CN101962203A - Method for synthesizing nano cerium oxide with different morphologies by hydrothermal method - Google Patents

Method for synthesizing nano cerium oxide with different morphologies by hydrothermal method Download PDF

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CN101962203A
CN101962203A CN 201010503448 CN201010503448A CN101962203A CN 101962203 A CN101962203 A CN 101962203A CN 201010503448 CN201010503448 CN 201010503448 CN 201010503448 A CN201010503448 A CN 201010503448A CN 101962203 A CN101962203 A CN 101962203A
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cerium oxide
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aqueous solution
temperature
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CN101962203B (en
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陶宇
王辉
吴海平
陶国良
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Liyang Chang Technology Transfer Center Co., Ltd.
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Changzhou University
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Abstract

The invention belongs to the technical field of nanomaterials, and in particular relates to a method for synthesizing nano cerium oxide with different morphologies by a hydrothermal method. The method comprises the following steps of: 1) preparing aqueous solution of Ce(NO3).6H2O with concentration of 0.01 to 0.1mol/L at the room temperature; 2) adding H2O2, aqueous solution of cerium nitrate and an organic solvent into the solution to form mixed solution according to a volume ratio of 1:1-8:1-10, wherein the organic solvent can be volatized into gas at the reaction temperature and does not participate in the reaction; 3) placing the mixed solution into a high-temperature reaction kettle and reacting the mixture at the temperature of between 140 and 240 DEG C for 2 to 72 hours; and 4) pouring off upper solution after the reaction and adding ethanol for dispersion, wherein the nano cerium oxide is directly settled at the bottom of the reaction kettle. Because any surfactant is not added, and residues are not remained after hydrogen peroxide serving as an oxidant is added for reaction, the post-treatment process required by the conventional nano preparation process can be saved and the industrial application of the nanomaterial is dramatically promoted.

