CN109704385A - A kind of method that ethylene glycol auxiliary polyvinyl alcohol prepares flower-shaped cerium oxide - Google Patents
A kind of method that ethylene glycol auxiliary polyvinyl alcohol prepares flower-shaped cerium oxide Download PDFInfo
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- CN109704385A CN109704385A CN201910079504.XA CN201910079504A CN109704385A CN 109704385 A CN109704385 A CN 109704385A CN 201910079504 A CN201910079504 A CN 201910079504A CN 109704385 A CN109704385 A CN 109704385A
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- polyvinyl alcohol
- ethylene glycol
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Abstract
A kind of method that ethylene glycol auxiliary polyvinyl alcohol prepares flower-shaped cerium oxide, belongs to rare earth material technical field.For the present invention with water and ethylene glycol collectively as solvent, polyvinyl alcohol passes through direct precipitation method synthesis of oxalic acid cerium precursor as dispersing agent, precipitating reagent of the ammonium oxalate as cerium source.Under the booster action of polyvinyl alcohol, water/oil microreactor is formed with water and ethylene glycol, on the one hand, the viscosity of ethylene glycol is bigger compared to water, can reinforce the combination of cerium precursor and polyvinyl alcohol, on the other hand, the peptizaiton of polyvinyl alcohol promotes cerium precursor to crack, and forms cerium precursor.Cerium precursor is calcined according to certain temperature program in high temperature reaction stove, obtains flower-shaped cerium oxide.Preparation process flow of the present invention is simple, required equipment is simple, it is raw materials used nontoxic, preparation cost is low, the flower-shaped cerium oxide of gained has high-specific surface area, quick adsorption pigment, the light-catalyzed reaction process of the dyestuffs such as quickening methyl blue, methyl orange, acid orange there can be good prospects for commercial application in the photocatalytic process.
Description
Technical field
The present invention relates to a kind of preparation method of rare earth material technical field, specifically a kind of ethylene glycol assists polyvinyl alcohol
The method for preparing flower-shaped cerium oxide.
Background technique
In recent years, cerium oxide causes the wide of researcher because playing most important effect in environment and energy related field
General concern.Ceria oxide powder has unique physics and chemical characteristic, as high mechanical strength, cationic conductivity, oxygen store energy
Power etc., refractory ceramics, catalyst, fuel cell, solar battery and in terms of be widely applied.It is special
The nano-cerium oxide of pattern, compared to block cerium oxide, the characteristics such as redox reaction and oxygen conveying are greatly improved.
Therefore, the excellent properties based on cerium oxide and potential application field, synthesis morphology controllable cerium oxide are more and more closed
Note.
Preparing the common method of cerium oxide at present is liquid phase method, mainly includes sol-gal process, the precipitation method, hydrothermal synthesis
Method, Hydrolyze method etc..Sol-gal process is that polycondensation is hydrolyzed in homogeneous phase solution using inorganic salts or metal organic alkoxide as raw material
Reaction, colloidal sol gradually become gel, by gel drying, roasting, obtain nano-powder.The preparation method can increase multicomponent body
The uniformity of system reacts easily controllable, is frequently utilized for preparation specific surface area very big gel and powder.The precipitation method are in the liquid phase
It chemically reacts, generates the presoma insoluble in solvent, presoma obtains nano-metal-oxide by dry, roasting.It should
Preparation method can be used for preparing a variety of nano oxidized because cost of material is low, simple process, easy to operate, low for equipment requirements
Object is suitble to synthesize single or composite oxides nanoparticle.
