CN106082298B - Preparation method of cerium-bismuth composite oxide nanorod material - Google Patents
Preparation method of cerium-bismuth composite oxide nanorod material Download PDFInfo
- Publication number
- CN106082298B CN106082298B CN201610446044.6A CN201610446044A CN106082298B CN 106082298 B CN106082298 B CN 106082298B CN 201610446044 A CN201610446044 A CN 201610446044A CN 106082298 B CN106082298 B CN 106082298B
- Authority
- CN
- China
- Prior art keywords
- cerium
- roasting
- hours
- composite oxide
- preparation
- 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.)
- Active
Links
Images
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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- 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
- C01P2004/10—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
-
- 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 invention relates to a preparation method of a cerium bismuth composite oxide nanorod material. The invention combines the hydrothermal synthesis method and the spray drying method, uses conventional equipment, has simple and easily controlled preparation process, and is suitable for industrial production. The cerium bismuth composite oxide nanorod material prepared by the method is uniform in appearance and controllable in length-diameter ratio, and can still keep a good rodlike appearance after being roasted at 500 ℃. The material has wide application prospect, can be applied to thermocatalysis, photocatalysis and electrocatalytic reaction, and can also be applied to the fields of biological medicine, luminescent materials and the like.
Description
Technical Field
The invention relates to a preparation method of a cerium bismuth composite oxide nanorod material, belonging to the technical field of preparation of nanomaterials.
Background
Cerium oxide (CeO)2) Due to its special characteristics
The redox cycle shows excellent oxygen storage performance, and is widely applied to heterogeneous catalyst systems such as automobile exhaust gas purification and fuel Cells as a catalytic material (patent US 5491120; US 6255249; 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.). The catalytic performance of the catalyst is closely related to the size, shape and composition of the material. The modulation of the size of the nano particles can change the adsorption and activation states of reactants, thereby influencing the catalytic reaction performance, which is a key field of nano catalytic research for many years. However, the physicochemical properties of the nano-materials not only depend on their size effect, but also are closely related to their morphologyAnd off. In recent years, with the rapid development of nano material science, the morphology of solid catalyst particles can be effectively modulated on a nano scale, and many researches are carried out on CeO on the basis of maintaining the nano size effect2The morphology of the base nano material is regulated and controlled, and a high-activity or specific energy crystal face can be selectively exposed, so that the catalytic reaction activity, selectivity and stability are greatly improved (Li Y., et al. chemical Society Reviews,2014,43: 1543).
Since CeO2The thermal stability is poor, and other elements such as Zr, La, Y and Ti are required to be added to enhance the 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.). Whether the special morphology of the single-component metal oxide can be continuously maintained after other elements are added or not and whether the morphology effect in the catalytic reaction can be continuously reflected or not after doping has important research value for the application of the nano catalytic material with the special morphology to the actual catalytic reaction. In recent years, CeO with different morphologies doped by different elements2Based nano materials such as CeO doped with La, Pr, Nd, Eu, Gd, Y, Ti, Mn, Zr and other elements are developed in succession2Based on nano-rods, CeO doped with Zr, Mn, Hf, Cu and other elements2Based composite oxide nano cube, CeO doped with Zr, Ti, Ag, Hf and other elements2Based on composite oxide nanotubes, and the like, and exhibit a nanocatalyst morphological effect (CN 101693520A; 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 Science, 2011,13: 16756; Li H., et al., Catalysis Science, and the like (CN 101693520A; Chen, W.T., et al., Chemical Communications, 2010.46; Li S., et al., Applied Catalysis C., Environmental,2014,144: 498; Mondragon-Galicia G., et al., Physical chemistry, 2011,13: 16756; Li H., et al., Catalysis Science, Inc., Co., Ltd.&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.). However, the preparation method of the Bi element doped cerium bismuth composite oxide nanorod material is not reported.
Disclosure of Invention
The invention aims to provide a preparation method of a cerium-bismuth composite oxide nanorod material aiming at the defects of the prior art, the method is simple in process, environment-friendly and high in yield, and the prepared nanomaterial is uniform in size and shape and is easy for industrial production.
The purpose of the invention is realized by the following technical scheme:
the invention is formed by doping Bi element and adding into CeO2The cerium bismuth composite oxide nanorod material is prepared by crystal lattices, and has uniform size and appearance.
