CN115259205A - Preparation method and application of nano cerium oxide - Google Patents
Preparation method and application of nano cerium oxide Download PDFInfo
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Abstract
The invention belongs to the technical field of nano materials, and discloses a preparation method and application of nano cerium oxide. The preparation method comprises the following steps: inputting a cerium salt solution, a precipitator and a surfactant into a multiphase interface reactor in a parallel flow manner, and reacting under a stirring state; then, ageing, centrifuging and washing the slurry obtained by the reaction to obtain a nano cerium carbonate precursor; then roasting the nano cerium carbonate precursor to obtain the cerium carbonate; ce in solution 3+ The molar concentration of (A) is 0.5-1.8mol/L; ce in cerium salt solution 3+ The molar concentration ratio of the precipitating agent to the surfactant is 1: (1-2.0): (0.3% -3%). The cerium dioxide prepared by the method is spherical-like, and has controllable morphology and particle size, good dispersibility and good batch stability of products. The polishing powder can improve the polishing efficiency and the polishing quality. The process of the preparationShort reaction time, high efficiency, good repeatability, simple process and easy industrialization.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method and application of nano cerium oxide.
Background
Cerium oxide (CeO) 2 ) As the polishing powder, the polishing powder has the advantages of high polishing rate, small roughness of the polished surface and micro-waviness of the surface, weak damage to the polished surface and the like, so the polishing powder has wide application in the aspect of polishing optical glass, ultra-large scale integrated circuits, monocrystalline silicon wafers and semiconductor substrate materials. Conventional CeO 2 The polishing powder still has great challenges and limitations in polishing selectivity, surface precision, slurry stability and the like, so that the nano-scale CeO is used 2 As a polishing material is a necessary trend.
At present, the preparation method of cerium dioxide mainly comprises a precipitation method, a hydrothermal method, a sol-gel method and the like. Yang Rong and the like use cerium nitrate and sodium hydroxide/potassium hydroxide as raw materials, and cerium dioxide nanosheets are prepared by a precipitation method, the cerium dioxide nanosheets have equivalent diameters of 0.15-1.2 mu m, noble metal catalysts can be loaded on the cerium dioxide nanosheets to improve the catalytic efficiency, but the method needs non-oxidizing gas for atmosphere protection during the precipitation reaction, so that the process complexity is increased. Tian Zhimin and the like use cerium nitrate and sodium hydroxide as raw materials, prepare nano cerium dioxide by a two-step hydrothermal method, have good biological safety when used as an ultraviolet protective agent, but have harsh reaction conditions, often need to carry out multiple hydrothermal reactions at the temperature of 100-180 ℃ for more than 20 hours at high temperature and high pressure, and need to centrifugally separate products at high speed after the reaction, so that industrial production is difficult to realize.
Generally, the existing methods for preparing cerium dioxide have complicated processes, and the prepared cerium dioxide has irregular shapes such as sheet or plate shapes, or uneven particle sizes. The particle size of the commercially available cerium oxide polishing powder is in the range of 2-7 μm, and when cerium oxide with irregular, uneven or large particle size is used as the polishing powder, the polishing efficiency is low, severe scratches are generated on the surface of a polished workpiece, the flatness is poor, and the quality of the polished workpiece is influenced.
Therefore, it is highly desirable to provide a preparation method which is simple in process, mild in conditions, and easy to industrialize, and can prepare the nano-ceria with a spherical shape and uniform particle size.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a preparation method and application of nano cerium oxide, and the preparation method has the advantages of simple process, mild conditions and easy industrialization; and can prepare the nano cerium dioxide with similar spherical shape and uniform particle size; the polishing powder is used as polishing powder, so that the polishing efficiency is high, and the flatness of the polished workpiece is high.
The invention provides a preparation method of nano cerium oxide.
Specifically, the preparation method of the nano cerium oxide comprises the following steps:
inputting a cerium salt solution, a precipitator and a surfactant into a multiphase interface reactor in a parallel flow manner, and reacting under a stirring state; then, ageing, centrifuging and washing the slurry obtained by the reaction to obtain a nano cerium carbonate precursor; then roasting the nanometer cerium carbonate precursor to prepare nanometer cerium oxide;
ce in the cerium salt solution 3+ The molar concentration of (b) is 0.5-1.8mol/L;
ce in the cerium salt solution 3+ The molar concentration ratio of the precipitating agent to the surface active agent is 1: (1-2.0): (0.3% -3%).