Summary of the invention
It is an object of that present invention to provide a kind of ethylene glycol auxiliary polyvinyl alcohol method for preparing flower-shaped cerium oxide, the present invention with
Collectively as solvent, polyvinyl alcohol passes through Direct precipitation as dispersing agent, precipitating reagent of the ammonium oxalate as cerium source for water and ethylene glycol
Method synthesizes cerium precursor.Specifically poly-vinyl alcohol solution is slowly added into the aqueous solution of cerium source, adds ethylene glycol as auxiliary
Cosolvent, ammonium oxalate are mixed thoroughly it as precipitating reagent, using ultrasonator, stirring at normal temperature 4-10 h, and filtering is heavy
Starch, 60-100 DEG C of dry 5-24 h, obtains oxalic acid cerium precursor.Polyvinyl alcohol belongs to macromolecule polyol, solution viscosity
Higher, suitable solution concentration can play the role of connection and dispersion, be conducive to the morphosis for controlling target product.Second two
Hydroxyl in alcohol has hydrophily, can be miscible with polyvinyl alcohol water solution, forms microreactor, has adjust in the reaction system
Save the effect of the presoma direction of growth.Contain polyvinyl alcohol in the presoma of preparation, easily resolves into vapor and dioxy through calcining
Change carbon, the reunion degree of final product can be improved.
For the present invention using polyvinyl alcohol as dispersing agent, water and ethylene glycol form water/oil systems, are prepared for cerium precursor and gather
The compound of vinyl alcohol obtains flower-shaped cerium oxide through calcining, provides well to prepare the rare earth oxide material of special appearance
Preparation approach.
The present invention is achieved by the following technical solutions, and the method for the present invention is related to a kind of ethylene glycol auxiliary polyvinyl alcohol system
The method of standby flower-shaped cerium oxide, mainly comprises the steps that
(1) preparation of poly-vinyl alcohol solution: weighing 0.4-3.6 g polyvinylalcohol solids, be placed in a beaker, and adds 50 mL and goes
Ionized water, 100-140 DEG C of oil bath heating, dissolves polyvinyl alcohol thoroughly, is cooled to room temperature；
(2) preparation of ammonium oxalate solution: 0.1-0.9 g ammonium oxalate solid is weighed, is placed in a beaker, 50 mL deionizations are added
Water and ethylene glycol, volume ratio 1:1-1:5；
(3) by the poly-vinyl alcohol solution and ammonium oxalate solution in step (1) and (2), be respectively added slowly to be to 50 mL concentration
In the cerium source solution of 0.1-2 mol/L, stirring at normal temperature reacts 4-10 h, filtering precipitate, and 60-100 DEG C of dry 5-24 h is obtained
Cerium precursor obtains flower-shaped cerium oxide through 400-700 DEG C of calcining 1-8 h.
Cerium source solution described in step (3) is cerous nitrate, cerium chloride, any one in cerium oxide.
The invention has the following beneficial effects: the present invention using water and ethylene glycol collectively as solvent, polyvinyl alcohol conduct
Dispersing agent, precipitating reagent of the ammonium oxalate as cerium source pass through direct precipitation method synthesis of oxalic acid cerium precursor.Cerium is reinforced using ethylene glycol
The combination effect of presoma and polyvinyl alcohol promotes presoma to crack, before forming flower-shaped cerium using the peptizaiton of polyvinyl alcohol
Body is driven, provides good preparation approach to prepare the rare earth oxide material of special construction.
The present invention is using polyvinyl alcohol as dispersing agent, in the mixed system of water and ethylene glycol, is assisted using ethylene glycol poly-
The direction of growth of vinyl alcohol adjusting cerium precursor.On the one hand, the viscosity of ethylene glycol is bigger compared to water, can reinforce cerium precursor
And the combination of polyvinyl alcohol, on the other hand, the peptizaiton of polyvinyl alcohol promote cerium precursor to crack, and form cerium precursor.?
Calcine cerium precursor according to certain temperature program in high temperature reaction stove, obtain flower-shaped cerium oxide, nanometer sheet with a thickness of 10-50
Nm, the size of flower-like structure are 1-5 μm, and specific surface area is 80-120 m2 g-1。
Preparation process flow of the present invention is simple, and required equipment is simple, and raw materials used nontoxic, preparation cost is low, and gained is flower-shaped
Cerium oxide has high-specific surface area, can quick adsorption pigment in the photocatalytic process, accelerate methyl blue, methyl orange, acid orange
The light-catalyzed reaction process of equal dyestuffs, has good prospects for commercial application.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of final product in embodiment 1；
Fig. 2 is the specific surface area of final product in embodiment 1.
Specific embodiment
The present embodiment be premised on inventive technique scheme under implemented, give detailed embodiment and process,
But protection scope of the present invention is not limited to following embodiments.
Embodiment 1.
0.4 g polyvinylalcohol solids are weighed, are placed in a beaker, 50 mL deionized waters, 100 DEG C of oil bath heatings 2 are added
H dissolves polyvinyl alcohol thoroughly, is cooled to room temperature, and obtains poly-vinyl alcohol solution.0.1g ammonium oxalate solid is weighed, beaker is placed in
In, 50 mL deionized waters and ethylene glycol are added, volume ratio 1:1 obtains ammonium oxalate solution.By two kinds of solution obtained above
It is respectively added slowly in the cerium source solution for being 0.5 mol/L to 50 mL concentration, stirring at normal temperature 4 h of reaction, filtering precipitate, 60
Dry 24 h, obtain cerium precursor, through 500 DEG C of calcining 1h, obtain flower-like structure cerium oxide, the thickness 20-50 nm of nanometer sheet,
The size of flower-like structure is 2-3 μm, and specific surface area is 90 m2 g-1。
Embodiment 2.
0.6 g polyvinylalcohol solids are weighed, are placed in a beaker, 50 mL deionized waters, 100 DEG C of oil bath heatings 2 are added
H dissolves polyvinyl alcohol thoroughly, is cooled to room temperature, and obtains poly-vinyl alcohol solution.0.3 g ammonium oxalate solid is weighed, beaker is placed in
In, 50 mL deionized waters and ethylene glycol are added, volume ratio 1:1 obtains ammonium oxalate solution.By two kinds of solution obtained above
It is respectively added slowly in the cerium source solution for being 0.1 mol/L to 50 mL concentration, stirring at normal temperature 4 h of reaction, filtering precipitate, 60
DEG C dry 24 h, obtain cerium precursor, through 500 DEG C of 2 h of calcining, obtain flower-like structure cerium oxide, the thickness 20-40 of nanometer sheet
Nm, the size of flower-like structure are 1-3 μm, and specific surface area is 95 m2 g-1。
Embodiment 3.
0.8 g polyvinylalcohol solids are weighed, are placed in a beaker, 50 mL deionized waters, 100 DEG C of oil bath heatings 3 are added
H dissolves polyvinyl alcohol thoroughly, is cooled to room temperature, and obtains poly-vinyl alcohol solution.0.5 g ammonium oxalate solid is weighed, beaker is placed in
In, 50 mL deionized waters and ethylene glycol are added, volume ratio 1:1 obtains ammonium oxalate solution.By two kinds of solution obtained above
It is respectively added slowly in the cerium source solution for being 0.1 mol/L to 50 mL concentration, stirring at normal temperature 4 h of reaction, filtering precipitate, 60
DEG C dry 24 h, obtain cerium precursor, through 500 DEG C of calcining 1-8 h, obtain flower-like structure cerium oxide, the thickness 10-30 of nanometer sheet
Nm, the size of flower-like structure are 1-2 μm, and specific surface area is 100 m2 g-1。
Embodiment 4.
