CN113003601A - Preparation method of spherical nano cerium dioxide - Google Patents
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- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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Abstract
The invention provides a preparation method of spherical nano cerium dioxide. The method is realized by the following steps: respectively dissolving cerium salt and alkali in an organic solvent, and then mixing the two solutions to perform a precipitation reaction; after the precipitation reaction is finished, adding a high molecular polymer into the reaction system, and stirring to obtain a reaction mixture; shearing and dispersing the obtained reaction mixture at a high speed for 30 min-48 h at the temperature of 40-220 ℃, and continuously blowing gas with oxidability into a reaction system during the shearing and dispersing; and centrifuging the obtained product to obtain a solid, washing and drying to obtain the spherical nano cerium dioxide. The method can prepare monodisperse spherical nano CeO with the particle size of 40 nm-200 nm2(ii) a Meanwhile, the method has the characteristics of high process stability, high yield, strong operability and the like, and is suitable for large-scale production.
Description
Technical Field
The invention relates to nano CeO2In particular to nano CeO2Wet preparation in organic solvent.
Background
Nano CeO2Has unique optical, acoustic, electric, magnetic, thermal and other properties,so that the catalyst can be widely applied to the fields of catalysis, grinding, glass, ceramics, cosmetics and the like. For example, CeO is used for the effective removal rate of oxide film and flexibility thereof2Becoming one of the main abrasive materials for chemical mechanical polishing processes in the semiconductor manufacturing industry. Especially in the Shallow Trench Isolation (STI) chemical mechanical polishing process formed by silicon dioxide and silicon nitride deposition, benefit from nanometer CeO2Meanwhile, the method has high efficiency in removing the silicon dioxide layer and high selectivity to silicon dioxide and silicon nitride. Using nano CeO2The polishing of the grinding material can realize high polishing and etching efficiency, high flatness and low defect rate of the shallow trench isolation structure. Thus, nano CeO2Becoming the most preferred abrasive material for current Shallow Trench Isolation (STI) chemical mechanical polishing.
The results of the last decades of research show that: nano CeO2The structural characteristics of the particles are one of the most important indexes of the application performance, wherein the spherical nanometer CeO with high dispersity and narrow particle size distribution2The particles are the best structure for abrasive materials, catalytic materials, anti-aging materials, and the like. Currently, the commercial production of nano-ceria is mainly achieved by thermal decomposition of cerium salt (such as cerium carbonate, cerium hydroxide or cerium nitrate), followed by mechanical grinding and classification to finally obtain the product. Although this method can obtain highly chemically active CeO2But the size and shape of the particles is difficult to control.
In order to overcome the above problems, various methods for preparing nano CeO2The process of (a) is proposed, and typically includes: hydrothermal method, sol-gel method, and flux thermal method. The hydrothermal method uses cerium salt as raw material, water or organic solvent as transfer medium, and CeO is generated at high temperature and high pressure2. The method can prepare CeO with ideal morphological characteristics by controlling reaction parameters or adding a mineralizer and a surfactant2However, the disadvantages are quite evident: in one aspect, the CeO prepared by the method2The particle size is generally less than 40 nanometers, and the small-sized particles can not meet the use requirement (such as the high removal rate requirement of a target layer in chemical mechanical polishing); on the other hand, in the hydrothermal reaction, only 1-5 kgCeO can be produced in each cubic reaction system2Product, this low yieldAnd is one of the obstacles limiting the industrialization thereof. The sol-gel method comprises adding precipitant (such as urea, alkali metal hydroxide, ammonia water, etc.) into aqueous solution containing cerium salt, separating, drying, and heat treating to obtain nanometer CeO2. The method does not depart from the essence of the traditional method, the agglomeration is very easy in the drying process, the hard agglomeration is easy to change in the high-temperature heat treatment, and the subsequent mechanical crushing and classification are still needed, so the product quality is difficult to improve fundamentally. The flux thermal method is the decomposition of cerium salt in high temperature molten salt, and in the process, the separation and cleaning of products have great problems. In general terms: the methods have obvious process characteristics, and the prepared products also show certain performance characteristics, but long-time exploration is still needed to achieve the industrial production scale.