Description

The method of the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method
Technical field
The invention belongs to the nano material preparation technical field, the method for the synthetic different-shape nano-cerium oxide of particularly a kind of hydrothermal method.
Background technology
Because the quantum mechanical effects of the nano particle that big small scale is given of nano particle, make nano material and traditional material some in nature (as optics, electricity etc.) bigger difference is arranged, and at electronics, optics, chemical ceramics, biological and field of medicaments has obtained widespread use.Nano-oxide is an integral part in the nano material, its preparation, and structure, performance and application have become one of focus of various countries researchist concern.Cerium oxide is the extremely wide light rare earths oxide compound of a kind of purposes, has N-type semiconductor character, is widely used in fuel cell, luminescent material, glass decolouring finings, catalyzer, electronic ceramics, fields such as uv-absorbing material and photochemical catalysis.
The method for preparing nano-cerium oxide is a lot, and at present the most frequently used is liquid phase method, mainly comprises: the precipitator method, sol-gel method, hydrothermal method, microemulsion method etc.These methods can prepare the nano-cerium oxide of various patterns, but these preparation methods' shortcoming is also especially obvious:
1) needs the starting material of adding more, cause cost higher.With the microemulsion method is example, needs to add tensio-active agent, cosurfactant, solvent etc.
2) preparation technology is comparatively complicated.With the sol-gel method is row, need carry out the precursor reaction, leaves standstill the variation that produces sol-gel, need the cycle longer, and the later stage needs high temperature sintering.
3) aftertreatment comparatively bothers.Most of liquid phase methods all need precipitation because preparation time adds tensio-active agent, and are centrifugal, technologies such as supersound washing.
These shortcomings have caused at preparatory phase, and the preparation cost of nano material is higher, and the production cycle is long, are difficult to reach industrial production requirement; And when aftertreatment, present existing equipment is difficult to satisfy the aftertreatment of nano material in enormous quantities, and more technology has also increased substantially cost during aftertreatment.So present preparation method has seriously limited the development of nano material.
Therefore, under this prerequisite, investigators constantly simplify preparation technology and solve this difficult problem.In preparation process, the adding all ingredients of trying one's best few not only reduces cost, and can simplify aftertreatment technology.Therefore this method can solve the problems of present existence, has bright development prospect, to the production of nano material with use bigger pushing effect is also arranged.
Summary of the invention
Purpose of the present invention provides a kind of technology comparatively simply to prepare the preparation method of pattern controllable nano cerium oxide.
The scheme of the technological step that the present invention adopts is as follows
One material mixture ratio
Concentration is 99.9% cerous nitrate Ce (NO 3) 6H 2O
Concentration is 99.9% ethanol C 2H 6O, concentration are 99.9% acetone C 3H 6O or concentration are 99.9% toluene C 7H 10
Concentration is 30% oxydol H 2O 2
Above-mentioned concentration all refers to mass percentage concentration.
1, the method for the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method is characterized in that; Adopt following steps:
1) compound concentration is the Ce (NO of 0.01-0.1mol/L under the room temperature 3) 6H 2The O aqueous solution;
2) add H according to volume ratio 1: 1-8: 1-10 2O 2, can evaporate into gas under the cerous nitrate aqueous solution and the temperature of reaction and the organic solvent that do not participate in reacting forms mixing solutions;
3) mixing solutions is put into the pyroreaction still, 140-240 ℃ is reacted 2-72h down;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to the reactor bottom, adds ethanol and disperses to get final product.
2, the method for the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method as claimed in claim 1 is characterized in that; Described organic solvent is toluene, ethanol or acetone.
3, the method for the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method as claimed in claim 1 is characterized in that; Ce (NO 3) 6H 2The O aqueous solution is 0.01～0.05mol/L, H 2O 2, the cerous nitrate aqueous solution and organic solvent volume ratio be 1: 1～4: 1～4, temperature of reaction is 140～210 ℃, the reaction times, the nano-cerium oxide of preparing was for octahedra when being 2～24h.
4, the method for the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method as claimed in claim 1 is characterized in that: Ce (NO 3) 6H 2The O aqueous solution is 0.06～0.07mol/L, H 2O 2, the cerous nitrate aqueous solution and volume of organic solvent ratio be 1: 4～7: 4～7, temperature of reaction is 180～200 ℃, the reaction times, the nano-cerium oxide of preparing was the nanometer square when being 12～48h.
5, the method for the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method as claimed in claim 1 is characterized in that: Ce (NO 3) 6H 2The O aqueous solution is 0.05～0.1mol/L, H 2O 2, the cerous nitrate aqueous solution and volume of organic solvent ratio be 1: 6～10: 6～10, temperature of reaction is 210 ℃～240 ℃, the reaction times, the nano-cerium oxide of preparing was a nanometer rod when being 36～72 ℃.
