymer precursor. The precursor has stable property and certain spinnability.
2. The process for the preparation of a lanthanide rare earth-organic polymer precursor as claimed in claim 1, wherein the metal source: ligand: the molar ratio of triethylamine is 1: 0.5-1.2: 1.5-4, and the mass of anhydrous methanol added in each 100 g of metal source is 300-600 g;
preferably, the reduced pressure drying temperature after adding triethylamine is 30-40 ℃;
preferably, the addition amount of the extracting agent is 2000-3000 ml per mol of the metal source, and the standing time is 48-96 hours.
3. The method of claim 1, wherein the metal source is one or more of lanthanum source, cerium source, spectrum source, neodymium source, samarium source, europium source, gadolinium source, terbium source, dysprosium source, holmium source, erbium source, thulium source, ytterbium source, or lutetium source;
preferably, the lanthanum source is one or a mixture of crystalline lanthanum chloride and anhydrous lanthanum chloride;
the cerium source is one or a mixture of crystallized cerium chloride and anhydrous cerium chloride;
the spectrum source is one or a mixture of crystalline praseodymium chloride and anhydrous praseodymium chloride;
the neodymium source is one or a mixture of crystalline neodymium chloride and anhydrous neodymium chloride;
the samarium source is one or a mixture of crystalline samarium chloride and anhydrous samarium chloride;
the europium source is one or a mixture of crystal europium chloride and anhydrous europium chloride;
the gadolinium source is one or a mixture of crystalline gadolinium chloride and anhydrous gadolinium chloride;
the terbium source is one or a mixture of crystal terbium chloride and anhydrous terbium chloride;
the dysprosium source is one or a mixture of crystalline dysprosium chloride and anhydrous dysprosium chloride;
the holmium source is one or a mixture of crystalline holmium chloride and anhydrous holmium chloride;
the erbium source is one or a mixture of crystal erbium chloride and anhydrous erbium chloride;
the thulium source is one or a mixture of crystal thulium chloride and anhydrous thulium chloride;
the ytterbium source is one or a mixture of crystal ytterbium chloride and anhydrous ytterbium chloride;
the lutetium source is one or a mixture of crystalline lutetium chloride and anhydrous lutetium chloride.
4. The method for preparing the lanthanide rare earth-organic polymer precursor as claimed in claim 1, wherein the ligand is one or more of β -diketone such as acetylacetone, ethyl acetoacetate, methyl acetoacetate, etc.;
preferably, the extracting agent is one or a mixture of acetone and tetrahydrofuran.
5. A lanthanide rare earth-organic polymer precursor prepared according to any one of claims 1-4.
6. A method of making a lanthanide rare earth oxide fiber comprising using the lanthanide rare earth-organic polymer precursor prepared according to any one of claims 1-4, comprising the steps of:
adding a lanthanide rare earth-organic polymer precursor into a spinning auxiliary agent, preparing a spinning solution in an organic solvent, carrying out electrostatic spinning on the spinning solution to obtain precursor fiber, and then carrying out heat treatment to obtain the lanthanide rare earth oxide fiber.
7. The method for preparing lanthanide series rare-earth oxide fiber according to claim 6, wherein the mass ratio of the rare-earth-organic polymer precursor, the spinning auxiliary agent and the organic solvent is as follows: 50-150: 1: 100-800;
preferably, the organic solvent is one or more of absolute methanol, absolute ethanol and N, N-Dimethylformamide (DMF);
preferably, the spinning auxiliary agent is one or a mixture of polyvinylpyrrolidone (PVP) and polyethylene oxide (PEO).
8. The method of claim 6, wherein the electrospinning conditions are: spinning voltage is 5-20 kV, the distance between a spinning nozzle and a receiving device is 10-30 cm, the advancing speed of a spinning solution is 0.5-4 ml/h, the ambient temperature is 5-45 ℃, and the humidity is 20-75%;
preferably, the electrospinning conditions are: the spinning voltage is 6-18 kV, the propelling speed of an injection pump is 0.8-3 ml/h, the spinning environment temperature is 15-40 ℃, and the spinning environment humidity is 20-55%;
preferably, the heat treatment process is performed in an air environment;
preferably, the heat treatment temperature is 600-1200 ℃;
preferably, the heat treatment process is as follows: heating to the heat treatment temperature at the speed of 0.5-5 ℃/min, preserving the heat for 10-240 minutes at the highest temperature, and then cooling along with the furnace.
9. A lanthanide rare earth oxide fiber material prepared according to any one of claims 6-8.
10. Use of the lanthanide rare earth oxide fiber material as defined in claim 9 in the fields of catalysis, lighting, nuclear industry, lasers, storage, sensing, display, biomarkers, ceramic materials and refractory materials.
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| WO2021159646A1 (en) * | 2020-02-14 | 2021-08-19 | 山东大学 | Lanthanide rare earth-organic polymer precursor, lanthanide rare earth oxide fiber, preparation method therefor and application thereof |
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