Preferably, the precipitant is selected from at least one of sodium carbonate solution, sodium hydroxide solution, and sodium bicarbonate solution.
Preferably, the surfactant is selected from at least one of polyethylene glycol solution, cetyl trimethyl ammonium bromide solution, sodium oleate solution and citric acid solution.
Preferably, ce is in the cerium salt solution 3+ The molar concentration of (b) is 0.5-1.75mol/L.
Preferably, ce is in the cerium salt solution 3+ The molar concentration ratio of the precipitating agent to the surfactant is 1: (1-1.5): (0.3% -3%).
Preferably, the reaction raw material co-currently fed with the cerium salt solution, the precipitant, and the surfactant further includes a dispersant.
Preferably, the dispersant is polyvinylpyrrolidone.
Preferably, the stirring speed in the stirring process is 1000-5000rpm; further preferably, the rotation speed of stirring during the stirring process is 2500-4000rpm.
Preferably, the flow rates of the cerium salt solution, the precipitator and the surfactant which are input into the multiphase interface reactor in a parallel flow mode are 100-500mL/min respectively; further preferably, the flow rates of the cerium salt solution, the precipitator and the surfactant which are input into the multiphase interface reactor in a parallel flow mode are 250-400mL/min respectively.
Preferably, the temperature of the reaction is 10-50 ℃; further preferably, the temperature of the reaction is 15-40 ℃.
Preferably, the aging time is 1 to 4 hours.
Preferably, the roasting process is that the nano cerium carbonate precursor is heated to 450-750 ℃ from room temperature (5-40 ℃) at a heating rate of 0.5-5 ℃/min, and then is kept for 1-3h; further preferably, the roasting process is to heat the nano cerium carbonate precursor to 500-750 ℃ from room temperature (5-40 ℃) at a heating rate of 1-3 ℃/min, and then keep the temperature for 1-2h.
In a second aspect, the present invention provides a nano-cerium oxide.
The nano cerium oxide is prepared by the preparation method, is in a sphere-like shape, and has the particle size of 10-60nm.
Further preferably, the particle size of the nano cerium oxide is 20-50nm.
In a third aspect, the present invention provides a polishing powder.
Specifically, the polishing powder comprises the nano cerium oxide.
The multiphase interface reactor has the advantages of good product batch stability, high production efficiency and the like. However, in the preparation of nano cerium oxide, the morphology of the nano cerium oxide is difficult to control by using a multiphase interface reactor, and the nano cerium oxide with irregularity and nonuniform particle size is easy to generate. The invention strictly controls Ce in the cerium salt solution 3+ The molar concentration ratio of the precursor to a precipitator and a surfactant and the selection of a special surfactant can form a rich and fine bubble liquid film when materials react in the microreactor, and micro-zone precipitation is carried out in the bubble liquid film to prevent the particles from growing and agglomerating, so that the prepared precursor is nano particles; in the subsequent roasting process, the agglomeration and growth of particles can be further reduced by controlling the roasting temperature, so that the finally prepared nano cerium oxide is in a sphere-like shape, the particle size distribution is uniform, and the dispersibility is good.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention strictly controls Ce in the cerium salt solution 3+ The molar concentration ratio of the cerium dioxide to a precipitator and a surfactant, and the selection of a special surfactant, and the preparation of the nano cerium dioxide by adopting a multiphase interfacial reactor. The cerium dioxide prepared by the method is spherical, and has the advantages of controllable morphology and particle size, good dispersibility, good product batch stability and the like. The nano cerium dioxide prepared by the method is used as polishing powder, so that the polishing efficiency and the polishing quality can be improved.
(2) The preparation method provided by the invention has the advantages of short reaction time, high efficiency, good repeatability, simple process and easy industrialization.
Drawings
FIG. 1 is an XRD pattern of a nano cerium carbonate precursor prepared in example 1;
FIG. 2 is an XRD pattern of nano-cerium oxide prepared in example 1;
FIG. 3 is an SEM photograph of nano-cerium oxide prepared in example 1;
FIG. 4 is an SEM photograph of cerium oxide prepared in comparative example 1;
FIG. 5 is an SEM photograph of cerium oxide prepared in comparative example 2;
FIG. 6 is an SEM photograph of cerium oxide prepared in comparative example 3;
fig. 7 is an SEM image of cerium oxide prepared in comparative example 3.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The heterogeneous interfacial reactors used in the following examples or comparative examples were obtained according to the International publication No. WO 2021/217550 A1. The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
A preparation method of nano cerium oxide comprises the following steps:
(1) A sodium carbonate solution with a concentration of 1.75mol/L, a cerium chloride solution with a concentration of 1.75mol/L, a surfactant solution with a concentration of 0.006mol/L (in this example, cetyl Trimethyl Ammonium Bromide (CTAB)) and a polyvinylpyrrolidone solution with a concentration of 0.00014mol/L were prepared for use. In this example, cerium ion (Ce) 3+ ) The molar concentration ratio of the precipitating agent (P) to the surfactant (S) is as follows: n (Ce) 3+ ):n(P - ):n(S)＝1:1:0.34％。
(2) And (3) carrying out parallel flow and equal volume on the four solutions by a metering pump, conveying the solutions into a continuous multiphase interface reactor, starting a stirring motor of the reactor, and carrying out continuous synthesis reaction, wherein the flow rate of each solution is 300mL/min, and the stirring speed is 3000rpm.
(3) And (3) standing the slurry obtained by the reaction in the step (2) for 2h for aging, centrifuging, washing and drying to obtain a nano cerium carbonate precursor, placing the nano cerium carbonate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 2h at the heating rate of 2 ℃/min, cooling to room temperature after roasting is finished, and taking out to obtain spheroidal nano cerium dioxide, wherein the yield of the nano cerium dioxide is 99.5% and the purity of the nano cerium dioxide is 99.9% through calculation and test.
The XRD pattern of the nano cerium carbonate prepared in the example is shown in figure 1, the diffraction peak of the nano cerium carbonate is identical with the standard pattern PDF #30-0295 of cerium carbonate hexahydrate, and other miscellaneous peaks do not exist, which indicates that pure phase nano cerium carbonate is prepared. The nano-cerium dioxide prepared in the embodiment is light yellow powder, the XRD pattern is shown in figure 2, the diffraction peak of the nano-cerium dioxide is well matched with the standard pattern PDF #34-0394 of the cerium dioxide, and the pure-phase nano-cerium dioxide with good crystallinity is prepared. The microscopic morphology analysis of the nano ceria is carried out by adopting a scanning electron microscope, and the SEM image is shown as figure 3, wherein a in figure 3 is the SEM image under the scale of 20nm, and b in figure 3 is the SEM image under the scale of 100 nm. As can be seen from a in FIG. 3, the nano-ceria is spheroidal, and the particle size is about 20 nm; it can be seen from b in fig. 3 that the nano ceria has a uniform particle size distribution and good dispersibility.
Example 2
A preparation method of nano cerium oxide comprises the following steps:
(1) Preparing a sodium carbonate solution with a concentration of 1.0mol/L, a cerium chloride solution with a concentration of 0.8mol/L and a surfactant solution with a concentration of 0.0178mol/L (in the embodiment, the surfactant is sodium oleate) for standby. In this example, cerium ion (Ce) 3+ ) The molar concentration ratio of the precipitating agent (P) to the surfactant (S) is as follows: n (Ce) 3+ ):n(P - ):n(S)＝1:1.25:2.23％。
(2) And (3) carrying out parallel flow and equal volume on the three solutions by a metering pump, conveying the three solutions into a continuous multiphase interface reactor, starting a stirring motor of the reactor, and carrying out continuous synthesis reaction, wherein the flow rate of each solution is 300mL/min, and the stirring speed is 3000rpm.
(3) And (3) standing the slurry obtained by the reaction in the step (2) for 2h for aging, centrifuging, washing and drying to obtain a nano cerium carbonate precursor, placing the nano cerium carbonate in a muffle furnace for roasting at the roasting temperature of 750 ℃ for 2h, wherein the heating rate is 2 ℃/min, and taking out after the roasting is finished and the temperature is reduced to room temperature to obtain the faint yellow spherical nano cerium dioxide with the particle size of about 30nm. The yield of nano cerium dioxide is 99.0% and the purity is 99.8% by calculation and test.
Example 3
A preparation method of nano cerium oxide comprises the following steps:
(1) A sodium carbonate solution with a concentration of 1.75mol/L, a cerium chloride solution with a concentration of 1.16mol/L, and a surfactant solution with a concentration of 0.010mol/L (in the embodiment, the surfactant is polyethylene glycol) are prepared for standby. In this example, cerium ion (Ce) 3+ ) The molar concentration ratio of the precipitating agent (P) to the surfactant (S) is as follows: n (Ce) 3+ ):n(P - ):n(S)＝1:1.5:0.86％。
(2) And (3) carrying out parallel flow and equal volume on the three solutions by a metering pump, conveying the three solutions into a continuous multiphase interface reactor, starting a stirring motor of the reactor, and carrying out continuous synthesis reaction, wherein the flow rate of each solution is 300mL/min, and the stirring speed is 3500rpm.
(3) And (3) standing the slurry obtained by the reaction in the step (2) for 2h for aging, centrifuging, washing and drying to obtain a nano cerium carbonate precursor, placing the nano cerium carbonate in a muffle furnace for roasting at the roasting temperature of 750 ℃ for 2h, wherein the heating rate is 2 ℃/min, and taking out after the roasting is finished and the temperature is reduced to room temperature to obtain the faint yellow spherical nano cerium dioxide with the particle size of about 50nm. The nano cerium dioxide yield is 98.5% and the purity is 99.6% by calculation and test.
Comparative example 1
A method for preparing cerium oxide, comprising the steps of:
(1) A sodium carbonate solution having a concentration of 1.75mol/L, a cerium chloride solution having a concentration of 0.58mol/L, and a surfactant solution having a concentration of 0.002mol/L (in this example, cetyltrimethylammonium bromide (CTAB)) and a polyvinylpyrrolidone solution having a concentration of 0.00014mol/L were preparedAnd standing by. In this example, cerium ion (Ce) 3+ ) The molar concentration ratio of the precipitating agent (P) to the surfactant (S) is as follows: n (Ce) 3+ ):n(P - ):n(S)＝1:3.02:0.34％。
(2) And (3) carrying out parallel flow and equal volume on the four solutions by a metering pump, conveying the solutions into a continuous multiphase interface reactor, starting a stirring motor of the reactor, and carrying out continuous synthesis reaction, wherein the flow rate of each solution is 300mL/min, and the stirring speed is 3000rpm.
(3) And (3) standing the slurry obtained by the reaction in the step (2) for 2h for aging, centrifuging, washing and drying to obtain a nano cerium carbonate precursor, placing the nano cerium carbonate in a muffle furnace for roasting at the roasting temperature of 600 ℃, keeping the temperature for 2h, and taking out the nano cerium carbonate precursor after the roasting is finished and the temperature is reduced to room temperature to obtain cerium dioxide, wherein the yield of the cerium dioxide is 97.0% and the purity of the cerium dioxide is 98.0% through calculation and test.
The microscopic morphology of cerium oxide was analyzed by scanning electron microscopy, and the SEM image of the cerium oxide prepared in this comparative example is shown in FIG. 4, where a is an SEM image on a scale of 4 μm and b is an SEM image on a scale of 5 μm in FIG. 4. As can be seen from FIG. 4, the cerium oxide particles prepared in this comparative example had a particle size of more than 1 μm, and had non-uniform particle size and irregular morphology. This may be due to the fact that the concentration of the precipitant sodium carbonate is relatively high, so that the local concentration is too high.
