CN109133140A - A method of preparing cerium oxide nanoparticles - Google Patents
A method of preparing cerium oxide nanoparticles Download PDFInfo
- Publication number
- CN109133140A CN109133140A CN201810977417.1A CN201810977417A CN109133140A CN 109133140 A CN109133140 A CN 109133140A CN 201810977417 A CN201810977417 A CN 201810977417A CN 109133140 A CN109133140 A CN 109133140A
- Authority
- CN
- China
- Prior art keywords
- cerium
- cerous nitrate
- oxide nanoparticles
- nano
- cerium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention provides a kind of methods for preparing cerium oxide nanoparticles: first, by cerous nitrate, pyridine -2,5- dicarboxylic acids is dissolved in dehydrated alcohol and the in the mixed solvent of DMF respectively, the volume ratio of two kinds of solvents is 1:1, and it is 7.3~9.0 that ammonium hydroxide is added after then two kinds of solution are mixed evenly and adjusts its pH value；Then mixed solution is set in a round bottom flask, 10~40min is reacted in laboratory microwave reaction unit, centrifuge washing after reaction is cooling, 60 DEG C are dried to obtain cerium polymerization of olefin using catalyst polymer nano-particle；Finally, obtained drying sample is placed in Muffle furnace, 1~4h is calcined at 500~800 DEG C, obtains CeO after being cooled to room temperature2Nano particle.The present invention has 1. homogeneous heatings, thermal gradient small；2. side reaction is few, product purity is high；3. low energy consumption, energy utilization rate is high；4. heating speed is fast, the reaction time is short；5. series of advantages such as heating environment cleanings.This method provides a kind of method rapidly and efficiently for the synthesis of nanoscale ceria.
Description
Technical field
The present invention relates to cerium dioxide nano materials, and in particular to the method for preparing cerium oxide nanoparticles.
Background technique
Rare earth coordination polymer is a big important class in plurality of coordination polymer, because of it in optics, urge
The extensive use of change, magnetics etc. has obtained the universal concern of researcher.In the research of various rare earth materials, rare-earth oxidation
The preparation and application of object are always primary study object.By regulate and control rare earth oxide morphology and size come control its performance and
Using and one of the emphasis of current research.By the rare earth oxide one for simply calcining synthesis to rare earth coordination polymer
As have many advantages, such as porous structure, and biggish specific surface, therefore also have more excellent performance.Nano ceric oxide removes
Special performance with general nano material also has the distinctive architectural characteristics such as nano material morphology and size itself, certainly
Its irreplaceable status in numerous nano materials is determined.Due to its it is unique chemistry and electron configuration, mechanical stability and
Biocompatibility and include interesting catalysis and electrochemical properties.Nano ceric oxide can make also as quantum size effect
" blue shift " occurs for ultra-violet absorption spectrum, is used as ultraviolet absorber.For ecological environment and energy resources related fields
For, the controllable nano ceric oxide of synthesis morphology and size has boundless application prospect.It is well known that various
Different-shape and the nano ceric oxide of size are often different in nature, thus prepare the nano ceric oxide of different-shape at
For the hot spot of nano materials research.
More research work is carried out to being synthetically prepared for ceria both at home and abroad at present, the system of nano ceric oxide
Preparation Method has very much, wherein different according to the condition of preparation, preparation method can be divided into gas phase, solid phase and liquid phase method, and hydro-thermal
Method is a kind of most common method in liquid phase method.Such as: Maheswari and his partner have synthesized hexagon with hydro-thermal method
CeO2Nano particle.Takaaki Taniguchi etc. uses oleic acid cerium as the presoma of chemical modification, the water in ammonia spirit
Solution condensation, the controlledly synthesis nanocrystalline ceria of size adjustable and the ceria nano-crystalline structure of doping.In addition, may be used also
The cerium micro-/ nano composite material with flower-like structure has been synthesized using the method for mediation, and has passed through calcined oxide cerium precursor
It is prepared for cerium oxide with similar structure.
