CN109704385B - Method for preparing flower-like cerium oxide by using ethylene glycol-assisted polyvinyl alcohol - Google Patents
Method for preparing flower-like cerium oxide by using ethylene glycol-assisted polyvinyl alcohol Download PDFInfo
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Abstract
A method for preparing flower-like cerium oxide by using ethylene glycol to assist polyvinyl alcohol belongs to the technical field of rare earth materials. The invention synthesizes the precursor of cerium oxalate by a direct precipitation method by using water and ethylene glycol as solvents, polyvinyl alcohol as a dispersing agent and ammonium oxalate as a precipitator of a cerium source. Under the auxiliary action of polyvinyl alcohol, the cerium precursor and water and ethylene glycol form a water/oil microreactor, on one hand, the viscosity of the ethylene glycol is higher than that of the water, the combination of the cerium precursor and the polyvinyl alcohol can be strengthened, and on the other hand, the cerium precursor is promoted to crack by the dispersion action of the polyvinyl alcohol to form the cerium precursor. And calcining the cerium precursor in a high-temperature reaction furnace according to a certain temperature-rising program to obtain flower-shaped cerium oxide. The preparation process has the advantages of simple flow, simple required equipment, nontoxic raw materials and low preparation cost, and the obtained flower-like cerium oxide has high specific surface area, can quickly adsorb pigments in the photocatalysis process, accelerates the photocatalysis reaction process of dyes such as methyl blue, methyl orange, acid orange and the like, and has good industrial application prospect.
Description
Technical Field
The invention relates to a preparation method in the technical field of rare earth materials, in particular to a method for preparing flower-like cerium oxide by using ethylene glycol to assist polyvinyl alcohol.
Background
In recent years, cerium oxide has attracted considerable attention from researchers because it plays a crucial role in environmental and energy-related fields. Cerium oxide powder has unique physical and chemical properties such as high mechanical strength, cationic conductivity, oxygen storage capacity, etc., and is widely used in high-temperature ceramics, catalysts, fuel cells, solar cells, polishing materials, etc. Compared with bulk cerium oxide, the nano cerium oxide with special morphology has greatly improved characteristics of oxidation-reduction reaction, oxygen transmission and the like. Therefore, the synthesis of cerium oxide with controllable morphology is receiving more and more attention based on the excellent performance and potential application field of cerium oxide.
The conventional method for preparing cerium oxide is a liquid phase method, and mainly comprises a sol-gel method, a precipitation method, a hydrothermal synthesis method, a hydrolysis method and the like. The sol-gel method is to take inorganic salt or metal organic alkoxide as raw materials, carry out hydrolytic polycondensation reaction in homogeneous solution, gradually turn sol into gel, dry and bake the gel to obtain nano powder. The preparation method can increase the uniformity of a multi-component system, is easy to control the reaction, and is often used for preparing gel and powder with large specific surface area. The precipitation method is to carry out chemical reaction in a liquid phase to generate a precursor which is insoluble in a solvent, and the precursor is dried and roasted to obtain the nano metal oxide. The preparation method has the advantages of low raw material cost, simple process, simple and convenient operation and low equipment requirement, can be used for preparing various nano oxides, and is suitable for synthesizing single or composite oxide nanoparticles.
Disclosure of Invention
The invention aims to provide a method for preparing flower-like cerium oxide by using glycol-assisted polyvinyl alcohol. The method comprises the steps of slowly adding a polyvinyl alcohol solution into a cerium source water solution, adding ethylene glycol as an auxiliary solvent, adding ammonium oxalate as a precipitator, completely and uniformly mixing the materials by using an ultrasonic oscillator, stirring the mixture at normal temperature for 4 to 10 hours, filtering precipitates, and drying the precipitates at 60 to 100 ℃ for 5 to 24 hours to obtain a cerium oxalate precursor. The polyvinyl alcohol belongs to high-molecular polyol, the solution viscosity of the polyvinyl alcohol is high, and the polyvinyl alcohol can play a role in connection and dispersion at a proper solution concentration, so that the morphological structure of a target product can be controlled. Hydroxyl in the ethylene glycol has hydrophilicity, can be mixed and dissolved with a polyvinyl alcohol aqueous solution to form a micro-reactor, and has the function of adjusting the growth direction of a precursor in a reaction system. The prepared precursor contains polyvinyl alcohol, and is easy to decompose into water vapor and carbon dioxide after calcination, so that the agglomeration degree of the final product can be improved.
