CN110040760A - A kind of method of controllable preparation cerium lanthanum-oxides solid solution nanometer rods - Google Patents
A kind of method of controllable preparation cerium lanthanum-oxides solid solution nanometer rods Download PDFInfo
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- CN110040760A CN110040760A CN201910382981.3A CN201910382981A CN110040760A CN 110040760 A CN110040760 A CN 110040760A CN 201910382981 A CN201910382981 A CN 201910382981A CN 110040760 A CN110040760 A CN 110040760A
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- lanthanum
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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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- 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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Abstract
The invention belongs to rare earth material fields, and in particular to a kind of method of controllable preparation cerium lanthanum-oxides solid solution nanometer rods.The beneficial effects of the present invention are: the preparation method is relatively simple, preparation condition is easy to control, and is generated in preparation process without poisonous and harmful substance, and the nanometer rods cerium lanthanum-oxides solid solution pattern prepared is uniform, stable structure, has certain application value.
Description
Technical field
The invention belongs to rare earth material field, in particular to a kind of preparation method of nanometer rods cerium lanthanum-oxides solid solution,
Preparation process is simple, can achieve the purpose of nano particle morphology controllable synthesis.
Background technique
The rare earth element of rich content is because of it with 4f in the earth's crustx5d166f2Electron structure, electric state height, radius
Greatly, the advantages that polarizability is strong, chemical property is active, development and utilization are at low cost is widely applied to catalytic field, as petroleum is split
Solution, catalysis burning, photocatalysis etc..More cerium (Ce) is wherein studied now because having Ce3+And Ce4+Two kinds of compound states, can be with
Carry out redox cycle under proper condition, that is, achieve the purpose that store up and oxygen and put oxygen, and adulterate non-equivalence metal ion it
Afterwards, because charge compensation mechanism can be more likely formed electrically charged Lacking oxygen in cerium oxide lattice, so that shape after doping
At solid solution or composite oxides have in cerium oxide lattice and flow oxygen characteristic, it may have the spy of foreign atom oxide
Property, so that the purpose of improving catalyst reaction Activity and stabill from many aspects even more noteworthy aoxidizes in rare earth metal
In object, the alkalinity of lanthana is higher than other rare-earth oxides, has for needing the actual industrial of base catalyst to react
Important developmental research meaning.
Nm-class catalyst pattern will affect rate of catalysis reaction, can also selectivity obtain purpose product, reduce by-product
The generation of object, essence are selectively to expose active crystal face, reactant molecule by the controllability synthesis to catalyst morphology
Combination is different on different crystal faces, to generate different intermediates, changes reaction path, be finally reached improve conversion ratio and
The purpose of selectivity.Early in last century the eighties, Volta and Jacek find that the MoO in propylene oxidation reaction3Catalyst
Apparent anisotropic characteristic aligned is shown, methacrylaldehyde is selectively generating on (100) face, but is then generated on (010) face
The product CO of complete oxidation2(J.Catal.,1983,80:263–273；Appl.Catal.,1985,18:1–32.).
Morphology controllable Journal of Sex Research (Appl.catal.B, 2018,227:209-217 of the research to simple cerium oxide at present；
J.Phys.Chem.B, 2005,109,24380-24385) it have been relatively mature, but at present for lanthanum is inserted into cerium oxide lattice
Morphology controllable Journal of Sex Research after interior formation cerium lanthanum solid solution is very few, therefore is particularly important to the research of this project, is
The synthesis of multicomponent morphology controllable provides important scientific research basis.
The comprehensive analysis above problem, it is to Guan Chong that controllable synthesis, which has specific morphology cerium lanthanum-oxides solid solution catalyst,
It wants, further contribution is done to actual industrial catalyst requirement.
Summary of the invention
The technical problem to be solved by the present invention is based on the above issues, the present invention provides a kind of nano bar-shape pattern cerium lanthanum
The preparation method of oxide solid solution.
It is nano bar-shape cerium lanthanum-oxides solid solution that the present invention, which solves a technical solution used by its technical problem,
Preparation method carries out as steps described below:
(1) it weighs NaOH to be dissolved in deionized water, is subsequently poured into constant volume in 200ml volumetric flask, for use.
(2) cerium nitrate hexahydrate and nitric hydrate lanthanum are added in 10-40ml distilled water, stirring is to two components in distilled water
It is completely dissolved, is denoted as a.