Disclosure of Invention
The invention aims to provide spherical nano CeO with narrow particle distribution and high dispersibility2The preparation method of (1).
The technical scheme adopted by the invention is as follows: a preparation method of spherical nano cerium dioxide comprises the following steps:
1) respectively dissolving cerium salt and alkali in an organic solvent, and then mixing the two solutions to perform a precipitation reaction;
2) after the precipitation reaction is finished, adding a high molecular polymer into the reaction system, and stirring to obtain a reaction mixture;
3) shearing and dispersing the reaction mixture obtained in the step 2) at a high speed for 30 min-48 h at the temperature of 40-220 ℃, and continuously blowing gas with oxidability into a reaction system; the high-speed shearing rotating speed is 2000 rpm-15000 rpm;
4) and (3) centrifugally separating the product obtained in the step 3) to obtain a solid, washing and drying to obtain the spherical nano cerium dioxide.
Preferably, in the above method for preparing spherical nano-ceria, in step 1), the organic solvent is one or a mixture of two or more of alcohols, ethers, and ketones with a boiling point of more than 50 ℃.
More preferably, in the above method for preparing spherical nano ceria, the alcohol is selected from ethanol, methanol, ethylene glycol and glycerol; the ethers are selected from n-butyl ether and tert-butyl ether; the ketones are selected from the group consisting of pentanone and propiophenone. More preferably, the organic solvent is selected from alcohols. Most preferably, the organic solvent is ethylene glycol.
Preferably, in the above method for preparing spherical nano-ceria, in step 1), the cerium salt is soluble in an organic solvent, and the cerium salt is selected from one or a mixture of two or more of cerium sulfate, cerium nitrate, cerium chloride and cerium ammonium nitrate. More preferably, the cerium salt is selected from the group consisting of cerous nitrate and cerous chloride, and most preferably, the cerium salt is selected from the group consisting of cerous nitrate.
Preferably, the cerium salt is formulated at a concentration of 0.05mol/L to 0.90 mol/L. When the concentration is lower than 0.05mol/L, the preparation cost is increased; when the concentration exceeds 0.90mol/L, the uniformity of the particle size of the product is reduced; more preferably, the cerium salt is prepared at a concentration of 0.10mol/L to 0.80 mol/L; more preferably, the cerium salt is formulated at a concentration of 0.2 to 0.70mol/L, and most preferably, at a concentration of 0.3 to 0.60 mol/L.
Preferably, in the above method for preparing spherical nano-ceria, in step 1), the base is soluble in an organic solvent, and the base is selected from one or a mixture of two or more of sodium hydroxide, potassium hydroxide, ammonia water, hydrazine hydrate, tetramethylammonium hydroxide and urea. More preferably, the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, hydrazine hydrate, methyl ammonium hydroxide and urea; most preferably, the base is selected from the group consisting of sodium hydroxide, potassium hydroxide and urea.
Preferably, in the preparation method of the spherical nano cerium dioxide, the alkali preparation concentration is 0.01 mol/L-6.00 mol/L. When the concentration is lower than 0.01mol/L, the preparation cost is increased; when the concentration exceeds 6.00mol/L, the uniformity of the particle size of the product is lowered. More preferably, the alkali preparation concentration is 0.1mol/L to 6.00 mol/L. More preferably, the alkali preparation concentration is 0.2mol/L to 4.00 mol/L. Most preferably, the base formulation concentration is 0.3mol/L to 2.00 mol/L.
Preferably, in the above method for preparing spherical nano ceria, in step 2), the high molecular polymer is a linear high molecular polymer with a molecular weight greater than 2000. The high molecular polymer is selected from one or more of polyvinylpyrrolidone, hydroxypropyl cellulose and hydroxypropyl methyl cellulose. If, for example, a high-molecular polymer with branched chains is selected, spherical particles cannot be synthesized. When a linear high molecular polymer having a molecular weight of less than 2000 is used, the synthesized particles are easily agglomerated to form large non-spherical particles. More preferably, the high molecular polymer is selected from the group consisting of polyvinylpyrrolidone and hydroxypropylcellulose. Most preferably, the high molecular weight polymer is selected from hydroxypropyl cellulose.
Preferably, in the preparation method of spherical nano cerium dioxide, the addition amount of the high molecular polymer is 30 g/L-160 g/L. When the addition amount is less than 30g/L, the product is obviously agglomerated, and when the addition amount is more than 160g/L, the solution viscosity is too large, which is not beneficial to the implementation of high-speed shearing dispersion and subsequent solid-liquid separation. More preferably, the amount of the high molecular weight polymer added is 40g/L to 150 g/L. More preferably, the amount of the high molecular weight polymer added is 40g/L to 130 g/L. Most preferably, the amount of the high molecular weight polymer added is 40g/L to 120 g/L.
Blowing of an oxidizing gas is necessary in the present invention, especially with respect to the trivalent cerium salt, in order to oxidize the cerous hydroxide in the solution and finally to smoothly convert it into CeO2. Preferably, in step 3), the oxidizing gas is air, oxygen or chlorine.
In the invention, the heating temperature in the step 3) is 40-220 ℃. At a temperature below 40 deg.C, cerium hydroxide is oxidized and decomposed into CeO2Too slow. When the temperature exceeds 220 ℃, the formed cerium oxide is further converted into an organic compound of cerium. Preferably, the heating temperature is 110 ℃ to 190 ℃.
In the invention, the time in the step 3) is controlled to be 30 min-48 h. When the time is less than 30min, the cerous hydroxide can not be completely converted into CeO2Meanwhile, the crosslinking degree of the high molecular polymer is low, and the sphericity of the final product is poor. Above 48h, no significant change in product organization occurred.
In the invention, the high-speed shearing rotating speed in the step 3) is 2000 rpm-15000 rpm. When the high-speed shearing rotation speed is lower than 2000rpm, the particle size distribution is not uniform. When the high shear rate exceeds 15000rpm, the linear polymer is easily broken, and the particle size distribution is also uneven. Preferably, the high-speed shearing rotating speed is 3000 rpm-12000 rpm, and most preferably, the high-speed shearing rotating speed is 4000 rpm-6000 rpm.
The invention has the beneficial effects that:
1. in the invention, cerium salt reacts with alkali, and the generated cerous hydroxide reacts with an oxidation medium gradually at a certain temperature to generate CeO2The whole process of the nanocrystalline is carried out in the organic solvent with low dielectric constant, so that the agglomeration phenomenon is avoided.
2. In the invention, the introduction of the linear high molecular polymer can uniformly divide CeO in the solution2And (3) carrying out a crosslinking reaction on the nanocrystals and the high molecular polymer in the organic solution, wherein a certain amount of cerium dioxide nanocrystals are wrapped by a crosslinking product, and finally forming the polycrystalline cerium dioxide spherical particles.
3. In the present invention, CeO in the range of 40nm to 200nm is realized by controlling the conditions such as cerium salt concentration and the addition amount of the high molecular polymer2Controllable synthesis of nanospheres.
Drawings
FIG. 1 shows the results of laser particle size analysis of the bright yellow mixed solution obtained after 12 hours in example 1.
FIG. 2 shows the results of X-ray diffraction analysis of the powder obtained in example 1.
FIG. 3 shows the results of SEM analysis of the powder obtained in example 1.
FIG. 4 shows the results of SEM analysis of the powder obtained in example 2.
FIG. 5 shows the results of SEM analysis of the powder obtained in example 3.
FIG. 6 shows the results of SEM analysis of the powder obtained in example 4.
FIG. 7 shows the results of SEM analysis of the powder obtained in example 5.
FIG. 8 shows the results of SEM analysis of the powder obtained in comparative example 1.
FIG. 9 shows the results of SEM analysis of the powder obtained in comparative example 2.
FIG. 10 shows the results of SEM analysis of the powder obtained in comparative example 3.
FIG. 11 shows the results of SEM analysis of the powder obtained in comparative example 4.
Detailed Description
The following examples further illustrate embodiments of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
The preparation method of the spherical nano cerium dioxide comprises the following steps:
1) cerous nitrate hexahydrate (analytically pure) was dissolved in ethylene glycol to prepare a 0.4mol/L cerous nitrate ethylene glycol solution. Sodium hydroxide (analytically pure) was dissolved in ethylene glycol to prepare a 1.2mol/L sodium hydroxide ethylene glycol solution. 250ml of sodium hydroxide glycol solution was slowly poured into 250ml of cerous nitrate glycol solution with stirring, and stirred at 600rpm for 10min, to cause precipitation reaction.
2) After completion of the precipitation reaction, 40g of hydroxypropylcellulose (analytical grade) was added to the reaction system, and the mixture was stirred at 600rpm for 1 hour to obtain a reaction mixture.
3) Putting the reaction mixture obtained in the step 2) into an oil bath, continuously injecting air into the reaction mixture and stirring by using a high-speed shearing machine. Wherein the oil bath temperature is 140 deg.C, and the air injection speed is 5cm3The high-speed shearing speed is 6000 rpm/min. Meanwhile, the solution changed from milky white to tan, and after 12h, the solution finally changed to bright yellow.
4) Centrifuging the bright yellow mixed solution obtained in the step 3) in a centrifugal machine with the centrifugal force of 10000g, taking a solid, washing the solid product with deionized water and ethanol for three times, and drying the solid product in a forced air drying oven at 80 ℃ for 12 hours to finally obtain yellow powder, namely spherical nano cerium dioxide.
FIG. 1 shows the results of particle size analysis of the bright yellow mixed solution obtained after the high-speed shear dispersion in step 3) for 12 hours after dilution with water by 1000 times. The results showed a D50 of 129nm for the solid particles in the solution.
FIG. 2 is an X-ray diffraction analysis (XRD) pattern showing that the yellow powder is CeO having a cubic fluorite structure2. Calculating CeO according to the Xiele formula2The grain size was 5nm, indicating that the spherical particles belong to a polycrystalline aggregate.
FIG. 3 is a Scanning Electron Microscope (SEM) of the dried powder of step 4). The results show that: the powder consists of spherical particles exhibiting monodispersed characteristics, uniformly distributed, and having a size of about 100 nm.
Example 2
The preparation method of the spherical nano cerium dioxide comprises the following steps:
1) cerous nitrate hexahydrate (analytically pure) was dissolved in ethylene glycol to prepare a 0.7mol/L cerous nitrate ethylene glycol solution. Sodium hydroxide (analytically pure) was dissolved in ethylene glycol to prepare a sodium hydroxide ethylene glycol solution with a concentration of 2.1 mol/L. 250mL of sodium hydroxide glycol solution was slowly poured into 250mL of cerous nitrate glycol solution with stirring, and the mixture was stirred at 600rpm for 10min to cause precipitation reaction.
2) After completion of the precipitation reaction, 40g of hydroxypropylcellulose (analytical grade) was added to the reaction system, and the mixture was stirred at 600rpm for 1 hour to obtain a reaction mixture.
3) Putting the reaction mixture obtained in the step 2) into an oil bath, continuously injecting air into the reaction mixture and stirring by using a high-speed shearing machine. Wherein the oil bath temperature is 140 deg.C, and the air injection speed is 5cm3The high-speed shearing speed is 6000 rpm/min. The high-speed shearing dispersion time is 12h, and a bright yellow mixed solution is obtained.
4) Centrifuging the bright yellow mixed solution obtained in the step 3) in a centrifugal machine with the centrifugal force of 10000g, taking a solid, washing the solid product with deionized water and ethanol for three times, and drying the solid product in a forced air drying oven at 80 ℃ for 12 hours to finally obtain yellow powder, namely spherical nano cerium dioxide.
FIG. 4 shows the SEM of the final sample, and the results show that CeO2The size distribution of the spheres is between 100nm and 200 nm. The results show that: tong (Chinese character of 'tong')By adjusting the concentration of cerous nitrate and sodium hydroxide, the particle size of the product can be controlled.
Example 3
The preparation method of the spherical nano cerium dioxide comprises the following steps:
1) cerous nitrate hexahydrate (analytically pure) was dissolved in ethylene glycol to prepare a 0.3mol/L cerous nitrate ethylene glycol solution. Sodium hydroxide (analytically pure) was dissolved in ethylene glycol to prepare a 0.9mol/L sodium hydroxide ethylene glycol solution. 250ml of sodium hydroxide glycol solution was slowly poured into 250ml of cerous nitrate glycol solution with stirring, and stirred at 600rpm for 10min, to cause precipitation reaction.
2) After completion of the precipitation reaction, 60g of hydroxypropylcellulose (analytical grade) was added to the reaction system, and stirred at 600rpm for 1 hour to obtain a reaction mixture.
3) Putting the reaction mixture obtained in the step 2) into an oil bath, continuously injecting air into the reaction mixture and stirring by using a high-speed shearing machine. Wherein the oil bath temperature is 140 deg.C, and the air injection speed is 5cm3The high-speed shearing speed is 6000 rpm/min. After high-speed shearing and dispersing for 12h, a bright yellow mixed solution is obtained.
4) Centrifuging the bright yellow mixed solution obtained in the step 3) in a centrifugal machine with the centrifugal force of 10000g, taking a solid, washing the solid product with deionized water and ethanol for three times, and drying the solid product in a forced air drying oven at 80 ℃ for 12 hours to finally obtain yellow powder, namely spherical nano cerium dioxide.
FIG. 5 is an SEM of the final sample showing CeO2The size of the spheres is reduced to 40-50 nm. The results show that: by adjusting the addition amount of hydroxypropyl cellulose, the particle size of the product can be controlled.
Example 4
The preparation method of the spherical nano cerium dioxide comprises the following steps:
1) cerous nitrate hexahydrate (analytically pure) was dissolved in ethylene glycol to prepare a 0.4mol/L cerous nitrate ethylene glycol solution. Sodium hydroxide (analytically pure) was dissolved in ethylene glycol to prepare a 1.2mol/L sodium hydroxide ethylene glycol solution. 250ml of sodium hydroxide glycol solution was slowly poured into 250ml of cerous nitrate glycol solution with stirring, and stirred at 600rpm for 10min, to cause precipitation reaction.
2) After completion of the precipitation reaction, 40g of hydroxypropylcellulose (analytical grade) was added to the reaction system, and the mixture was stirred at 600rpm for 1 hour to obtain a reaction mixture.
3) Putting the reaction mixture obtained in the step 2) into an oil bath, continuously injecting air into the reaction mixture and stirring by using a high-speed shearing machine. Wherein the oil bath temperature is 120 deg.C, and the air injection speed is 5cm3The high-speed shearing speed is 6000 rpm/min. After high-speed shearing and dispersing for 36h, a bright yellow mixed solution is obtained.
4) Centrifuging the bright yellow mixed solution obtained in the step 3) in a centrifugal machine with the centrifugal force of 10000g, taking a solid, washing the solid product with deionized water and ethanol for three times, and drying the solid product in a forced air drying oven at 80 ℃ for 12 hours to finally obtain yellow powder, namely spherical nano cerium dioxide.
FIG. 6 is an SEM of the final sample, showing CeO2The size of the spheres is about 100 nm.
Example 5
The preparation method of the spherical nano cerium dioxide comprises the following steps:
1) cerous nitrate hexahydrate (analytically pure) was dissolved in ethylene glycol to prepare a 0.4mol/L cerous nitrate ethylene glycol solution. Sodium hydroxide (analytically pure) was dissolved in ethylene glycol to prepare a 1.2mol/L sodium hydroxide ethylene glycol solution. 250ml of sodium hydroxide glycol solution was slowly poured into 250ml of cerous nitrate glycol solution with stirring, and stirred at 600rpm for 10min, to cause precipitation reaction.
2) After completion of the precipitation reaction, 40g of hydroxypropylcellulose (analytical grade) was added to the reaction system, and the mixture was stirred at 600rpm for 1 hour to obtain a reaction mixture.
3) Putting the reaction mixture obtained in the step 2) into an oil bath, continuously injecting air into the reaction mixture and stirring by using a high-speed shearing machine. Wherein the oil bath temperature is 150 deg.C, and the air injection speed is 5cm3The high-speed shearing speed is 6000 rpm/min. After high-speed shearing and dispersing for 6h, bright yellow is obtainedAnd (4) color mixing solution.