According to the invention, polyvinyl alcohol is used as a dispersing agent, water and ethylene glycol form a water/oil system, a compound of a cerium precursor and the polyvinyl alcohol is prepared, and flower-shaped cerium oxide is obtained by calcining, so that a good preparation way is provided for preparing a rare earth oxide material with a special morphology.
The invention is realized by the following technical scheme, and relates to a method for preparing flower-shaped cerium oxide by using ethylene glycol-assisted polyvinyl alcohol, which mainly comprises the following steps:
(1) preparing a polyvinyl alcohol solution: weighing 0.4-3.6 g of polyvinyl alcohol solid, placing the polyvinyl alcohol solid in a beaker, adding 50 mL of deionized water, heating in an oil bath at the temperature of 140 ℃ to completely dissolve the polyvinyl alcohol, and cooling to room temperature;
(2) preparing an ammonium oxalate solution: weighing 0.1-0.9 g of ammonium oxalate solid, placing the solid in a beaker, and adding 50 mL of deionized water and ethylene glycol according to the volume ratio of 1: 1-1: 5;
(3) and (3) respectively and slowly adding the polyvinyl alcohol solution and the ammonium oxalate solution in the steps (1) and (2) into 50 mL of cerium source solution with the concentration of 0.1-2 mol/L, stirring and reacting at normal temperature for 4-10 h, filtering the precipitate, drying at 60-100 ℃ for 5-24 h to obtain a cerium precursor, and calcining at 400-700 ℃ for 1-8 h to obtain the flower-shaped cerium oxide.
The cerium source solution in the step (3) is any one of cerium nitrate, cerium chloride and cerium oxide.
The invention has the following beneficial effects: the invention adopts water and glycol as solvent, polyvinyl alcohol as dispersant and ammonium oxalate as precipitant of cerium source, and synthesizes cerium oxalate precursor by direct precipitation method. The method has the advantages that the combination effect of the cerium precursor and the polyvinyl alcohol is reinforced by the ethylene glycol, the precursor is promoted to crack by the dispersion effect of the polyvinyl alcohol, the flower-shaped cerium precursor is formed, and a good preparation way is provided for preparing the rare earth oxide material with a special structure.
The invention takes polyvinyl alcohol as a dispersant, and utilizes ethylene glycol to assist polyethylene in a mixed system of water and ethylene glycolThe alcohol adjusts the growth direction of the cerium precursor. On one hand, the viscosity of the glycol is higher than that of water, so that the combination of the cerium precursor and the polyvinyl alcohol can be reinforced, and on the other hand, the dispersion effect of the polyvinyl alcohol promotes the cracking of the cerium precursor to form the cerium precursor. Calcining the cerium precursor in a high-temperature reaction furnace according to a certain temperature rise program to obtain flower-shaped cerium oxide, wherein the thickness of the nanosheet is 10-50 nm, the size of the flower-shaped structure is 1-5 mu m, and the specific surface area is 80-120 m2 g-1。
The preparation process has the advantages of simple flow, simple required equipment, nontoxic raw materials and low preparation cost, and the obtained flower-like cerium oxide has high specific surface area, can quickly adsorb pigments in the photocatalysis process, accelerates the photocatalysis reaction process of dyes such as methyl blue, methyl orange, acid orange and the like, and has good industrial application prospect.
Drawings
FIG. 1 is a scanning electron micrograph of the final product of example 1;
FIG. 2 is the specific surface area of the final product in example 1.
Detailed Description
The present embodiment is implemented on the premise of the technical solution of the invention, and a detailed implementation manner and a process are given, but the scope of the invention is not limited to the following embodiments.
Example 1.