(3) NaOH solution prepared in right amount is measured with graduated cylinder and poured into a solution, stir 10-30min, gained is mixed
It closes solution to pour into hydrothermal reaction kettle, liquid volume is the 70%-80% of water heating kettle total volume.Carry out hydro-thermal reaction.
(4) after taking out water heating kettle, it is cooled to room temperature, filters, is washed with deionized neutrality, and with being put after ethanol washing
Enter in 333-353K baking oven, products obtained therefrom is ground and roasted, naturally cool to room temperature, received by dry 7-12h
The rodlike cerium lanthanum-oxides solid solution of rice.
Further, in the step (1), sodium hydrate aqueous solution is that 10-100g solid sodium hydroxide is dissolved in 100-
Sodium hydroxide solution is formed in 150ml deionized water；
Further, in the step (2), 1-2g cerium nitrate hexahydrate and 0.1-1g water are added in 10-40ml distilled water
Close lanthanum nitrate；
Further, in the step (3), hydrothermal temperature 373-473K, the reaction time is 10-15h.
Further, in the step (3), the amount for pouring into sodium hydroxide in a solution is 50-100ml.
Further, in the step (4), the sample after drying is roasted, maturing temperature 773K, calcining time
4h, Muffle furnace heating rate are 2 DEG C/min.
The cerium lanthanum-oxides solid solution of above method preparation has nanorod structure of uniform morphology.
The beneficial effects of the present invention are: the preparation method is relatively simple, preparation condition is easy to control, and raw material is easy to get, reaction
It is generated in the process without poisonous and harmful product, prepared nano bar-shape cerium lanthanum-oxides solid solution, pattern is uniform, stable structure, tool
There is certain application value.
The following further describes the present invention with reference to the drawings.
Detailed description of the invention
Fig. 1 is using a series of different alkali concentration nano bar-shape cerium lanthanum-oxides solid solution catalyst X prepared by the present invention
X ray diffration pattern x.
Fig. 2 is to use alkali concentration prepared by the present invention for 4M NaOH, and hydrothermal temperature is 423K nano bar-shape cerium lanthanum-oxides
Solid solution catalyst transmission electron microscope picture.
Fig. 3 is to use alkali concentration prepared by the present invention for 6M NaOH, and hydrothermal temperature is 423K nano bar-shape cerium lanthanum-oxides
Solid solution catalyst transmission electron microscope picture.
Fig. 4 is to use alkali concentration prepared by the present invention for 8M NaOH, and hydrothermal temperature is 423K nano bar-shape cerium lanthanum-oxides
Solid solution catalyst transmission electron microscope picture.
Fig. 5 is to use alkali concentration prepared by the present invention for 10M NaOH, and hydrothermal temperature is the oxidation of 423K nano bar-shape cerium lanthanum
Object solid solution catalyst transmission electron microscope picture.
Fig. 6 is to use alkali concentration prepared by the present invention for 10M NaOH, and hydrothermal temperature is 453K cerium lanthanum-oxides solid solution
Catalyst transmission electron microscope picture.
Specific embodiment
The present invention is further explained in the light of specific embodiments, following embodiment be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1
1) it weighs 48g NaOH to be dissolved in 150ml deionized water (NaOH concentration 6M), be subsequently poured into 200ml volumetric flask
Constant volume, for use.1.22g cerium nitrate hexahydrate and 0.51g nitric hydrate lanthanum are added in 20ml distilled water, stirring to two components is being steamed
It is completely dissolved in distilled water.It is measured the NaOH solution 60ml prepared in right amount with graduated cylinder and is poured into and dissolved complete mixed solution
In, 20min is stirred, gained mixed solution is poured into hydrothermal reaction kettle, liquid volume is the 70%- of water heating kettle total volume
80%.Carry out hydro-thermal reaction, hydrothermal temperature 423K, time 12h.After taking out water heating kettle, it is cooled to room temperature, filters, spends
For ion water washing to neutrality, and with being put into 333-353K baking oven after ethanol washing, dry 9h is ground products obtained therefrom simultaneously
It is roasted, maturing temperature 773K, maintains 4h, Muffle furnace heating rate is 2 DEG C/min, naturally cools to room temperature, is received
The rodlike cerium lanthanum-oxides solid solution of rice.
The nano bar-shape cerium lanthanum-oxides prepared using Japanese 2100 type transmission electron microscope observation embodiment 1 of JEOL
Solid solution, transmission electron microscope picture are received as shown in figure 3, as can be seen from the figure nano bar-shape cerium lanthanum-oxides solid solution is successfully prepared
Rice stick side length is about 200-300nm, width 15-20nm.
The crystal phase structure of nano bar-shape pattern cerium lanthanum-oxides solid solution catalyst is by Rigaku prepared by embodiment 1
D/max 2500PC rotation x-ray diffractometer analysis, wherein X-ray is Cu target K αVoltage 40kV,
Electric current 100mA, step-length are 0.02 °, 5 °~80 ° of scanning range.X ray diffracting spectrum as shown in Figure 1, as seen from the figure, preparation
Cerium lanthanum-oxides solid solution is successfully synthesized, and only occurs cerium oxide characteristic peak in spectrogram, does not occur the peak of the oxide of lanthanum, explanation
La is successively inserted into cerium oxide lattice, forms cerium lanthanum-oxides solid solution.
Embodiment 2
It weighs 32g NaOH to be dissolved in 150ml deionized water (NaOH concentration 4M), it is fixed to be subsequently poured into 200ml volumetric flask
Hold, for use.Remaining step and case study on implementation 1 are identical.
As shown in Fig. 2, the cerium lanthanum-oxides solid solution of synthesis is mostly Rod-like shape, pattern is relatively uniform.
Embodiment 3
It weighs 64g NaOH to be dissolved in 150ml deionized water (NaOH concentration 8M), it is fixed to be subsequently poured into 200ml volumetric flask
Hold, for use.Remaining step and case study on implementation 1 are identical.
As shown in figure 4, the cerium lanthanum-oxides solid solution of synthesis is mostly Rod-like shape, rodlike length and different widths are not away from
Greatly.
Embodiment 4
It weighs 80g NaOH to be dissolved in 150ml deionized water (NaOH concentration 10M), be subsequently poured into 200ml volumetric flask
Constant volume, for use.Remaining step and case study on implementation 1 are identical.
As shown in figure 5, the cerium lanthanum-oxides solid solution of synthesis is mostly Rod-like shape, the pattern uniformity is 4M6M8M compared with NaOH
There is relative increase, illustrates that alkali concentration will affect the synthesis of rodlike cerium lanthanum-oxides solid solution.
Embodiment 5
It weighs 80g NaOH to be dissolved in 150ml deionized water, is subsequently poured into constant volume in 200ml volumetric flask, for use.Hydro-thermal temperature
Degree is 453K, i.e. change hydrothermal temperature probes into its influence to structure and morphology.
As shown in fig. 6, the cerium lanthanum-oxides solid solution of synthesis is mostly rodlike and cube pattern mixing, illustrate hydro-thermal temperature
Degree can largely influence the synthesis of cerium lanthanum-oxides solid solution pattern.
It is enlightenment with embodiments of the invention described above, through the above description, relevant staff completely can be
In the range of this invention technical idea, various changes and amendments are carried out.The technical scope of this invention is simultaneously
The content being not limited on specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (7)
1. a kind of method of controllable preparation cerium lanthanum-oxides solid solution nanometer rods, which is characterized in that the method comprises the following steps:
(1) it weighs NaOH to be dissolved in deionized water, is subsequently poured into constant volume in 200ml volumetric flask, for use；
(2) cerium nitrate hexahydrate and nitric hydrate lanthanum are added in distilled water, stirring to two components is completely dissolved in distilled water, is remembered
For a solution；
(3) NaOH solution prepared is measured with graduated cylinder and poured into a solution, stir 10-30min, gained mixed solution is fallen
Enter in hydrothermal reaction kettle, liquid volume is the 70%-80% of water heating kettle total volume, carries out hydro-thermal reaction；
(4) after taking out water heating kettle, it is cooled to room temperature, filters, is washed with deionized neutrality, and with being put into baking after ethanol washing
It is dry in case, products obtained therefrom is ground and roasted, room temperature is naturally cooled to, it is solid to obtain nano bar-shape cerium lanthanum-oxides
Solution.
2. the method for controllable preparation cerium lanthanum-oxides solid solution nanometer rods according to claim 1, which is characterized in that described
The step of (1) in, 10-100g solid sodium hydroxide is dissolved in 100-150ml deionized water and forms sodium hydroxide solution.
3. the method for controllable preparation cerium lanthanum-oxides solid solution nanometer rods according to claim 1, which is characterized in that step
(2) in, 1-2g cerium nitrate hexahydrate and 0.1-1g nitric hydrate lanthanum are added in 10-40ml distilled water.