The reaction that takes place in the said process is:
2H 2O 2→2H 2O+O 2
4Ce 3++O 2+2H 2O→4Ce 4++4OH -
4Ce 4++4OH -→Ce(OH) 4
Ce(OH) 4→CeO 2+2H 2O
In thermal and hydric environment, organic solution evaporates into gas under the high temperature, and the aqueous solution is formed certain pressure, because Ce (OH) 4Be a kind of unstable compounds, under High Temperature High Pressure, resolve into and CeO 2Crystalline growth, the high pressure of toluene can quicken Ce (OH) 4Decomposition, and at CeO 2During crystallization, bigger pressure can limit the crystalline growth, makes its limitation of size in the nano level scope.The present invention is not owing to add any tensio-active agent, and the oxidant hydrogen peroxide that adds reflection back noresidue can be saved the needed aftertreatment technology of traditional nano preparation technique, and the industrial applications of nano material is had huge pushing effect.
The invention has the advantages that:
1) this preparation method is simple, and cost is low, and technology is simple, has removed the needed precipitation of traditional liquid phase method from, filters supersound washing, the centrifugal aftertreatment technology that waits;
2) this preparation method can prepare the nano-cerium oxide of different-shape, comprises the cerium oxide nano octahedron, nanometer square, nanometer rod.
3), reached artificial controllability for the microtexture and the size of synthetic cerium oxide nano materials by regulating test parameter.
This preparation method has obtained the nano-cerium oxide of different-shape, and existing condition harshness in the time of can overcoming nano material preparation, raw materials cost is higher, a series of shortcomings such as aftertreatment trouble, and with compare with class methods, this method reaction conditions is comparatively even, needs raw material less, has removed precipitation from, filter, supersound washing, numerous aftertreatment measures such as centrifugal had been compared great advance with former reported method.
Description of drawings
Fig. 1 is the octahedral scanning electron microscope picture of cerium oxide nano according to embodiment one preparation;
Fig. 2 is the scanning electron microscope picture according to the cerium oxide nano square of embodiment two preparations;
Fig. 3 is the transmission electron microscope picture according to the cerium oxide nano-rod of embodiment three preparations;
Fig. 4 is the octahedral X ray electron diffraction of the cerium oxide nano picture according to embodiment one preparation;
Embodiment
Embodiment 1:
1) compound concentration is the Ce (NO of 0.02mol/L under the room temperature 3) 6H 2The O aqueous solution;
2) in order successively with 4mlCe (NO 3) 6H 2The O aqueous solution, 4m toluene and 2mlH 2O 2, joining and have tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 2h down at 150 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to the reactor bottom, adds ethanol and disperses to get final product.
Embodiment 2:
1) compound concentration is the Ce (NO of 0.06mol/L under the room temperature 3) 6H 2The O aqueous solution;
2) in order successively with 12mlCe (NO 3) 6H 2The O aqueous solution, 14m toluene and 3mlH 2O 2, joining and have tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 36h down at 180 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to the reactor bottom, adds ethanol and disperses to get final product.
Embodiment 3:
1) compound concentration is the Ce (NO of 0.09mol/L under the room temperature 3) 6H 2The O aqueous solution;
2) in order successively with 24mlCe (NO 3) 6H 2The O aqueous solution, 24m toluene and 3mlH 2O 2, joining and have tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 72h down at 240 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to the reactor bottom, adds ethanol and disperses to get final product.
Embodiment 4:
1) compound concentration is the Ce (NO of 0.07mol/L under the room temperature 3) 6H 2The O aqueous solution;
2) in order successively with 25mlCe (NO 3) 6H 2The O aqueous solution, 25m toluene and 5mlH 2O 2, joining and have tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 18h down at 180 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to the reactor bottom, adds ethanol and disperses to get final product.
Embodiment 5:
1) compound concentration is the Ce (NO of 0.1mol/L under the room temperature 3) 6H 2The O aqueous solution;
2) in order successively with 72mlCe (NO 3) 6H 2The O aqueous solution, 80m toluene and 8mlH 2O 2, joining and have tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 54h down at 230 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to the reactor bottom, adds ethanol and disperses to get final product.
Embodiment 6:
1) compound concentration is the Ce (NO of 0.05mol/L under the room temperature 3) 6H 2The O aqueous solution;
2) in order successively with 40mlCe (NO 3) 6H 2The O aqueous solution, 24m ethanol and 4mlH 2O 2, joining and have tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 60h down at 240 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to the reactor bottom, adds ethanol and disperses to get final product, and obtains the rod-like nano cerium oxide.
Embodiment 7:
1) compound concentration is the Ce (NO of 0.03mol/L under the room temperature 3) 6H 2The O aqueous solution;
2) in order successively with 32mlCe (NO 3) 6H 2The O aqueous solution, 30m acetone and 8mlH 2O 2, joining and have tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 24h down at 160 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to the reactor bottom, adds ethanol and disperses to get final product, and obtains octahedra nano-cerium oxide.

Claims (5)

1. the method for the synthetic different-shape nano-cerium oxide of hydrothermal method is characterized in that; Adopt following steps:
1) compound concentration is the Ce (NO of 0.01-0.1mol/L under the room temperature 3) 6H 2The O aqueous solution;
2) add H according to volume ratio 1: 1-8: 1-10 2O 2, can evaporate into gas under the cerous nitrate aqueous solution and the temperature of reaction and the organic solvent that do not participate in reacting forms mixing solutions;
3) mixing solutions is put into the pyroreaction still, 140-240 ℃ is reacted 2-72h down;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to the reactor bottom, adds ethanol and disperses to get final product.
2. the method for the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method as claimed in claim 1 is characterized in that; Described organic solvent is toluene, ethanol or acetone.
3. the method for the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method as claimed in claim 1 is characterized in that; Ce (NO 3) 6H 2The O aqueous solution is 0.01～0.05mol/L, H 2O 2, the cerous nitrate aqueous solution and organic solvent volume ratio be 1: 1～4: 1～4, temperature of reaction is 140～210 ℃, the reaction times, the nano-cerium oxide of preparing was for octahedra when being 2～24h.
4. the method for the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method as claimed in claim 1 is characterized in that: Ce (NO 3) 6H 2The O aqueous solution is 0.06～0.07mol/L, H 2O 2, the cerous nitrate aqueous solution and volume of organic solvent ratio be 1: 4～7: 4～7, temperature of reaction is 180～200 ℃, the reaction times, the nano-cerium oxide of preparing was the nanometer square when being 12～48h.
5. the method for the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method as claimed in claim 1 is characterized in that: Ce (NO 3) 6H 2The O aqueous solution is 0.05～0.1mol/L, H 2O 2, the cerous nitrate aqueous solution and volume of organic solvent ratio be 1: 6～10: 6～10, temperature of reaction is 210 ℃～240 ℃, the reaction times, the nano-cerium oxide of preparing was a nanometer rod when being 36～72 ℃.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102992384A (en) * 2012-12-12 2013-03-27 黑龙江大学 Preparation method of triangular prism-shape ceric oxide
CN104843762A (en) * 2015-04-29 2015-08-19 山东科技大学 Preparation method of phthalocyanin modified cerium dioxide nano particles
CN108325525A (en) * 2018-03-01 2018-07-27 中国科学技术大学 A kind of catalyst of catalytic oxidation of low-concentration methane and preparation method thereof and application
CN110040760A (en) * 2019-05-09 2019-07-23 常州大学 A kind of method of controllable preparation cerium lanthanum-oxides solid solution nanometer rods

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101508456A (en) * 2009-03-17 2009-08-19 江苏工业学院 Method for auxiliary preparation of different-shape nano-cerium oxide with microwave
CN101759221A (en) * 2008-12-25 2010-06-30 国家纳米技术与工程研究院 Method for preparing nano cerium dioxide powder

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101759221A (en) * 2008-12-25 2010-06-30 国家纳米技术与工程研究院 Method for preparing nano cerium dioxide powder
CN101508456A (en) * 2009-03-17 2009-08-19 江苏工业学院 Method for auxiliary preparation of different-shape nano-cerium oxide with microwave

Non-Patent Citations (2)

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Title
《Materials Letters》 20041231 Jin-Seok Lee et al. Crystallization behavior of nano-ceria powders by hydrothermal synthesis using a mixture of H2O2 and NH4OH 第390-393页 1-5 第58卷, 2 *
《中国稀土学报》 20100831 陶宇等 微波辅助法制备形貌可控CeO2纳米材料 第414-419页 1-5 第28卷, 第4期 2 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102992384A (en) * 2012-12-12 2013-03-27 黑龙江大学 Preparation method of triangular prism-shape ceric oxide
CN102992384B (en) * 2012-12-12 2014-07-23 黑龙江大学 Preparation method of triangular prism-shape ceric oxide
CN104843762A (en) * 2015-04-29 2015-08-19 山东科技大学 Preparation method of phthalocyanin modified cerium dioxide nano particles
CN108325525A (en) * 2018-03-01 2018-07-27 中国科学技术大学 A kind of catalyst of catalytic oxidation of low-concentration methane and preparation method thereof and application
CN110040760A (en) * 2019-05-09 2019-07-23 常州大学 A kind of method of controllable preparation cerium lanthanum-oxides solid solution nanometer rods

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