CN109694100B - Preparation of LaF by self-sacrifice template method3Method (2) - Google Patents
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Abstract
Preparation of LaF by self-sacrifice template method3The method comprises the following steps: (1) preparing a lanthanum nitrate solution; (2) stirring and adding ammonium sulfate particles; (3) stirring, adding ammonia water to adjust the pH value, and continuously stirring to obtain a primary suspension; (4) placing the reaction kettle in a reaction kettle for primary precipitation reaction, and precipitating the generated reaction nanosheet layered compound at the bottom; (5) washing the centrifugally separated solid phase with water; (6) washing the solid phase with water, and then oscillating with ultrasonic waves; (7) addition of NH4Performing secondary precipitation reaction on the solution F under a sealed condition; (8) centrifuging to separate out a secondary centrifugal solid phase, washing with water and alcohol, and drying. The method of the invention is simple and easy to implement, does not need calcination and organic solvent, and has good product performance.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to a method for preparing LaF by a self-sacrifice template method3The method of (1).
Background
Rare earth fluoride LaF3Has low vibration energy and has the advantages of minimizing the quenching of excited state molecules of rare earth ions and generating high fluorescence quantum yield; LaF3Can be used as luminescent matrix material, biological probe, chemical sensor, and moisteningThe lubricating oil additive, the electrode material and the like are good solid electrolytes and have high ionic conductivity; as a luminescent material, the rare earth doped fluoride nano material has excellent optical characteristics and stable physicochemical properties, and has good application prospects in high-resolution displays, solid-state lasers, infrared detection, biological analysis, medical diagnosis and other fields.
Preparation of LaF at present3The nano particle method includes solid phase method, direct precipitation method, micro emulsion method, polyhydroxy method, thermal decomposition method, water/solvent thermal method, etc.; some preparation methods need anhydrous and anaerobic or high-temperature reaction conditions, the reaction time is long, and the experimental operation is complex; the traditional high-temperature solid-phase method for synthesizing the rare earth fluoride luminescent material needs to use highly toxic elemental fluorine, hydrogen fluoride and the like with great environmental hazard as a fluorinating agent, so that the theoretical research and the application research of the fluoride luminescent material are severely limited; therefore, the development of green synthesis of the rare earth fluoride luminescent material not only has important theoretical value, but also has important significance for application research of the rare earth fluoride luminescent material.
As is well known, the performance of most functional materials, such as luminous efficiency, catalytic property, machining property and the like, strongly depends on the grain size, micro morphology, crystal structure and the like of the functional materials, and the luminous efficiency of the functional materials is greatly enhanced due to the surface effect, the quantum size effect and the like when the functional material particles are subjected to nanocrystallization; exploration of LaF3New synthesis method of nano particles, how to control LaF3The dispersibility of the nano particles, the realization of environmental friendliness in the synthesis process and the cost reduction are still LaF3The key problems to be solved in the process of preparing the nano particles and industrial application are urgent.
Disclosure of Invention
The invention aims to provide a method for preparing LaF by a self-sacrifice template method3The method comprises the steps of precipitating a lamellar compound by utilizing ammonium sulfate and lanthanum ions under an alkaline condition, and then precipitating the lamellar compound against lanthanum fluoride LaF3Problems in the synthesis and incorporation of the ultrathin layered compound La2(OH)4SO4·2H2And O. Aims to enrich the prior lanthanum fluoride LaF3Preparation method of (1), rich fluorinationLanthanum is in microscopic shape, and nano powder with uniform size and good dispersibility is obtained.
