CN106082298A - A kind of preparation method of cerium bismuth composite oxide nano-bar material - Google Patents
A kind of preparation method of cerium bismuth composite oxide nano-bar material Download PDFInfo
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- CN106082298A CN106082298A CN201610446044.6A CN201610446044A CN106082298A CN 106082298 A CN106082298 A CN 106082298A CN 201610446044 A CN201610446044 A CN 201610446044A CN 106082298 A CN106082298 A CN 106082298A
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- bar material
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- composite oxide
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- 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 relates to the preparation method of a kind of cerium bismuth composite oxide nano-bar material.Hydrothermal synthesis method is combined by this invention with spray drying method, uses conventional equipment, and preparation process is the most easily controllable, is suitable for industrialized production.Cerium bismuth composite oxide nano-bar material prepared by the method, pattern is uniform, and draw ratio is controlled, remains to keep good Rod-like shape through 500 DEG C of roastings.This materials application has a extensive future, and can be applied not only to thermocatalytic, photocatalysis and electrocatalytic reaction, it may also be used for the field such as biological medicine, luminescent material.
Description
Technical field
The present invention relates to the preparation method of a kind of cerium bismuth composite oxide nano-bar material, belong to nano material preparation technology
Field.
Background technology
Cerium oxide (CeO2) special due to itRedox cycle show excellence store oxygen performance,
It is widely used in the heterogeneous catalyst system (patent such as motor vehicle tail-gas purifying, fuel cell as catalysis material
US5491120；US6255249；Huang X.S.et al.Applied Catalysis B:Environmental,2009,
90:224；Zahir M.H.et al.Fuel Cells,2009,9:164-169；Yaroslava L.,et al.Physical
Chemistry Chemical Physics,2016,18:7672.).Its catalytic performance and the size of material, pattern, composition are close
Cut is closed.Modulation nano-particles size can change absorption and the state of activation of reactant, thus affects catalytic perfomance, and this is
Nano-catalytic priority fields of study for many years.But, the physicochemical properties of nano material depend not only upon its dimensional effect,
And with its pattern is closely related.In recent years, along with the fast development of nanometer material science, it is already possible on nanoscale
The effectively pattern of modulation solid catalyst particle, many research work are the most right on the basis of maintaining nanometer size effect
CeO2The pattern of based nano-material regulates and controls, and optionally exposes high activity or particular energy crystal face, thus significantly carries
High catalytic reaction activity, selectivity and stability (Li Y., et al.Chemical Society Reviews, 2014,43:
1543)。
Due to CeO2Heat stability is poor, needs to add other yuan such as Zr, La, Y, Ti and usually strengthens its thermal stability
(Turko G.A.,et al.Kinetics and Catalysis,2005,46,932；Zhang Z.L.,et al.Applied
Catalysis B:Environmental,2007,76:335.).Can so special appearance of one-component metal-oxide
Adding the continuation of insurance of other element succesor to hold, after doping, can the pattern effect in catalytic reaction continue to embody, for special appearance
Nano catalytic material is applied to actual catalytic reaction and has important researching value.In recent years, the not similar shape of different element dopings
The CeO of looks2Based nano-material is developed successively, such as the CeO of the element dopings such as La, Pr, Nd, Eu, Gd, Y, Ti, Mn, Zr2Ji Na
Rice rod, the CeO of the element doping such as Zr, Mn, Hf, Cu2Base composite oxidate nanocube, the element doping such as Zr, Ti, Ag, Hf
CeO2Base composite oxidate nanotube etc., and show nano-catalytic pattern effect (CN 101693520 A；Chen,W.T.,
et al.,Chemical Communications,2010.46:3286；Li S.,et al.,Applied Catalysis B:
Environmental,2014,144:498；Mondragon-Galicia G.,et al.,Physical Chemistry
Chemical Physics,2011,13:16756；Li H.,et al.,Catalysis Science&Technology,
2011,1:1677；Chen,Y.C.,et al.,Journal of Physical Chemistry C,2009,113:5031；
Zhao F.Z.,et al.,Physical Chemistry Chemical Physics,2014,16:17183.).But Bi is first
The preparation method of the cerium bismuth composite oxide nano-bar material of element doping have not been reported.