4. the method for controllable preparation cerium lanthanum-oxides solid solution nanometer rods according to claim 1, which is characterized in that step
(3) in, hydrothermal temperature 373-473K, the reaction time is 10-20h.
5. the method for controllable preparation cerium lanthanum-oxides solid solution nanometer rods according to claim 1, which is characterized in that step
(3) in, the amount for pouring into sodium hydroxide in a solution is 50-100ml.
6. the method for controllable preparation cerium lanthanum-oxides solid solution nanometer rods according to claim 1, which is characterized in that step
(4) in, drying temperature 333-353K, drying time 7-12h；Sample after drying is roasted, maturing temperature 773K,
Calcining time 4h, heating rate are 2 DEG C/min.
7. the cerium lanthanum-oxides solid solution that one kind is prepared method according to claim 1, which is characterized in that the cerium lanthanum oxidation
Object solid solution has nanorod structure of uniform morphology.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112844396A (en) * | 2020-12-31 | 2021-05-28 | 常州工学院 | Copper/cerium lanthanum composite oxide nanorod catalyst, preparation method and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552517A (en) * | 2003-12-19 | 2004-12-08 | 广东工业大学 | Preparation of nano cerium-zirconium rare-earth composite fluorine compound solid solution based catalyst |
| CN101962203A (en) * | 2010-09-30 | 2011-02-02 | 常州大学 | Method for synthesizing nano cerium oxide with different morphologies by hydrothermal method |
| CN103539193A (en) * | 2013-09-24 | 2014-01-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cerium-praseodymium composite oxide nanoparticle and nanorod |
| CN105800666A (en) * | 2016-05-23 | 2016-07-27 | 河北科技大学 | Preparing method for yttrium-doped dysprosium oxide nano-rods |
| CN107746069A (en) * | 2017-10-18 | 2018-03-02 | 西北师范大学 | The method that hydro-thermal method prepares different-shape ceria |
| US20180127588A1 (en) * | 2015-04-08 | 2018-05-10 | Societe Nouvelle Des Couleurs Zinciques | Anti-corrosion pigments made of aluminium polyphosphate and rare earth |
| CN108178179A (en) * | 2018-01-31 | 2018-06-19 | 江苏大学 | A kind of cerium lanthanum solid solution nanometer rods preparation method of high-temperature stable and its application as catalyst carrier |
| CN108557862A (en) * | 2018-05-28 | 2018-09-21 | 东北大学 | A kind of rare-earth-based light absorbing material, preparation method and application |
-
2019
- 2019-05-09 CN CN201910382981.3A patent/CN110040760A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552517A (en) * | 2003-12-19 | 2004-12-08 | 广东工业大学 | Preparation of nano cerium-zirconium rare-earth composite fluorine compound solid solution based catalyst |
| CN101962203A (en) * | 2010-09-30 | 2011-02-02 | 常州大学 | Method for synthesizing nano cerium oxide with different morphologies by hydrothermal method |
| CN103539193A (en) * | 2013-09-24 | 2014-01-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cerium-praseodymium composite oxide nanoparticle and nanorod |
| US20180127588A1 (en) * | 2015-04-08 | 2018-05-10 | Societe Nouvelle Des Couleurs Zinciques | Anti-corrosion pigments made of aluminium polyphosphate and rare earth |
| CN105800666A (en) * | 2016-05-23 | 2016-07-27 | 河北科技大学 | Preparing method for yttrium-doped dysprosium oxide nano-rods |
| CN107746069A (en) * | 2017-10-18 | 2018-03-02 | 西北师范大学 | The method that hydro-thermal method prepares different-shape ceria |
| CN108178179A (en) * | 2018-01-31 | 2018-06-19 | 江苏大学 | A kind of cerium lanthanum solid solution nanometer rods preparation method of high-temperature stable and its application as catalyst carrier |
| CN108557862A (en) * | 2018-05-28 | 2018-09-21 | 东北大学 | A kind of rare-earth-based light absorbing material, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 江瑞: "形貌可控的饰基氧化物的制备及催化氧化性能研究", 《中国优秀硕士学位论文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112844396A (en) * | 2020-12-31 | 2021-05-28 | 常州工学院 | Copper/cerium lanthanum composite oxide nanorod catalyst, preparation method and application |
| CN112844396B (en) * | 2020-12-31 | 2023-04-07 | 常州工学院 | Copper/cerium lanthanum composite oxide nanorod catalyst, preparation method and application |
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