1 g polyvinylalcohol solids are weighed, are placed in a beaker, 50 mL deionized waters, 140 DEG C of oil bath heatings 3 are added
H dissolves polyvinyl alcohol thoroughly, is cooled to room temperature, and obtains poly-vinyl alcohol solution.0.8 g ammonium oxalate solid is weighed, beaker is placed in
In, 50 mL deionized waters and ethylene glycol are added, volume ratio 1:2 obtains ammonium oxalate solution.By two kinds of solution obtained above
It is respectively added slowly in the cerium source solution for being 0.5 mol/L to 50 mL concentration, stirring at normal temperature 6 h of reaction, filtering precipitate,
100 DEG C of 2 h of drying, obtain cerium precursor, through 600 DEG C of 2 h of calcining, obtain flower-like structure cerium oxide, the thickness 10-20 of nanometer sheet
Nm, the size of flower-like structure are 1-2 μm, and specific surface area is 110 m2 g-1。
Embodiment 5.
1.2 g polyvinylalcohol solids are weighed, are placed in a beaker, 50 mL deionized waters, 140 DEG C of oil bath heatings 4 are added
H dissolves polyvinyl alcohol thoroughly, is cooled to room temperature, and obtains poly-vinyl alcohol solution.0.5 g ammonium oxalate solid is weighed, beaker is placed in
In, 50 mL deionized waters and ethylene glycol are added, volume ratio 1:2 obtains ammonium oxalate solution.By two kinds of solution obtained above
It is respectively added slowly in the cerium source solution for being 0.2 mol/L to 50 mL concentration, stirring at normal temperature 6 h of reaction, filtering precipitate,
100 DEG C of 2 h of drying, obtain cerium precursor, through 600 DEG C of 2 h of calcining, obtain flower-like structure cerium oxide, the thickness 20-30 of nanometer sheet
Nm, the size of flower-like structure are 1-3 μm, and specific surface area is 105 m2 g-1。
Claims (3)
1. a kind of method that ethylene glycol auxiliary polyvinyl alcohol prepares flower-shaped cerium oxide, it is characterised in that: polyvinyl alcohol is dissolved in heat
Water forms uniform poly-vinyl alcohol solution, is slowly added into the aqueous solution of cerium source, adds ethylene glycol as secondary solvent, grass
Sour ammonium is mixed thoroughly it as precipitating reagent, using ultrasonator, stirring at normal temperature 4-10 h, filtering precipitate, 60-
100 DEG C of dry 5-24 h, obtain oxalic acid cerium precursor；According to 8 in high temperature reaction stoveoThe temperature program of C/min, through 400-
700 DEG C of calcining 1-8 h, obtain flower-shaped cerium oxide, and nanometer sheet thickness is 10-50 nm, and flower-like structure is having a size of 1-5 μm, specific surface
Product is 80-120 m2 g-1。
2. the method that a kind of ethylene glycol auxiliary polyvinyl alcohol according to claim 1 prepares flower-shaped cerium oxide, feature exist
In, comprising the following steps:
(1) preparation of poly-vinyl alcohol solution: weighing 0.4-3.6 g polyvinylalcohol solids, be placed in a beaker, and adds 50 mL and goes
Ionized water, 100-140 DEG C of oil bath heating 2-6 h, dissolves polyvinyl alcohol thoroughly, is cooled to room temperature；
(2) preparation of ammonium oxalate solution: 0.1-0.9 g ammonium oxalate solid is weighed, is placed in a beaker, 50 mL deionizations are added
Water and ethylene glycol, volume ratio 1:1-1:5；
(3) by the poly-vinyl alcohol solution and ammonium oxalate solution in step (1) and (2), be respectively added slowly to be to 50 mL concentration
In the cerium source solution of 0.1-2 mol/L, stirring at normal temperature reacts 4-10 h, filtering precipitate, and 60-100 DEG C of dry 5-24 h is obtained
Cerium precursor obtains flower-shaped cerium oxide through 400-700 DEG C of calcining 1-8 h.
3. the method that a kind of ethylene glycol auxiliary polyvinyl alcohol according to claim 2 prepares flower-shaped cerium oxide, feature exist
In: cerium source solution described in step (3) be cerous nitrate, cerium chloride, any one in cerium oxide.
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Citations (5)
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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 |
-
2019
- 2019-01-28 CN CN201910079504.XA patent/CN109704385B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
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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》 * |
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