In recent years, our seminars have been realized in a series of micro-/ nano coordination polymer preparation nano materials as aoxidized
Cerium, other rare earth oxides etc..For example, being successfully synthetically prepared out the ceria of various morphology and sizes with hydro-thermal method, such as
Cerium polymerization of olefin using catalyst polymer is first prepared by simple hydro-thermal method, then the nucleocapsid that partial size is about 400nm is obtained by high-temperature calcination
Ceria.We also use Microwave-assisted firing method to be synthesized in confined conditions with the microwave for having pressure apparatus at the same time
Then cerium polymerization of olefin using catalyst polymer (CeCPs) ultra micro ball obtains the multilayer that partial size is about 300~500nm by calcining presoma again
Core-shell structure ceria ball.Above-mentioned this hydro-thermal method is although easy to operate but very time consumption and energy consumption, and this microwave-assisted
Although heating substantially reduces the time of reaction, product purity is also higher, but it is needed in the microwave tank with pressure
It is reacted, while needing higher temperature that could complete series reaction.
Summary of the invention
To solve to prepare CeO in the prior art2The more harsh problem of the condition of nano particle, the present invention provide one kind and adopt
CeO is synthesized with microwave-assisted no template microwave method2The method of nano particle, this method without template, rapidly and efficiently, low cost, it is low
Energy consumption.
The invention adopts the following technical scheme:
A method of cerium oxide nanoparticles are prepared, high-temperature and high-pressure conditions and surfactant are not necessarily to, using no pressure
Power microwave method, the nano particle of efficient rapid synthesis cerium polymerization of olefin using catalyst polymer in this unlimited system, then by simple
One-step calcination prepares CeO2Nano particle；Not only method is simple, but also rapidly and efficiently, can effectively reduce cost and saving
The energy.This method carries out as follows:
Step 1: being dissolved in dehydrated alcohol and the in the mixed solvent of DMF for cerous nitrate, pyridine -2,5- dicarboxylic acids respectively, and two kinds
The volume ratio of solvent is 1:1, is 7.3~9.0 with the pH value that ammonium hydroxide (25%~30%) adjusts its solution, is obtained after mixing dense
Degree is the Ce (NO of 0.01~0.03mol/L3)3Solution；
Step 2: the mixed solution of step 1 is set and is placed in micro computer microwave chemical reactor (WBFY- in a round bottom flask
201) in, the power that microwave reactor is arranged is 210~350W, and 10~40min of back flow reaction, cold after reaction under the conditions of unlimited
But centrifuge washing, it is dry at 60 DEG C, obtain the super microsphere powder of cerium coordination polymer；
Step 3: the super microsphere powder of cerium coordination polymer of step 2 is placed in Muffle furnace, is forged at 500~800 DEG C
1~4h is burnt, obtains CeO after being cooled to room temperature2Nano particle.
For the present invention with cerous nitrate, pyridine -2,5- dicarboxylic acids for raw material, dehydrated alcohol and N-N dimethylformamide are mixing
Solvent, first back flow reaction obtains cerium coordination polymer superfines in microwave device, then calcines in Muffle furnace high temperature
To CeO2Nanoparticle.Nano Ce O is synthesized using template-free method2Particle is synthesized, synthesis step under the conditions of low temperature reflux
Simply, and the higher product of a large amount of purity can rapidly and efficiently be synthesized.Presoma is synthesized using microwave heating method, due to microwave method
Homogeneous heating, thermal gradient are small and shaping speed is fast, and the coordination polymer nano particle of cerium can be formed under conditions of no template, close
At presoma size uniformly and partial size it is smaller.
The present invention is by the selection to composition of raw materials, with pyridine -2,5- dicarboxylic acids for organic linker, mainly due to
(i) n-heterocyclic ligand of pyridine -2,5- dicarboxylic acids as a kind of similar terephthalic acid (TPA), is provided simultaneously with more carboxyl ligands and virtue
The advantage of fragrant race's ligand；(ii) pyridine -2,5- dicarboxylic acids not only can completely deprotonation but also can part deprotonation, Ke Yiyou
A variety of acidity coordination modes；(iii) pyridine -2,5- dicarboxylic acids can be not only coordinated with oxygen coordination but also with nitrogen, possess coordination abundant
Mode is conducive to construct organometallic skeletal.