Comparative example 2
A method for preparing cerium oxide, comprising the steps of:
(1) A sodium carbonate solution with a concentration of 1.75mol/L, a cerium chloride solution with a concentration of 1.75mol/L, a surfactant solution with a concentration of 0.006mol/L (in the embodiment, the surfactant is sodium dodecyl benzene sulfonate) and a polyvinylpyrrolidone solution with a concentration of 0.00014mol/L are prepared for standby. In this example, cerium ion (Ce) 3+ ) The molar concentration ratio of the precipitating agent (P) to the surfactant (S) is as follows: n (Ce) 3+ ):n(P - ):n(S)＝1:1:0.34％。
(2) And (3) carrying out parallel flow and equal volume on the four solutions by a metering pump, conveying the solutions into a continuous multiphase interface reactor, starting a stirring motor of the reactor, and carrying out continuous synthesis reaction, wherein the flow rate of each solution is 300mL/min, and the stirring speed is 3000rpm.
(3) Standing the slurry obtained by the reaction in the step (2) for 2h for aging, centrifuging, washing and drying to obtain a nano cerium carbonate precursor, placing the nano cerium carbonate in a muffle furnace for roasting at the roasting temperature of 600 ℃, keeping the temperature for 2h, and taking out the nano cerium carbonate precursor after the roasting is finished and the temperature is reduced to room temperature to obtain spheroidal nano cerium dioxide, wherein the yield of the nano cerium dioxide is 97.5% and the purity is 98.5% through calculation and test.
The microscopic morphology of the cerium oxide was analyzed by scanning electron microscopy, and the SEM image of the cerium oxide prepared in this comparative example is shown in FIG. 5. As can be seen from fig. 5, the cerium oxide prepared in this comparative example has a regular shape and a uniform size, and the size of the flake cerium oxide is several micrometers.
Comparative example 3
A method for preparing cerium oxide, comprising the steps of:
(1) A sodium carbonate solution having a concentration of 2.0mol/L, a cerium chloride solution having a concentration of 2.0mol/L, and a surfactant solution having a concentration of 0.006mol/L (in this example, cetyltrimethylammonium bromide (CTAB)) and a polyvinylpyrrolidone solution having a concentration of 0.00014mol/L were prepared for use. In this example, cerium ion (Ce) 3+ ) The molar concentration ratio of the precipitating agent (P) to the surfactant (S) is as follows: n (Ce) 3+ ):n(P - ):n(S)＝1:1:0.3％。
(2) And (3) carrying out parallel flow and equal volume on the four solutions by a metering pump, conveying the solutions into a continuous multiphase interface reactor, starting a stirring motor of the reactor, and carrying out continuous synthesis reaction, wherein the flow rate of each solution is 300mL/min, and the stirring speed is 3000rpm.
(3) And (3) standing the slurry obtained by the reaction in the step (2) for 2h for aging, centrifuging, washing and drying to obtain a nano cerium carbonate precursor, placing the nano cerium carbonate in a muffle furnace for roasting at the roasting temperature of 600 ℃ for 2h at the heating rate of 2 ℃/min, cooling to room temperature after roasting is finished, and taking out to obtain spheroidal nano cerium dioxide, wherein the yield of the nano cerium dioxide is 97.2% and the purity is 98.3% through calculation and test.
The microscopic morphology of the cerium oxide was analyzed by scanning electron microscopy, and the SEM image of the cerium oxide prepared in this comparative example is shown in FIG. 6. It can be seen from fig. 6 that the cerium oxide prepared in this comparative example has a large particle size of about several micrometers, a small particle size of 300 to 500nm, non-uniform particle size, irregular morphology, low polishing efficiency when used as a polishing powder, and poor surface flatness of a workpiece to be polished.
Comparative example 4
(1) A sodium carbonate solution having a concentration of 1.75mol/L, a cerium chloride solution having a concentration of 1.75mol/L, and a surfactant solution having a concentration of 0.006mol/L (in this example, cetyltrimethylammonium bromide (CTAB)) and a polyvinylpyrrolidone solution having a concentration of 0.00014mol/L were prepared for use. In this example, cerium ion (Ce) 3+ ) The molar concentration ratio of the precipitating agent (P) to the surfactant (S) is as follows: n (Ce) 3+ ):n(P - ):n(S)＝1:1:0.35％。
(2) And (3) enabling the four solutions to flow in parallel through a metering pump and convey to a continuous microreactor in an isometric manner, starting a stirring motor of the reactor to perform continuous synthetic reaction, wherein the flow rate of each solution is 300mL/min, and the stirring speed is 3000rpm.
(3) And (3) standing the slurry obtained by the reaction in the step (2) for 2h for aging, centrifuging, washing and drying to obtain a nano cerium carbonate precursor, placing the nano cerium carbonate in a muffle furnace for roasting at the roasting temperature of 900 ℃ for 2h, wherein the temperature rise rate is 2 ℃/min, and taking out after the roasting is finished and the temperature is reduced to room temperature to obtain spheroidal nano cerium dioxide, wherein the yield of the nano cerium dioxide is 96.5% and the purity is 96.8% through calculation and test.
The microscopic morphology of the cerium oxide was analyzed by scanning electron microscopy, and the SEM image of the cerium oxide prepared in this comparative example is shown in FIG. 7. As can be seen from FIG. 7, the cerium oxide particles prepared in this comparative example have serious agglomeration, non-uniform particle size and irregular morphology, and other impurities are attached to the surface of the cerium oxide particles, so that the purity is reduced; in addition, when the temperature is too high, the hardness of cerium oxide is high, which limits the application of cerium oxide in polishing powder.
Claims (10)
1. A preparation method of nano cerium oxide is characterized by comprising the following steps:
inputting a cerium salt solution, a precipitator and a surfactant into a multiphase interface reactor in a parallel flow manner, and reacting under a stirring state; then, ageing, centrifuging and washing the slurry obtained by the reaction to obtain a nano cerium carbonate precursor; then roasting the nano cerium carbonate precursor to prepare nano cerium oxide;
ce in the cerium salt solution 3+ The molar concentration of (A) is 0.5-1.8mol/L;
ce in the cerium salt solution 3+ The molar concentration ratio of the precipitating agent to the surfactant is 1: (1-2.0): (0.3% -3%).
2. The method according to claim 1, wherein the precipitant is at least one selected from the group consisting of a sodium carbonate solution, a sodium hydroxide solution, and a sodium bicarbonate solution.
3. The method according to claim 1, wherein the surfactant is at least one selected from the group consisting of a polyvinylpyrrolidone solution, a polyethylene glycol solution, a cetyltrimethylammonium bromide solution, a sodium oleate solution, and a citric acid solution.
4. The method according to any one of claims 1 to 3, wherein Ce is contained in the cerium salt solution 3+ The molar concentration of (b) is 0.5-1.75mol/L.
5. The method according to any one of claims 1 to 3, wherein Ce is contained in the cerium salt solution 3+ The molar concentration ratio of the precipitating agent to the surfactant is 1: (1-1.5): (0.3% -3%).
6. The production method according to claim 1, wherein the rotation speed of stirring during the stirring is 1000 to 5000rpm; preferably, the rotation speed of stirring during the stirring process is 2500-4000rpm.
7. The method according to claim 5, wherein the flow rates of the cerium salt solution, the precipitant and the surfactant which are co-currently fed into the multiphase interfacial reactor are 100-500mL/min, respectively.
8. The preparation method of claim 1, wherein the calcination is performed by heating the nano cerium carbonate precursor to 450-750 ℃ at a heating rate of 0.5-5 ℃/min from 5-40 ℃ and then maintaining the temperature for 1-3h.
9. The nano cerium oxide prepared by the preparation method of any one of claims 1 to 8, wherein the nano cerium oxide is in a sphere-like shape, and the particle size of the nano cerium oxide is 10 to 60nm.
10. A polishing powder comprising the nano cerium oxide according to claim 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115974127A (en) * | 2022-11-25 | 2023-04-18 | 深圳市聚芯半导体材料有限公司 | Quasi-spherical nano cerium dioxide, suspension thereof, preparation method and application |
| CN117843046A (en) * | 2024-01-04 | 2024-04-09 | 兰州兰石中科纳米科技有限公司 | Preparation method of high-purity nano nickel oxide |
| CN117843020A (en) * | 2024-01-04 | 2024-04-09 | 兰州兰石中科纳米科技有限公司 | Preparation method of nano alumina powder |
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