4) Centrifuging the bright yellow mixed solution obtained in the step 3) in a centrifugal machine with the centrifugal force of 10000g, taking a solid, washing the solid product with deionized water and ethanol for three times, and drying the solid product in a forced air drying oven at 80 ℃ for 12 hours to finally obtain yellow powder, namely spherical nano cerium dioxide.
FIG. 7 is an SEM of the final sample showing CeO2The size of the nanospheres is about 100 nm.
The results of example 4 and example 5 show that: in the range of 120 plus 150 ℃, the reaction temperature influences CeO2The generation speed of the nanospheres is high, but the appearance of the final product is not influenced significantly.
Comparative example 1
The concentration of cerous nitrate was 1mol/L and the concentration of sodium hydroxide was 3mol/L, and the other conditions were the same as in example 1.
FIG. 8 shows SEM, CeO of the final sample2The size distribution of the spheres is in the range of 50-200 nm. The results show that the particle size uniformity is reduced when the concentration of cerous nitrate and sodium hydroxide is outside a certain range.
Comparative example 2
The oil bath temperature was 200 ℃. The other conditions were the same as in example 1.
Fig. 9 is an SEM of the final sample. The results show that: the product was not spherical but consisted of 10 μm needles.
Comparative example 3
During the experiment 20g of hydroxypropyl cellulose was added, otherwise the conditions were identical to those of example 1.
Fig. 10 shows the SEM of the final sample. The results show that: after the addition amount of the hydroxypropyl cellulose is reduced to 20g, the spherical particles are obviously agglomerated.
Comparative example 4
No high shear was used during the experiment and the other conditions were the same as in example 1.
Fig. 11 shows the SEM of the final sample. The results show that: high-speed shearing is not adopted, and the product agglomeration phenomenon is obvious.
Claims (10)
1. The preparation method of the spherical nano cerium dioxide is characterized by comprising the following steps:
1) respectively dissolving cerium salt and alkali in an organic solvent, and then mixing the two solutions to perform a precipitation reaction;
2) after the precipitation reaction is finished, adding a high molecular polymer into the reaction system, and stirring to obtain a reaction mixture;
3) shearing and dispersing the reaction mixture obtained in the step 2) at a high speed for 30 min-48 h at the temperature of 40-220 ℃, and continuously blowing gas with oxidability into a reaction system; the high-speed shearing rotating speed is 2000 rpm-15000 rpm;
4) and (3) centrifugally separating the product obtained in the step 3) to obtain a solid, washing and drying to obtain the spherical nano cerium dioxide.
2. The method for preparing spherical nano-ceria according to claim 1, wherein in step 1), the organic solvent is one or a mixture of two or more of alcohols, ethers or ketones with a boiling point of more than 50 ℃.
3. The method for preparing spherical nano ceria according to claim 2, wherein the alcohol is selected from ethanol, methanol, ethylene glycol and glycerol; the ethers are selected from n-butyl ether and tert-butyl ether; the ketones are selected from the group consisting of pentanone and propiophenone.
4. The method for preparing spherical nano-ceria according to claim 1, wherein in step 1), the cerium salt is selected from one or a mixture of two or more of cerium sulfate, cerous nitrate, cerous chloride and ceric ammonium nitrate.
5. The method for preparing spherical nano-ceria according to claim 4, wherein the cerium salt is formulated at a concentration of 0.05mol/L to 0.90 mol/L.
6. The method for preparing spherical nano-ceria according to claim 1, wherein in step 1), the base is selected from one or a mixture of two or more of sodium hydroxide, potassium hydroxide, ammonia water, hydrazine hydrate, tetramethylammonium hydroxide and urea.
7. The method for preparing spherical nano-ceria according to claim 6, wherein the alkali concentration is 0.01mol/L to 6.00 mol/L.
8. The method for preparing spherical nano-ceria according to claim 1, wherein in step 2), the high molecular polymer is selected from one or a mixture of two or more of polyvinylpyrrolidone, hydroxypropyl cellulose and hydroxypropyl methyl cellulose.
9. The method for preparing spherical nano cerium dioxide according to claim 8, wherein the addition amount of the high molecular polymer is 30g/L to 160 g/L.
10. The method for preparing spherical nano ceria of claim 1, wherein in step 3), the oxidizing gas is air, oxygen or chlorine.
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