The CeO that the present invention synthesizes2Nano particle average grain diameter is about 35nm, is evenly distributed.By the way that different volumes are added
Ammonia spirit adjusts the pH value of its mixed solution, can in various degree control cerium oxide nanoparticles dispersibility and shape
Looks.This also provides a kind of more simply and easily fast synthesis method to prepare cerium oxide nanoparticles.
As most active one of rare-earth oxide, ceria catalyst, fuel cell, sensor,
Extensive research has been carried out in the crucial application of UV absorption and luminous several related fieldss.Due to nano material in chemistry
The fields such as catalysis, biomedical engineering, energy storage, photonics, gas sensor, optical image and drug release have very big
Application potential.Still the CeO that synthesizes2Also there is potential excellent performance.
The present invention is under the conditions of flowing back no pressure, by the method rapid synthesis CeCPs of microwave heating, then by simple
The smaller ceria particles of partial size are prepared in calcining, and are further studied its performance.It is not required to addition surfactant,
Synthetic method is succinctly efficient, has that homogeneous heating, energy utilization rate are high, the reaction time is short and heating environment cleaning etc. is a series of excellent
Point.Compared to the above-mentioned time for being but provided simultaneously with using the method for having pressure microwave and shortening and reacting, increase the yield of product, and consumes
It can more low advantage.
Detailed description of the invention
CeO prepared by Fig. 1 embodiment 12The XRD diagram of nanoparticle.
CeO prepared by Fig. 2 embodiment 12The transmission electron microscope picture of nanoparticle.
CeO prepared by Fig. 3 embodiment 12The abosrption spectrogram of the ultraviolet-visible light of nanoparticle.
CeO prepared by Fig. 4 embodiment 22The transmission electron microscope picture of nanoparticle.
Specific embodiment
Embodiment 1:
Step 1: by 0.1mmol cerous nitrate and 0.3mmol pyridine -2,5- dicarboxylic acids be dissolved in 16ml dehydrated alcohol and
The in the mixed solvent of 16mlN-N dimethylformamide；
Step 2: it is 8.0 that ammonium hydroxide (30 μ L, concentration 30%) is added into above-mentioned mixed solution and adjusts its pH value, and is stirred
20min is mixed, mixed solution is transferred in round-bottomed flask is again placed in laboratory microwave device after mixing, 210W's
30min is reacted under power condition, centrifuge washing after reaction, 60 DEG C are dried to obtain cerium coordination polymer superfines (dry sample
Product)；
Step 3: drying sample obtained above is placed in Muffle furnace, calcines 4h at 600 DEG C, after being cooled to room temperature
CeO2Nanoparticle.
Embodiment 2:
Step 1: by 0.1mmol Ce (NO3)3·6H2O cerous nitrate and 0.3mmol pyridine -2,5- dicarboxylic acids are dissolved in 16ml
The in the mixed solvent of dehydrated alcohol and 16ml N-N dimethylformamide；
Step 2: it is 8.5 that ammonium hydroxide (40 μ L, concentration 25%) is added into above-mentioned mixed solution and adjusts its pH value, and is stirred
20min is mixed, pours into round-bottomed flask be placed in laboratory microwave device again after mixing, is reacted under the power condition of 350W
30min, centrifuge washing after reaction, 60 DEG C are dried to obtain cerium coordination polymer superfines (drying sample)；
Step 3: drying sample obtained above is placed in Muffle furnace at 600 DEG C and calcines 4h, is obtained after being cooled to room temperature
CeO2Nanoparticle is as shown in Figure 4.
For the performance for measuring product in above-described embodiment, XRD diffraction pattern is measured with Rigaku/Max-3A X-ray diffractometer
(CuK α radiation,)；Transmission electron microscope picture is obtained on Japanese JEOL-2010 transmission electron microscope
It arrives, acceleration voltage 200kV.
Fig. 1 is CeO prepared by embodiment 12The XRD diagram of nanoparticle, it can be seen that all peak of sample with cube
The CeO of phase2Standard card (JCPDS 34-0394) fit like a glove, illustrate that calcined coordination polymer is fully converted to
CeO2, determine that final product is the ceria of high-purity.
Fig. 2 is CeO prepared by embodiment 12The TEM of particle schemes, and is nano Ce O from what is synthesized known to Fig. 2 (a)2?
Grain, average grain diameter about 30~50nm, and most of nano particles are an irregular polygons.It is examined in Fig. 2 (c)
Know that the particle is solid and pattern is irregular shape.Fig. 2 (d) shows that the interplanar distance of 0.30nm is high-visible, and vertical
(311) crystal face of square phase ceria is corresponding.
Fig. 3 is CeO prepared by embodiment 12Ultraviolet-visible light absorption map.Powder absorption spectrum equation is
Eg=1240/ λ AE, λ AE is absorbing wavelength threshold value, and thus formula can calculate forbidden bandwidth value Eg.Institute is obtained by division lines method
The ceria absorbing wavelength threshold value for preparing product is 460nm, and corresponding Eg is 2.69eV, than commercial value 2.82eV
Want small.Compared with the nucleocapsid ceria of solvent structure (2.84eV), ultraviolet absorption ability is improved.
Claims (5)
1. a method of cerium oxide nanoparticles are prepared, are included the following steps:
Step 1: cerous nitrate, pyridine -2,5- dicarboxylic acids are dissolved in organic solvent, and the pH value for adjusting solution is 7.3~9.0, are obtained
To cerous nitrate solution；
Step 2: the cerous nitrate solution of step 1 is placed in microwave reaction device, and the power of setting microwave reaction device is 210
~350W, 10~40min of back flow reaction under the conditions of unlimited, cooling centrifuge washing, obtains cerium coordination polymerization after dry after reaction
The super microsphere powder of object；
Step 3: the super microsphere powder of cerium coordination polymer of step 2 is calcined into 1~4h at 500~800 DEG C, is cooled to room temperature
After obtain cerium oxide nanoparticles.
2. according to the method described in claim 1, it is characterized by: the organic solvent is the mixing of dehydrated alcohol and DMF
Solvent, the volume ratio of two kinds of solvents are 1:1.
3. according to the method described in claim 1, it is characterized by: in step 1, the concentration of cerous nitrate solution is 0.01~
0.03mol/L。
4. according to the method described in claim 1, it is characterized by: the microwave reaction device is micro computer in step 2
Microwave chemical reactor.
5. according to the method described in claim 1, it is characterized by: the super microsphere powder of cerium coordination polymer is placed in step 3
It is calcined in Muffle furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810977417.1A CN109133140A (en) | 2018-08-27 | 2018-08-27 | A method of preparing cerium oxide nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810977417.1A CN109133140A (en) | 2018-08-27 | 2018-08-27 | A method of preparing cerium oxide nanoparticles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109133140A true CN109133140A (en) | 2019-01-04 |
Family
ID=64827999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810977417.1A Pending CN109133140A (en) | 2018-08-27 | 2018-08-27 | A method of preparing cerium oxide nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109133140A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586193A (en) * | 2019-10-14 | 2019-12-20 | 东北大学秦皇岛分校 | Organic frame supporting CeO2Preparation method and application of/CuO electrocatalytic material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008002323A2 (en) * | 2005-12-23 | 2008-01-03 | Eastman Kodak Company | Production of cerium containing metal oxide grains |
