CN101962203B - 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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CN101962203B
CN101962203B CN 201010503448 CN201010503448A CN101962203B CN 101962203 B CN101962203 B CN 101962203B CN 201010503448 CN201010503448 CN 201010503448 CN 201010503448 A CN201010503448 A CN 201010503448A CN 101962203 B CN101962203 B CN 101962203B
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cerium oxide
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aqueous solution
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CN101962203A (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 preparing technical field, particularly the method for the synthetic different-shape nano-cerium oxide of a kind of hydrothermal method.
Background technology
Quantum mechanical effects due to the nano particle that large small scale is given of nano particle makes nano material and traditional material on properties (as optics, electricity etc.) that larger difference be arranged, and at electronics, optics, chemical ceramics, biological and field of medicaments is widely applied.Nano-oxide is an integral part in 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, the 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:
The starting material that 1) need to add are more, cause cost higher.Take microemulsion method as example, need to add tensio-active agent, cosurfactant, solvent etc.
2) preparation technology is comparatively complicated.Take sol-gel method as row, need to carry out the precursor reaction, the variation of standing generation sol-gel needs 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 the time adds tensio-active agent, and are centrifugal, the techniques such as supersound washing.
These shortcomings have caused at preparatory phase, and the preparations of nanomaterials cost is higher, and the production cycle is long, are difficult to reach the requirement of suitability for industrialized production; And when aftertreatment, present existing equipment is difficult to satisfy the aftertreatment of nano material in enormous quantities, and more technique 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, few all ingredients that adds of trying one's best not only reduces costs, and can simplify aftertreatment technology.Therefore this method can solve the problems of present existence, has good development prospect, to the production of nano material with use larger pushing effect is also arranged.
Summary of the invention
Purpose of the present invention provides a kind of technique 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) under room temperature, compound concentration is the Ce (NO of 0.01-0.1mol/L 3) 6H 2The O aqueous solution;
2) according to volume ratio 1: 1-8: 1-10 adds H 2O 2, can evaporate into gas under the cerous nitrate aqueous solution and 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, reacted 2-72h under 140-240 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to bottom reactor, adds ethanol to disperse 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, when being 2～24h, the nano-cerium oxide of preparing was for octahedra.
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 organic solvent volume ratio be 1: 4～7: 4～7, temperature of reaction is 180～200 ℃, the reaction times, when being 12～48h, the nano-cerium oxide of preparing was nano square.
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 organic solvent volume ratio be 1: 6～10: 6～10, temperature of reaction is 210 ℃～240 ℃, the reaction times, when being 36～72 ℃, the nano-cerium oxide of preparing was nanometer rod.
The reaction that occurs in 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, under high temperature, organic solution evaporates into gas, and the aqueous solution is formed certain pressure, due to Ce (OH) 4Be a kind of unsettled compound, resolve into and CeO under High Temperature High Pressure 2Crystalline growth, the high pressure of toluene can accelerate Ce (OH) 4Decomposition, and at CeO 2During crystallization, larger pressure can limit the growth of crystal, makes its limitation of size in the nano level scope.The present invention is not owing to adding any tensio-active agent, and noresidue after the oxidant hydrogen peroxide that adds reflection 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 technique 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 that cerium oxide nano is octahedra, nano square, nanometer rod.
3) by the adjusting test parameter, reached artificial controllability for microtexture and the size of synthetic cerium oxide nano materials.
This preparation method has obtained the nano-cerium oxide of different-shape, and in the time of can overcoming nano material and prepare, existing condition is harsh, and 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 post-treatment measures such as centrifugal, comparing with the method for former report has huge progress.
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) under room temperature, compound concentration is the Ce (NO of 0.02mol/L 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 with tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 2h under 150 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to bottom reactor, adds ethanol to disperse to get final product.
Embodiment 2:
1) under room temperature, compound concentration is the Ce (NO of 0.06mol/L 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 with tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 36h under 180 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to bottom reactor, adds ethanol to disperse to get final product.
Embodiment 3:
1) under room temperature, compound concentration is the Ce (NO of 0.09mol/L 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 with tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 72h under 240 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to bottom reactor, adds ethanol to disperse to get final product.
Embodiment 4:
1) under room temperature, compound concentration is the Ce (NO of 0.07mol/L 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 with tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 18h under 180 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to bottom reactor, adds ethanol to disperse to get final product.
Embodiment 5:
1) under room temperature, compound concentration is the Ce (NO of 0.1mol/L 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 with tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 54h under 230 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to bottom reactor, adds ethanol to disperse to get final product.
Embodiment 6:
1) under room temperature, compound concentration is the Ce (NO of 0.05mol/L 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 with tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 60h under 240 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to bottom reactor, adds ethanol to disperse to get final product, and obtains the rod-like nano cerium oxide.
Embodiment 7:
1) under room temperature, compound concentration is the Ce (NO of 0.03mol/L 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 with tightness system, inner bag is coated with in the pyroreaction still of one deck tetrafluoroethylene, without any need for stirring;
3) react 24h under 160 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to bottom reactor, adds ethanol to disperse to get final product, and obtains octahedra nano-cerium oxide.

Claims (3)

1. the method for the synthetic different-shape nano-cerium oxide of hydrothermal method, is characterized in that; Adopt following steps:
1) under room temperature, compound concentration is the Ce (NO of 0.01-0.1mol/L 3) 36H 2The O aqueous solution;
2) according to volume ratio 1: 1-8: 1-10 adds H 2O 2, Ce (NO 3) 36H 2The organic solvent that can evaporate into gas under the O aqueous solution and temperature of reaction and not participate in reacting forms mixing solutions;
3) mixing solutions is put into the pyroreaction still, reacted 2-72h under 140-240 ℃;
4) after reaction finishes, go upper solution, nano-cerium oxide directly sinks to bottom reactor, adds ethanol to disperse to get final product; Described organic solvent is toluene, ethanol or acetone.
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; Ce (NO 3) 36H 2The O aqueous solution is 0.01～0.05mol/L, H 2O 2, Ce (NO 3) 36H 2The O aqueous solution and organic solvent volume ratio are 1: 1～4: 1～4, and temperature of reaction is 140～210 ℃, and the reaction times, when being 2～24h, the nano-cerium oxide of preparing was for octahedra.
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) 36H 2The O aqueous solution is 0.06～0.07mol/L, H 2O 2, Ce (NO 3) 36H 2The volume ratio of the O aqueous solution and organic solvent is 1: 4～7: 4～7, and temperature of reaction is 180～200 ℃, and the reaction times, when being 12～48h, the nano-cerium oxide of preparing was nano square.
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CN102992384B (en) * 2012-12-12 2014-07-23 黑龙江大学 Preparation method of triangular prism-shape ceric oxide
CN104843762B (en) * 2015-04-29 2016-04-27 山东科技大学 The preparation method of the cerium oxide nanoparicles that a kind of phthalocyanine is modified
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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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
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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

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陶宇等.微波辅助法制备形貌可控CeO2纳米材料.《中国稀土学报》.2010,第28卷(第4期),第414-419页. *

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