The cerium-bismuth composite oxide nanorod material has a molar ratio of cerium to bismuth of 0.8-0.99: 0.2-0.01.
The invention adopts a hydrothermal-spray drying method to obtain the nano rod-shaped material, and the preparation process is simple. The method comprises the following specific steps: according to the dosage proportion, the aqueous solution of bismuth nitrate is added into the aqueous solution of cerium salt which is soluble in water, and excess precipitator is added under the condition of continuously stirring at room temperature to obtain a mixture. And packaging the obtained mixture in a closed container, and aging for more than 20h to obtain a reaction product. And filtering and washing the reaction product, then spray-drying, and roasting to obtain the nanorod material. .
In the above preparation method, the cerium salt is preferably cerium nitrate or ammonium cerium nitrate. The precipitant is sodium hydroxide solution or potassium hydroxide solution. The aging temperature is generally 80-150 ℃, and the better aging temperature is 100-120 ℃. Aging for more than 20h, filtering and washing the reaction product, and adding CeO2And (3) mixing the slurry with 10-50 wt% of polyethylene glycol solution, spray drying, and controlling the average particle size of the powder to be 5-10 microns. The powder obtained after spray drying was dried under vacuum. The dried catalyst was calcined again in a given atmosphere. The atmosphere for calcination is typically air or oxygen. The calcination temperature is generally 400 to 500 ℃.
In the above preparation method, the drying and baking processes are as follows: vacuum drying at 80 ℃ for 12 hours, roasting at 150-200 ℃ for 1-2 hours, and roasting at 400-500 ℃ for 2-5 hours to obtain the nanorod material.
The invention has the advantages that:
(1) the invention adopts a hydrothermal-spray drying method, has no harsh requirements on temperature and pressure, uses conventional equipment, has simple and easily controlled preparation process and is suitable for industrial production.
(2) The nanorod material prepared by the method has uniform appearance and controllable length-diameter ratio, and can still keep good rod-like appearance after being roasted at 500 ℃.
(3) The material has wide application prospect, can be applied to thermocatalysis, photocatalysis and electrocatalytic reaction, and can also be applied to the fields of biological medicine, luminescent materials and the like.
Drawings
FIG. 1 is a TEM photograph of a product obtained in example 1 of the present invention.
FIG. 2 is a TEM photograph of a product obtained in example 2 of the present invention.
FIG. 3 is a TEM photograph of a product obtained in example 3 of the present invention.
FIG. 4 is a TEM photograph of a product obtained in example 4 of the present invention.
FIG. 5 is a HRTEM photograph of the product obtained in example 4 of the present invention.
Fig. 6 is an XRD spectrum of the material obtained in the present invention, wherein the abscissa is the 2 θ diffraction angle and the ordinate is the intensity.
Detailed Description
Example 1
Ce0.99Bi0.01Oδ(the molar ratio of Ce to Bi is 0.99:0.01) preparation of composite oxide nanorods.
Firstly, 5.21g of cerium nitrate and 0.0588g of bismuth nitrate are dissolved in 10mL of deionized water, after the cerium nitrate and the 0.0588g of bismuth nitrate are dissolved by magnetic stirring, 40mL of 10mol/L sodium hydroxide solution is added, the solution is stirred for 30min by magnetic stirring, and the solution is transferred to a 100mL stainless steel hot kettle containing a polytetrafluoroethylene lining. Placing the sealed reaction kettle into an oven, keeping the reaction kettle at 80 ℃ for 20 hours, naturally cooling, filtering and washing a reaction product, mashing an obtained filter cake, adding deionized water to prepare an emulsion, adding an aqueous solution containing 0.21g of polyethylene glycol to mix, spray-drying, controlling the average particle size of powder to be 5 microns, vacuum-drying the obtained powder at 80 ℃ for 12 hours, roasting at 150 ℃ in an air atmosphere for 1 hour, and roasting at 400 ℃ for 2 hours to obtain Ce with the length of 50-200 nm and the diameter of 5-10 nm0.99Bi0.01OδA composite oxide nanorod.
Example 2
Ce0.95Bi0.05Oδ(the molar ratio of Ce to Bi is 0.95:0.05) preparation of composite oxide nanorods.