| 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 |
| CN102020306A (en) * | 2010-12-22 | 2011-04-20 | 江西师范大学 | Microwave rapid synthetic method of nanometer cerium oxide |
| CN104925845A (en) * | 2015-07-08 | 2015-09-23 | 江西师范大学 | Multi-layer core shell structure CeO2 nanometer hollow sphere template-free composite method |
| CN107043121A (en) * | 2017-04-14 | 2017-08-15 | 江西师范大学 | A kind of preparation method of cerium dioxide nano hollow ball |
-
2018
- 2018-08-27 CN CN201810977417.1A patent/CN109133140A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008002323A2 (en) * | 2005-12-23 | 2008-01-03 | Eastman Kodak Company | Production of cerium containing metal oxide grains |
| 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 |
| CN102020306A (en) * | 2010-12-22 | 2011-04-20 | 江西师范大学 | Microwave rapid synthetic method of nanometer cerium oxide |
| CN104925845A (en) * | 2015-07-08 | 2015-09-23 | 江西师范大学 | Multi-layer core shell structure CeO2 nanometer hollow sphere template-free composite method |
| CN107043121A (en) * | 2017-04-14 | 2017-08-15 | 江西师范大学 | A kind of preparation method of cerium dioxide nano hollow ball |
Non-Patent Citations (1)
| Title |
|---|
| 廖媛媛: ""二氧化铈及其负载贵金属催化剂的制备与性能研究"", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586193A (en) * | 2019-10-14 | 2019-12-20 | 东北大学秦皇岛分校 | Organic frame supporting CeO2Preparation method and application of/CuO electrocatalytic material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101792164B (en) | Method for preparing nano aluminum oxide through vacuum freeze drying technology | |
| Patil et al. | Synthesis techniques and applications of rare earth metal oxides semiconductors: A review | |
| CN104370300B (en) | A kind of high dispersive, spherical cerium oxide powder and preparation method thereof | |
| CN103691421B (en) | A kind of CeVO 4micron ball photochemical catalyst and preparation method thereof | |
| CN105384193B (en) | Preparation method of niobium (V) pentoxide urchin-like nano sphere and application of nano sphere as photocatalyst | |
| CN105060351B (en) | Flower-like cobaltosic oxide material composed of nanoparticles and preparation method thereof | |
| CN105948098B (en) | A kind of spherical lanthana | |
| CN105668647A (en) | High-specific surface area perovskite nano-LaCoO3 porous hollow sphere material and preparation method thereof | |
| CN104477978B (en) | A kind of method preparing perovskite nano-powder | |
| CN104003448A (en) | [Alpha]-phase ferric oxide porous core-shell microspheres and controllable synthetic preparation method thereof | |
| CN109678193A (en) | A kind of preparation method of ceria nanoparticles | |
| CN102942206A (en) | Method for preparing cerium dioxide nanometer hollow spheres | |
| CN103553140A (en) | Method for preparing lanthanum ferrite nanodisk | |
| CN108675339B (en) | Preparation method of rodlike self-assembled spherical zinc-cadmium-sulfur solid solution material | |
| CN104528799A (en) | Preparation method of ultrafine magnesium-based rare earth hexaaluminate powder | |
| CN107043121A (en) | A kind of preparation method of cerium dioxide nano hollow ball | |
| CN102659154A (en) | Method for preparing nano alpha-Al2O3 powder | |
| CN101367539B (en) | Preparation of nano- luminescent powder body with colloidal sols gel rubber method | |
| CN104971703A (en) | Preparation method of polypyrrole coated magnetic reduced graphene nanometer material | |
| CN108722486A (en) | A kind of preparation method of narrowband carbonitride modification ferrous metals organic backbone composite photo-catalyst | |
| CN109133140A (en) | A method of preparing cerium oxide nanoparticles | |
| CN109133144A (en) | A kind of preparation method of monodisperse ultra-small grain size ceria nano-crystalline | |
| CN105883910A (en) | Preparation method and product for perovskite SrTiO3 porous nano particles | |
| CN106430289A (en) | Method for low temperature preparation of high specific surface area nanometer gallate spinel | |
| CN108083334A (en) | A kind of preparation method of monodisperse spherical nano zirconium dioxide powder body material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190104 |