To achieve the above object, the method of the present invention comprises the steps of:
1. lanthanum nitrate hexahydrate (La (NO)3)3·6H2O) is dissolved in deionized water to prepare La3+Lanthanum nitrate (La (NO) with a concentration of 0.03-0.20 mol/L3)3) A solution;
2. under stirring, ammonium sulfate ((NH)4)2SO4) Adding the particles into a lanthanum nitrate solution to prepare a mixed solution, and adding the particles into the mixed solution according to the molar ratio SO4 2-:La3+＝0.5～10；
3. Under the stirring condition, adding ammonia water into the mixed solution, adjusting the pH value to 8.5-10, and continuously stirring for 10-30 min to obtain a primary suspension;
4. placing the primary suspension in a reaction kettle, and carrying out primary precipitation reaction at the reaction temperature of 4-120 ℃ for 12-72 h; after the primary precipitation reaction is finished, the generated reactant nanosheet layered compound La2(OH)4SO4·2H2O is precipitated at the bottom;
5. centrifuging the material after the completion of the primary precipitation reaction at normal temperature by using a centrifuge to separate a primary centrifugal solid phase and a primary centrifugal liquid phase; washing the primary centrifugal solid phase with deionized water until the washing liquid is neutral, and washing unreacted NH4 +Removing to obtain a water-washing solid phase;
6. adding water into the water-washed solid phase until the volume of all materials is the same as that of the primary suspension, and then oscillating for at least 20min by using an ultrasonic cleaner to obtain a secondary suspension; the solid in the secondary suspension is a layered compound nanosheet;
7. adding NH with the concentration of 0.3-3.0M into the secondary suspension4Performing secondary precipitation reaction on the solution F under a sealed condition, wherein a layered compound nanosheet in the reaction process is used as a self-sacrificial template, the reaction temperature is Room Temperature (RT) -220 ℃, and the reaction time is 2-72 hours; NH (NH)4The dosage of the solution F is based on the molar ratio F in all the materials-:La3+＝3～100；
8. Centrifuging the product after the secondary precipitation reaction at normal temperature by using a centrifuge to separate a secondary centrifugal solid phase and a secondary centrifugal liquid phase; washing the secondary centrifugal solid phase with water and alcohol, drying to remove volatile components and obtain nanoscale LaF3。
The above-mentioned LaF3The particle size of (A) is 30 to 120 nm.
In the step 8, the drying temperature is 40-60 ℃ and the drying time is 12-24 h.
In the step 8, the washing step is to wash the second centrifugal solid phase by filtration until the washing solution is neutral; the alcohol washing is to wash the product after water washing with absolute ethyl alcohol to remove water.
The principle and the beneficial effects of the method of the invention are as follows:
1. preparing nano lamellar compound La at the early stage2(OH)4SO4·2H2O, the compound exists in the form of gel in suspension and serves as a self-sacrifice template, and La in the self-sacrifice template3+:OH-0.5; while the other templates are, for example, REs which are lamellar compounds2(OH)5NO3·2H2In O, RE3+:OH-＝0.4，La(OH)3Middle La3+:OH-About 0.33, the rare earth ion ratio is high; during the subsequent reaction, OH-And F-Higher La for competitive coordination3+:OH-Ratio of F to-More easily react with La3+Coordination is carried out, so that a target product is easier to form, and lanthanum fluoride LaF is more favorable3Forming;
2. during the secondary precipitation reaction, ammonium fluoride NH is adopted4F is used as a fluorine source, and the influence of other fluorides can be avoided, such as NaLaF caused by the existence of sodium fluoride4And (3) the phases are equal;
3. the method is simple and easy to implement, and the target product LaF can be directly obtained after secondary precipitation3Subsequent calcination is not required; compared with a plurality of conventional hydrothermal methods for obtaining intermediates after reaction, the method can obtain target products by further calcining, thereby savingLarge energy sources and complex operations; the specific calcining temperature can be determined only through experiments, and the problems of damaging the original micro-morphology of the hydrothermal product and causing particle agglomeration can be effectively avoided without a high-temperature calcining process;
4. using mild NH4F is a fluorine source, and has no harm to the environment and human body. In the process, water is used as a solvent, and harmful organic matters are not needed to be used as the solvent;
5. the obtained target product has wide parameter range, does not need to finely adjust operation parameters, and can obtain superfine nano powder with good dispersity and uniform size; the application of the fluorescent powder can be influenced from multiple directions by different microscopic shapes, if the fluorescent powder needs to be coated, the fluorescent powder is expected to have better coating performance, and the monodisperse spherical fluorescent powder can be easily self-assembled and arranged into a film or a plane, so that the fluorescent powder has wider application due to the diversification and homogenization of the shapes.
Drawings
FIG. 1 shows LaF prepared in example 1 of the present invention3XRD pattern of (a);
FIG. 2 shows LaF prepared in example 1 of the present invention3FE-SEM picture of (b);
FIG. 3 shows LaF prepared in example 2 of the present invention3XRD pattern of (a);
FIG. 4 shows LaF prepared in example 3 of the present invention3XRD pattern of (a);
FIG. 5 shows LaF prepared in example 4 of the present invention3XRD pattern of (a);
FIG. 6 shows LaF prepared in example 4 of the present invention3FE-SEM image of (b).
Detailed Description
The present invention will be described in further detail with reference to examples.
The chemical reagents used in the examples of the present invention are analytical grade products.
In the embodiment of the invention, the adopted water is deionized water.
In the embodiment of the invention, XRD analysis is carried out by adopting a RINT2200V/PC type X-ray diffractometer of Rigaku corporation in Japan; observing the appearance of the sample by using an S-5000 field emission scanning electron microscope (FE-SEM) of Hitachi corporation of Japan;
in the embodiment of the invention, when the precipitation reaction is carried out, the material is placed in the inner container of the reaction kettle, and the material of the inner container is polytetrafluoroethylene.
In the embodiment of the invention, the volume specification of the inner container is 100ml, and the steel sleeve is made of stainless steel.
When the precipitation reaction is carried out in the embodiment of the invention, if the material is heated, the adopted heating equipment is an electronic temperature control oven, and the temperature control precision is +/-1 ℃.
LaF in the examples of the invention3The particle size of (A) is 30 to 120 nm.
In the embodiment of the invention, when the water washing and the alcohol washing of the secondary centrifugal solid phase are carried out, the water washing is to filter and wash the secondary centrifugal solid phase until the washing liquid is neutral; the alcohol washing is to wash the product after water washing with absolute ethyl alcohol to remove water.
In the embodiment of the invention, when the primary precipitation reaction is lower than the room temperature, the temperature is controlled by adopting a brine bath.
The following are preferred embodiments of the present invention.
Example 1
Dissolving lanthanum nitrate hexahydrate in deionized water to prepare La3+Lanthanum nitrate solution with the concentration of 0.03 mol/L;
adding ammonium sulfate particles into a lanthanum nitrate solution under stirring to prepare a mixed solution, wherein the mixed solution contains SO according to a molar ratio4 2-:La3+＝10；
Under the stirring condition, adding ammonia water into the mixed solution, adjusting the pH value to 8.5, and continuously stirring for 30min to obtain a primary suspension;
placing the primary suspension in a reaction kettle, and carrying out primary precipitation reaction at the reaction temperature of 80 ℃ for 36 hours; after the primary precipitation reaction is finished, the generated reactant nanosheet layered compound La2(OH)4SO4·2H2O is precipitated at the bottom;
centrifuging the material after the completion of the primary precipitation reaction at normal temperature by using a centrifuge to separate a primary centrifugal solid phase and a primary centrifugal liquid phase; centrifuging once to obtain solid phaseWashing with deionized water until the washing liquid is neutral, and adding unreacted NH4 +Removing to obtain a water-washing solid phase;
adding water into the water-washed solid phase until the volume of all materials is equal to that of the primary suspension, and then oscillating for 20min by using an ultrasonic cleaner to obtain a secondary suspension; the solid in the secondary suspension is a layered compound nanosheet;
adding NH with concentration of 0.3M into the secondary suspension4Performing secondary precipitation reaction on the solution F under a sealed condition, wherein the layered compound nanosheet in the reaction process is used as a self-sacrifice template, the reaction temperature is 150 ℃, and the reaction time is 24 hours; NH (NH)4The dosage of the solution F is based on the molar ratio F in all the materials-:La3+＝3；
Centrifuging the product after the secondary precipitation reaction at normal temperature by using a centrifuge to separate a secondary centrifugal solid phase and a secondary centrifugal liquid phase; washing the secondary centrifugal solid phase with water and alcohol, drying at 40 deg.C for 24 hr to obtain nanoscale LaF3The XRD pattern is shown in FIG. 1, in which Hexagonal LaF is shown below3JCPDS 01-074-; the FE-SEM image is shown in FIG. 2.
Example 2
The method is the same as example 1, except that:
(1) the concentration of the lanthanum nitrate solution is 0.05 mol/L;
(2) in the mixed solution according to the molar ratio SO4 2-:La3+＝5；
(3) Adding ammonia water to adjust pH to 9, and stirring for 20 min;
(4) the temperature of the primary precipitation reaction is 120 ℃, and the time is 12 hours;
(5) shaking with ultrasonic cleaner for 25 min;
(6)NH4the concentration of the solution F is 1.0M, the temperature of the secondary precipitation reaction is 220 ℃, and the time is 2 hours; NH (NH)4The dosage of the solution F is based on the molar ratio F in all the materials-:La3+＝15；
(7) Washing the secondary centrifugal solid phase with water and alcohol, and drying at 50 ℃ for 20 hours;
(8)LaF3the XRD pattern of (A) is shown in FIG. 3.
Example 3
The method is the same as example 1, except that:
(1) the concentration of the lanthanum nitrate solution is 0.10 mol/L;
(2) in the mixed solution according to the molar ratio SO4 2-:La3+＝2；
(3) Adding ammonia water to adjust pH to 9.5, and stirring for 15 min;
(4) the temperature of the primary precipitation reaction is 4 ℃, and the time is 72 hours;
(5) shaking with ultrasonic cleaner for 30 min;
(6)NH4the concentration of the solution F is 2.0M, the temperature of the secondary precipitation reaction is room temperature, and the time is 72 hours; NH (NH)4The dosage of the solution F is based on the molar ratio F in all the materials-:La3+＝50；
(7) Washing the secondary centrifugal solid phase with water and alcohol, and drying at 55 ℃ for 16 h;
(8)LaF3the XRD pattern of (A) is shown in FIG. 4.
Example 4
The method is the same as example 1, except that:
(1) the concentration of the lanthanum nitrate solution is 0.20 mol/L;
(2) in the mixed solution according to the molar ratio SO4 2-:La3+＝0.5；
(3) Adding ammonia water to adjust pH to 10, and stirring for 10 min;
(4) the temperature of the primary precipitation reaction is 30 ℃, and the time is 48 hours;
(5) shaking with ultrasonic cleaner for 30 min;
(6)NH4the concentration of the solution F is 3.0M, the temperature of the secondary precipitation reaction is 50 ℃, and the time is 48 hours; NH (NH)4The dosage of the solution F is based on the molar ratio F in all the materials-:La3+＝100；
(7) Washing the secondary centrifugal solid phase with water and alcohol, and drying at 60 ℃ for 12 hours;
(8)LaF3the XRD pattern of (A) is shown in FIG. 5, and the FE-SEM pattern is shown in FIG. 6.
Claims (3)
1. Preparation of LaF by self-sacrifice template method3The method is characterized by comprising the following steps:
(1) dissolving lanthanum nitrate hexahydrate in deionized water to prepare La3+Lanthanum nitrate solution with the concentration of 0.03-0.20 mol/L;
(2) adding ammonium sulfate particles into a lanthanum nitrate solution under stirring to prepare a mixed solution, wherein the mixed solution contains SO according to a molar ratio4 2-:La3+=0.5~10；
(3) Under the stirring condition, adding ammonia water into the mixed solution, adjusting the pH value to 8.5-10, and continuously stirring for 10-30 min to obtain a primary suspension;
(4) placing the primary suspension in a reaction kettle, and carrying out primary precipitation reaction at the reaction temperature of 30-120 ℃ for 12-72 hours; after the primary precipitation reaction is finished, the generated reactant nanosheet layered compound La2(OH)4SO4·2H2O is precipitated at the bottom;
(5) centrifuging the material after the completion of the primary precipitation reaction at normal temperature by using a centrifuge to separate a primary centrifugal solid phase and a primary centrifugal liquid phase; washing the primary centrifugal solid phase with deionized water until the washing liquid is neutral, and washing unreacted NH4 +Removing to obtain a water-washing solid phase;
(6) adding water into the water-washed solid phase until the volume of all materials is the same as that of the primary suspension, and then oscillating for at least 20min by using an ultrasonic cleaner to obtain a secondary suspension; the solid in the secondary suspension is a layered compound nanosheet;
(7) adding NH with the concentration of 0.3-3.0M into the secondary suspension4Performing secondary precipitation reaction on the solution F under a sealed condition, wherein a layered compound nanosheet in the reaction process is used as a self-sacrificial template, the reaction temperature is room temperature-220 ℃, and the reaction time is 2-72 hours; NH (NH)4The dosage of the solution F is based on the molar ratio F in all the materials-:La3+=3~100；
(8) Centrifuging the product after the secondary precipitation reaction at normal temperature by using a centrifugal machineSeparating out a secondary centrifugal solid phase and a secondary centrifugal liquid phase; washing the secondary centrifugal solid phase with water and alcohol, drying to remove volatile components and obtain nanoscale LaF3The particle size is 30-120 nm.
2. The method of claim 1 for preparing LaF by using self-sacrifice template method3The method is characterized in that in the step (8), the drying temperature is 40-60 ℃ and the drying time is 12-24 hours.
3. The method of claim 1 for preparing LaF by using self-sacrifice template method3The method is characterized in that in the step (8), the washing is to wash the washing solution by secondary centrifugal solid phase filtration until the washing solution is neutral; the alcohol washing is to wash the product after water washing with absolute ethyl alcohol to remove water.
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