Summary of the invention
It is an object of the invention to for the deficiencies in the prior art, it is provided that the system of a kind of cerium bismuth composite oxide nano-bar material
Preparation Method, the method technique is simple, environmental protection, and productivity is high, and prepared nano material size, pattern are uniform, and are prone to work
Industry metaplasia is produced.
It is an object of the invention to be achieved through the following technical solutions:
The present invention is by Bi element doping and enters CeO2Lattice and make cerium bismuth composite oxide nano-bar material, this material
Size and pattern are uniform.
Described cerium bismuth composite oxide nano-bar material, wherein the mol ratio of cerium bismuth is 0.8～0.99:0.2～0.01.
The present invention uses hydro-thermal-spray drying method, obtains nano bar-shape material, and its preparation technology is simple.Its concrete steps
For: according to usage ratio, the aqueous solution of bismuth nitrate is joined in water-soluble cerium salt solution, is stirred continuously in room temperature
Under the conditions of, add the precipitant of excess, obtain mixture.The mixture obtained is encapsulated in hermetic container, aging 20h with
On, obtain product.Product is filtered, washs, be then spray-dried, then roasting, obtain this nano-bar material..
In above-mentioned preparation method, cerium salt is preferably cerous nitrate, cerous nitrate ammonia.Described precipitant be sodium hydroxide solution or
Potassium hydroxide solution.Aging temperature is generally 80～150 DEG C, and preferable aging temperature is 100～120 DEG C.Aging more than 20h
After, product is filtered, washs, add and account for CeO2The polyglycol solution of gross mass 10～50wt% is sized mixing, spray dried
Dry, control powder average particle size at 5～10 microns.The powder obtained after being spray-dried is vacuum dried.Dried urge
Agent roasting under given atmosphere again.The atmosphere of roasting is generally air or oxygen.Sintering temperature is generally 400～500 DEG C.
In above-mentioned preparation method, it is dried and roasting process is as follows: vacuum drying 12 hours under the conditions of 80 DEG C, the most again
Roasting 1～2 hours under the conditions of 150～200 DEG C, then roasting 2～5 hours under the conditions of 400～500 DEG C, obtain this nanometer
Bar material.
It is an advantage of the current invention that:
(1) present invention uses hydro-thermal-spray drying method, without harsh temperatures and pressure requirements, uses conventional equipment, prepared
Journey is the most easily controllable, is suitable for industrialized production.
(2) nano-bar material prepared by the method, pattern is uniform, and draw ratio is controlled, remains to keep good through 500 DEG C of roastings
Good Rod-like shape.
(3) this materials application has a extensive future, and can be applied not only to thermocatalytic, photocatalysis and electrocatalytic reaction, can also be used with
In the field such as biological medicine, luminescent material.
Accompanying drawing explanation
Fig. 1 is the TEM photo of the embodiment of the present invention 1 products obtained therefrom.
Fig. 2 is the TEM photo of the embodiment of the present invention 2 products obtained therefrom.
Fig. 3 is the TEM photo of the embodiment of the present invention 3 products obtained therefrom.
Fig. 4 is the TEM photo of the embodiment of the present invention 4 products obtained therefrom.
Fig. 5 is the HRTEM photo of the embodiment of the present invention 4 products obtained therefrom.
Fig. 6 is the XRD spectra of resulting materials of the present invention, and wherein abscissa is the 2 θ angles of diffraction, and vertical coordinate is intensity.
Detailed description of the invention
Embodiment 1
Ce0.99Bi0.01OδThe preparation of (mol ratio of Ce Yu Bi is 0.99:0.01) composite oxides nanometer rods.
First 5.21g cerous nitrate and 0.0588g bismuth nitrate are dissolved in 10mL deionized water, after magnetic agitation is dissolved, then
Add 40mL 10mol/L sodium hydroxide solution, magnetic agitation 30min, above-mentioned solution is transferred to 100mL containing politef
In the rustless steel water heating kettle of liner.Putting in baking oven by the reactor of sealing, 80 DEG C keep 20h, after natural cooling, reaction are produced
Thing filters, washing, is smashed to pieces by the filter cake obtained, and adds deionized water and makes emulsion, adds and contain the water-soluble of Polyethylene Glycol 0.21g
Liquid is sized mixing, and is spray-dried, and the powder obtained, at 5 microns, is vacuum dried 12h in 80 DEG C, then exists by control powder average particle size
The lower 150 DEG C of roasting 1h of air atmosphere, the most again at 400 DEG C of roasting 2h, obtain a length of 50～200nm, a diameter of 5～10nm
Ce0.99Bi0.01OδComposite oxides nanometer rods.
Embodiment 2
Ce0.95Bi0.05OδThe preparation of (mol ratio of Ce Yu Bi is 0.95:0.05) composite oxides nanometer rods.
First 6.57g ammonium ceric nitrate and 0.294g bismuth nitrate are dissolved in 10mL deionized water, after magnetic agitation is dissolved, then
Add 40mL 10mol/L potassium hydroxide solution, magnetic agitation 30min, above-mentioned solution is transferred to 100mL containing politef
In the rustless steel water heating kettle of liner.Putting in baking oven by the reactor of sealing, 100 DEG C keep 25h, after natural cooling, and will reaction
Product filters, washing, is smashed to pieces by the filter cake obtained, and adds deionized water and makes emulsion, adds containing Polyethylene Glycol 0.413g's
Aqueous solution is sized mixing, and is spray-dried, and the powder obtained, at 10 microns, is vacuum dried 12h in 80 DEG C, so by control powder average particle size
After under oxygen atmosphere 200 DEG C of roasting 2h, the most again at 500 DEG C of roasting 5h, obtaining average length is 50～200nm, a diameter of 5
～the Ce of 10nm0.95Bi0.05OδComposite oxides nanometer rods.
Embodiment 3
Ce0.9Bi0.1OδThe preparation of (mol ratio of Ce Yu Bi is 0.9:0.1) composite oxides nanometer rods.
First 5.21g cerous nitrate and 0.588g bismuth nitrate are dissolved in 10mL deionized water, after magnetic agitation is dissolved, then add
Enter 40mL 10mol/L sodium hydroxide solution, magnetic agitation 30min, above-mentioned solution is transferred to 100mL containing in politef
In the rustless steel water heating kettle of lining.Putting in baking oven by the reactor of sealing, 120 DEG C keep 20h, after natural cooling, reaction are produced
Thing filters, washing, is smashed to pieces by the filter cake obtained, and adds deionized water and makes emulsion, adds the water containing Polyethylene Glycol 1.033g
Solution is sized mixing, and is spray-dried, and the powder obtained, at 5 microns, is vacuum dried 12h in 80 DEG C, then by control powder average particle size
180 DEG C of roasting 1.5h in air atmosphere, the most again at 500 DEG C of roasting 3h, obtain a length of 10～50nm, a diameter of 8～25nm
Ce0.9Bi0.1OδComposite oxides nanometer rods.
Embodiment 4
Ce0.8Bi0.2OδThe preparation of (mol ratio of Ce Yu Bi is 0.8:0.2) composite oxides nanometer rods.With embodiment 3
Preparation process is identical, and difference is: aging temperature 100 DEG C；Bismuth nitrate consumption is different.As shown in table 3.According to table 3 parameter
Table 3 preparation parameter
Preparation, obtains a length of 10～50nm, a diameter of 8～the Ce of 25nm0.8Bi0.2OδComposite oxides nanometer rods.
Claims (4)
1. a cerium bismuth composite oxide nano-bar material, it is characterised in that by Bi element doping and enter CeO2 lattice and make
Becoming, the mol ratio of cerium bismuth is 0.8～0.99:0.2～0.01.
Cerium bismuth composite oxide nano-bar material the most according to claim 1, it is characterised in that use hydro-thermal-spray dried
Dry method, obtains nano bar-shape material, and its preparation technology is simple.It concretely comprises the following steps: according to usage ratio, water-soluble by bismuth nitrate
Liquid joins in water-soluble cerium salt solution, at room temperature, is stirred continuously, and adds the precipitant of excess, is mixed
Thing.The mixture obtained is encapsulated in hermetic container, aging more than 20h, obtains product.Product is filtered, washes
Wash, be then spray-dried, then roasting, obtain this nano-bar material.
The preparation method of cerium bismuth composite oxide nano-bar material the most according to claim 2, it is characterised in that cerium salt is
Cerous nitrate or cerous nitrate ammonia.Described precipitant is sodium hydroxide solution or potassium hydroxide solution.Aging temperature be generally 80～
150 DEG C, preferable aging temperature is 100～120 DEG C.After aging more than 20h, product filtered, wash, add and account for
The polyglycol solution of CeO2 gross mass 10～50wt% is sized mixing, and is spray-dried, and controls powder average particle size at 5～10 microns.
The powder obtained after being spray-dried is vacuum dried.The roasting under given atmosphere again of dried catalyst.Roasting
Atmosphere is generally oxygen or air.Sintering temperature is generally 400～500 DEG C.
The preparation method of cerium bismuth composite oxide nano-bar material the most according to claim 3, it is characterised in that be dried and
Roasting process is as follows: be vacuum dried under the conditions of 80 DEG C 12 hours, roasting 1～2 hours under the conditions of 150～200 DEG C the most again,
Then roasting 2～5 hours under the conditions of 400～500 DEG C, obtain this nano-bar material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944032A (en) * | 2017-04-13 | 2017-07-14 | 西南石油大学 | A kind of preparation method of Ce-Magnesium coumpoud oxide nano-bar material |
| CN107511154A (en) * | 2017-10-17 | 2017-12-26 | 枣庄学院 | A kind of sea urchin shape CeO2/Bi2S3Composite visible light catalyst and preparation method thereof |
| CN113644272A (en) * | 2021-08-12 | 2021-11-12 | 湖南杉杉能源科技有限公司 | Cerium-bismuth composite oxide doped lithium ion battery positive electrode material and preparation method thereof |
| CN116078372A (en) * | 2023-04-06 | 2023-05-09 | 中国科学院过程工程研究所 | Catalyst for synthesizing cyclic carbonate, preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944032A (en) * | 2017-04-13 | 2017-07-14 | 西南石油大学 | A kind of preparation method of Ce-Magnesium coumpoud oxide nano-bar material |
| CN107511154A (en) * | 2017-10-17 | 2017-12-26 | 枣庄学院 | A kind of sea urchin shape CeO2/Bi2S3Composite visible light catalyst and preparation method thereof |
| CN113644272A (en) * | 2021-08-12 | 2021-11-12 | 湖南杉杉能源科技有限公司 | Cerium-bismuth composite oxide doped lithium ion battery positive electrode material and preparation method thereof |
| CN113644272B (en) * | 2021-08-12 | 2023-01-24 | 巴斯夫杉杉电池材料有限公司 | Cerium-bismuth composite oxide doped lithium ion battery positive electrode material and preparation method thereof |
| CN116078372A (en) * | 2023-04-06 | 2023-05-09 | 中国科学院过程工程研究所 | Catalyst for synthesizing cyclic carbonate, preparation method and application thereof |
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