Firstly, 6.57g of ammonium ceric nitrate and 0.294g of bismuth nitrate are dissolved in 10mL of deionized water, after the solution is dissolved by magnetic stirring, 40mL of 10mol/L potassium hydroxide solution is added, the solution is stirred by magnetic stirring for 30min, and the solution is transferred to a 100mL stainless steel hot kettle containing a polytetrafluoroethylene lining. Placing the sealed reaction kettle into an oven, keeping the temperature of the reaction kettle at 100 ℃ for 25 hours, naturally cooling, filtering and washing a reaction product, mashing an obtained filter cake, adding deionized water to prepare an emulsion, adding an aqueous solution containing 0.413g of polyethylene glycol to mix, spray-drying, controlling the average particle size of powder to be 10 micrometers, vacuum-drying the obtained powder at 80 ℃ for 12 hours, roasting the powder at 200 ℃ for 2 hours in an oxygen atmosphere, and roasting at 500 ℃ for 5 hours to obtain Ce with the average length of 50-200 nm and the diameter of 5-10 nm0.95Bi0.05OδA composite oxide nanorod.
Example 3
Ce0.9Bi0.1Oδ(the molar ratio of Ce to Bi is 0.9:0.1) preparation of composite oxide nanorods.
Firstly, 5.21g of cerium nitrate and 0.588g of bismuth nitrate are dissolved in 10mL of deionized water, 40mL of 10mol/L sodium hydroxide solution is added after the cerium nitrate and the bismuth nitrate are dissolved by magnetic stirring, the solution is stirred for 30min by magnetic stirring, and the solution is transferred to a 100mL stainless steel hot kettle containing a polytetrafluoroethylene lining. Placing the sealed reaction kettle into an oven, keeping the temperature at 120 ℃ for 20 hours, naturally cooling, filtering and washing reaction products, mashing obtained filter cakes, adding deionized water to prepare emulsion, adding aqueous solution containing 1.033g of polyethylene glycol to prepare slurry, spray-drying, controlling the average particle size of powder to be 5 microns, vacuum-drying the obtained powder at 80 ℃ for 12 hours, roasting at the air atmosphere at 180 ℃ for 1.5 hours, and roasting at the temperature of 500 ℃ for 3 hours to obtain 10-50 nm Ce with the diameter of 8-25 nm0.9Bi0.1OδA composite oxide nanorod.
Example 4
Ce0.8Bi0.2Oδ(the molar ratio of Ce to Bi is 0.8:0.2) preparation of composite oxide nanorods. The same procedure as in example 3 was followed, except that: the aging temperature is 100 ℃; the dosage of bismuth nitrate is different. As shown in table 3. According to the parameters of Table 3
TABLE 3 preparation parameters
The preparation method is used for obtaining Ce with the length of 10-50 nm and the diameter of 8-25 nm0.8Bi0.2OδA composite oxide nanorod.
Claims (2)
1. The preparation method of the cerium bismuth composite oxide nanorod material is characterized in that the nanorod material is doped with Bi element and enters CeO2Lattice, the molar ratio of cerium to bismuth is 0.95: 0.05; the nano rod-shaped material is obtained by adopting a hydrothermal-spray drying method, and the preparation process is simple;
the method comprises the following specific steps: adding the aqueous solution of bismuth nitrate into the aqueous solution of cerium salt soluble in water according to the dosage proportion, continuously stirring at room temperature, adding excessive precipitator to obtain a mixture, packaging the obtained mixture in a closed container, aging at 100 ℃, filtering and washing a reaction product after aging for more than 20 hours, and adding CeO2Mixing 10-50 wt% of polyethylene glycol solution in total mass, spray drying, controlling the average particle size of powder to be 5-10 microns, carrying out vacuum drying on the powder obtained after spray drying, and roasting the dried catalyst in a given atmosphere to obtain the nanorod material;
the roasting atmosphere is oxygen or air;
the drying and roasting process is as follows: vacuum drying at 80 ℃ for 12 hours, roasting at 150-200 ℃ for 1-2 hours, and roasting at 400-500 ℃ for 2-5 hours to obtain the nanorod material.