Weighing 0.4 g of polyvinyl alcohol solid, placing the polyvinyl alcohol solid in a beaker, adding 50 mL of deionized water, heating in an oil bath at 100 ℃ for 2 h to completely dissolve polyvinyl alcohol, and cooling to room temperature to obtain a polyvinyl alcohol solution. 0.1g of ammonium oxalate solid is weighed and placed in a beaker, and 50 mL of deionized water and ethylene glycol are added according to the volume ratio of 1:1 to obtain an ammonium oxalate solution. Slowly adding the two solutions into 50 mL of 0.5 mol/L cerium source solution, stirring at normal temperature for reaction for 4 h, filtering the precipitate, drying at 60 for 24 h to obtain a cerium precursor, calcining at 500 ℃ for 1h to obtain flower-like structure cerium oxide, wherein the thickness of the nanosheet is 20-50 nm, the size of the flower-like structure is 2-3 mu m, and the specific surface area is 90 m2 g-1。
Example 2.
Weighing 0.6 g of polyvinyl alcohol solid, placing the polyvinyl alcohol solid in a beaker, adding 50 mL of deionized water, heating in an oil bath at 100 ℃ for 2 h to completely dissolve polyvinyl alcohol, and cooling to room temperature to obtain a polyvinyl alcohol solution. 0.3 g of ammonium oxalate solid is weighed and placed in a beaker, and 50 mL of deionized water and ethylene glycol are added according to the volume ratio of 1:1 to obtain an ammonium oxalate solution. Slowly adding the two solutions into 50 mL of 0.1 mol/L cerium source solution, stirring at normal temperature for reaction for 4 h, filtering the precipitate, drying at 60 ℃ for 24 h to obtain a cerium precursor, calcining at 500 ℃ for 2 h to obtain flower-like structure cerium oxide, wherein the thickness of the nanosheet is 20-40 nm, the size of the flower-like structure is 1-3 mu m, and the specific surface area is 95 m2 g-1。
Example 3.
Weighing 0.8 g of polyvinyl alcohol solid, placing the polyvinyl alcohol solid in a beaker, adding 50 mL of deionized water, heating in an oil bath at 100 ℃ for 3 h to completely dissolve polyvinyl alcohol, and cooling to room temperature to obtain a polyvinyl alcohol solution. 0.5 g of ammonium oxalate solid is weighed and placed in a beaker, and 50 mL of deionized water and ethylene glycol are added according to the volume ratio of 1:1 to obtain an ammonium oxalate solution. Slowly adding the two solutions into 50 mL of 0.1 mol/L cerium source solution, stirring at normal temperature for reaction for 4 h, filtering the precipitate, drying at 60 ℃ for 24 h to obtain a cerium precursor, calcining at 500 ℃ for 1-8 h to obtain flower-like structure cerium oxide, wherein the thickness of the nanosheet is 10-30 nm, the size of the flower-like structure is 1-2 mu m, and the specific surface area is 100 m2 g-1。
Example 4.
Weighing 1g of polyvinyl alcohol solid, placing the polyvinyl alcohol solid in a beaker, adding 50 mL of deionized water, heating in an oil bath at 140 ℃ for 3 h to completely dissolve polyvinyl alcohol, and cooling to room temperature to obtain a polyvinyl alcohol solution. 0.8 g of ammonium oxalate solid is weighed and placed in a beaker, and 50 mL of deionized water and ethylene glycol are added according to the volume ratio of 1:2 to obtain an ammonium oxalate solution. Slowly adding the two solutions into 50 mL of 0.5 mol/L cerium source solution, stirring at normal temperature for reaction for 6 h, filtering the precipitate, drying at 100 ℃ for 2 h to obtain a cerium precursor, calcining at 600 ℃ for 2 h to obtain flower-shaped cerium oxide nanosheet with thickness of 10-20 nm and flower-shaped knotThe size of the structure is 1-2 μm, and the specific surface area is 110 m2 g-1。
Example 5.
Weighing 1.2 g of polyvinyl alcohol solid, placing the polyvinyl alcohol solid in a beaker, adding 50 mL of deionized water, heating in an oil bath at 140 ℃ for 4 h to completely dissolve polyvinyl alcohol, and cooling to room temperature to obtain a polyvinyl alcohol solution. 0.5 g of ammonium oxalate solid is weighed and placed in a beaker, and 50 mL of deionized water and ethylene glycol are added according to the volume ratio of 1:2 to obtain an ammonium oxalate solution. Slowly adding the two solutions into 50 mL of 0.2 mol/L cerium source solution, stirring at normal temperature for reaction for 6 h, filtering the precipitate, drying at 100 ℃ for 2 h to obtain a cerium precursor, calcining at 600 ℃ for 2 h to obtain flower-like structure cerium oxide, wherein the thickness of the nanosheet is 20-30 nm, the size of the flower-like structure is 1-3 mu m, and the specific surface area is 105 m2 g-1。
Claims (3)
1. A method for preparing flower-like cerium oxide by using ethylene glycol to assist polyvinyl alcohol is characterized by comprising the following steps: dissolving polyvinyl alcohol in hot water to form a uniform polyvinyl alcohol solution, slowly adding the uniform polyvinyl alcohol solution into a cerium source water solution, adding ethylene glycol as an auxiliary solvent, adding ammonium oxalate as a precipitator, completely and uniformly mixing the solution by using an ultrasonic oscillator, stirring the solution at normal temperature for 4 to 10 hours, filtering precipitates, and drying the precipitates at 60 to 100 ℃ for 5 to 24 hours to obtain a cerium oxalate precursor; in a high-temperature reaction furnace according to 8oCalcining at 400-700 ℃ for 1-8 h by a temperature rise program of C/min to obtain the flower-shaped cerium oxide, wherein the thickness of the nano-sheet is 10-50 nm, the size of the flower-shaped structure is 1-5 mu m, and the specific surface area is 80-120 m2 g-1。
2. The method for preparing flower-like cerium oxide from ethylene glycol-assisted polyvinyl alcohol according to claim 1, comprising the following steps:
(1) preparing a polyvinyl alcohol solution: weighing 0.4-3.6 g of polyvinyl alcohol solid, placing the polyvinyl alcohol solid in a beaker, adding 50 mL of deionized water, heating in an oil bath at the temperature of 140 ℃ for 2-6 h to completely dissolve the polyvinyl alcohol, and cooling to room temperature;
(2) preparing an ammonium oxalate solution: weighing 0.1-0.9 g of ammonium oxalate solid, placing the solid in a beaker, and adding 50 mL of deionized water and ethylene glycol according to the volume ratio of 1: 1-1: 5;
(3) and (3) respectively and slowly adding the polyvinyl alcohol solution and the ammonium oxalate solution in the steps (1) and (2) into 50 mL of cerium source solution with the concentration of 0.1-2 mol/L, stirring and reacting at normal temperature for 4-10 h, filtering the precipitate, drying at 60-100 ℃ for 5-24 h to obtain a cerium precursor, and calcining at 400-700 ℃ for 1-8 h to obtain the flower-shaped cerium oxide.
3. The method for preparing flower-like cerium oxide from ethylene glycol-assisted polyvinyl alcohol according to claim 2, wherein: the cerium source solution in the step (3) is any one of cerium nitrate, cerium chloride and cerium oxide.
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| CN101978018A (en) * | 2008-03-20 | 2011-02-16 | 株式会社Lg化学 | Method for preparing cerium oxide, cerium oxide prepared therefrom and cmp slurry comprising the same |
| CN102531021A (en) * | 2010-12-13 | 2012-07-04 | 西安迈克森新材料有限公司 | Method for preparing size-uniform cerium dioxide nanometer hollow microsphere |
| CN105731515A (en) * | 2016-01-28 | 2016-07-06 | 郑州航空工业管理学院 | Mesoporous flower-shaped CeO2, as well as preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1704339A (en) * | 2004-06-03 | 2005-12-07 | 中南大学 | Process for preparing high purity active nano ceria |
| CN101104524A (en) * | 2006-07-14 | 2008-01-16 | 中南大学 | Process for preparing nanometer cerium dioxide |
| CN101978018A (en) * | 2008-03-20 | 2011-02-16 | 株式会社Lg化学 | Method for preparing cerium oxide, cerium oxide prepared therefrom and cmp slurry comprising the same |
| CN102531021A (en) * | 2010-12-13 | 2012-07-04 | 西安迈克森新材料有限公司 | Method for preparing size-uniform cerium dioxide nanometer hollow microsphere |
| CN105731515A (en) * | 2016-01-28 | 2016-07-06 | 郑州航空工业管理学院 | Mesoporous flower-shaped CeO2, as well as preparation method and application thereof |
Non-Patent Citations (1)
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| Pedro Dura＇n等.Cerium (IV) oxide synthesis and sinterable powders prepared by the polymeric organic complex solution method.《Journal of the European Ceramic Society》.2002,1711–1721. * |
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