2. The method of claim 1, wherein the cerium salt is cerium nitrate or ammonium cerium nitrate, and the precipitant is sodium hydroxide solution or potassium hydroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610446044.6A CN106082298B (en) | 2016-06-21 | 2016-06-21 | Preparation method of cerium-bismuth composite oxide nanorod material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610446044.6A CN106082298B (en) | 2016-06-21 | 2016-06-21 | Preparation method of cerium-bismuth composite oxide nanorod material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106082298A CN106082298A (en) | 2016-11-09 |
| CN106082298B true CN106082298B (en) | 2020-03-24 |
Family
ID=57237444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610446044.6A Active CN106082298B (en) | 2016-06-21 | 2016-06-21 | Preparation method of cerium-bismuth composite oxide nanorod material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106082298B (en) |
Families Citing this family (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 |
| CN107511154B (en) * | 2017-10-17 | 2022-11-18 | 枣庄学院 | Sea urchin-shaped CeO 2 /Bi 2 S 3 Composite visible light catalyst 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 |
| CN116078372B (en) * | 2023-04-06 | 2023-06-20 | 中国科学院过程工程研究所 | Catalyst for synthesizing cyclic carbonate, preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613123A (en) * | 2009-08-05 | 2009-12-30 | 邢长生 | The hydrothermal synthesis method of IVB family metal oxide |
| CN103263908B (en) * | 2013-05-22 | 2014-11-05 | 北京化工大学 | Synthesis of CeO2-based solid solution nanometer material and application of nanomaterial to catalytic degradation of dye |
-
2016
- 2016-06-21 CN CN201610446044.6A patent/CN106082298B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Hydrothermal Synthesis and in Situ Powder X‑ray Diffraction Study of Bismuth-Substituted Ceria Nanoparticles;Kasper Houlberg等;《Cryst. Growth Des.》;20150616;第3628-3636页 * |
| 铈基氧化物的制备及其催化氧化CO性能研究;赵宪成;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20131215;第24页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106082298A (en) | 2016-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2019109831A1 (en) | Method for preparing copper-nickel cobaltate nanowires and use thereof in catalyzing hydrolysis of ammonia borane to produce hydrogen | |
| CN103785859B (en) | Method for manufacturing nanometer mesoporous material | |
| CN106082298B (en) | Preparation method of cerium-bismuth composite oxide nanorod material | |
| Chen et al. | Benign synthesis of ceria hollow nanocrystals by a template-free method | |
| CN101792164B (en) | Method for preparing nano aluminum oxide through vacuum freeze drying technology | |
| CN104148047B (en) | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst | |
| CN103011306B (en) | Method for preparing nanometer-level cube-like cobaltosic oxide | |
| CN111545192A (en) | MOFs-derived perovskite catalyst, preparation method thereof and application of MOFs-derived perovskite catalyst in catalytic degradation of organic pollutants | |
| CN105536791B (en) | The preparation method of the octahedra cuprous oxide catalysis agent of synthesizing methyl-chloro-silane monomer | |
| CN102826608A (en) | Method for preparing bismuth ferrite powder by solvothermal method | |
| CN103030159B (en) | A kind of porous magnesia, preparation method and its usage | |
| CN112058298A (en) | Preparation method of high-concentration alkali solution modified carbon nitride | |
| CN109336161B (en) | CeO2 nanotube preparation method, CeO2 nanotube and application | |
| Du et al. | Morphology and structure features of ZnAl2O4 spinel nanoparticles prepared by matrix-isolation-assisted calcination | |
| CN105293567B (en) | Flaky porous nanometer zinc oxide and preparation method thereof | |
| CN103803664B (en) | A kind of preparation method of tricobalt tetroxide band core nano-hollow ball | |
| CN110813300B (en) | Cobalt-zinc-loaded bimetallic nano-carbon material, preparation method thereof and application thereof in catalytic oxidation of magnesium sulfite | |
| CN110937620B (en) | Non-stoichiometric zinc-aluminum spinel and preparation method thereof | |
| CN110694650B (en) | Bi loaded Bi 4 NbO 8 Preparation method of Cl composite visible light catalyst | |
| CN109384262B (en) | Flaky Li4Mn5O12Ion sieve precursor and preparation method of ion sieve | |
| CN108479761B (en) | Method for preparing spherical perovskite catalyst by taking casein as biological template | |
| CN111333128B (en) | Preparation method of high-uniformity nickel oxide | |
| CN110156069B (en) | Method for preparing indium oxide superfine powder | |
| CN112919523A (en) | Preparation method of hexagonal flaky rare earth cerium oxide | |
| CN108298597B (en) | Preparation method of ferrous spinel of divalent metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |