CN106745334A - A kind of method that ultrasonic wave added prepares nickel cerium solid solution material - Google Patents
A kind of method that ultrasonic wave added prepares nickel cerium solid solution material Download PDFInfo
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- CN106745334A CN106745334A CN201611109886.9A CN201611109886A CN106745334A CN 106745334 A CN106745334 A CN 106745334A CN 201611109886 A CN201611109886 A CN 201611109886A CN 106745334 A CN106745334 A CN 106745334A
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Abstract
The invention belongs to solid material preparing technical field, the method that specially a kind of ultrasonic wave added prepares nickel cerium solid solution material.The present invention utilizes the processing mode of solvent heat, by nickel salts and metallic cerium salt, organic acid and organic polymer structure directing agent using fully being interacted under ultrasonic wave added, and acted on by self assembly, formed with the homogeneous flower-shaped or spherical nickel cerium solid solution of crystalline phase.The relatively low nickel content of the nickel cerium solid solution materials'use for preparing of the invention, with specific surface area it is high, metal nickle atom decentralization is high, small crystal grain yardstick and the features such as homogeneous crystalline phase, there is excellent redox property and storage put oxygen performance simultaneously, oxygen storage capacity reaches 400-600 μm of ol O/g, is had a good application prospect in fields such as environmental catalysis, solid fuel cell, sensors.
Description
Technical field
The invention belongs to solid material preparing technical field, and in particular to a kind of method for preparing nickel cerium solid solution material.
Background technology
Cerium oxide as a kind of typical rare earth oxide, in its fluorite crystals structure simultaneously presence+trivalent and+4 valency ceriums from
Son, makes it have excellent redox property and storage put oxygen performance, therefore the cerium based composite metal based on cerium oxide
Material is widely used in environmental catalysis and energy catalytic field, such as automotive exhaust catalysis oxidation, volatile organic matter（VOCs）
Catalysis oxidation, steam reforming etc..Wherein, will in metal ion mixing to cerium oxide lattice formed cerium based solid solution material because
With Lacking oxygen content higher, the catalytic reaction activity of faster ion mobility and Geng Gao and receive significant attention.
Research finds that the performance of cerium based solid solution material is mainly by grain size, crystalline phase composition and doped metal ion
The factors such as species influence.At present, the method for preparing cerium based solid solution material mainly has：Coprecipitation, colloidal sol-gel method, chemistry
Combustion method, microemulsion method and hydrothermal crystallization method etc..Coprecipitation is easily operated and is widely used in industrial life because of process is simple
In product, but its cerium based solid solution material grains for preparing is larger, and crystalline phase skewness causes catalysis activity relatively low.Using change
Learn combustion method, the solid solution crystal grain that the method such as microemulsion method is prepared can reach several nanosizeds, its specific surface area and sky
Cave relative amount showed increased, with preferable catalytic performance.For example, Li Can（Li Can, Appl. Catal. A: Gen.,
2003,246,1）Nano nickel cerium solid solution material is prepared for using combustion method of citric acid, and it was found that when nickel cerium ratio is 3: 7
When, catalyst has optimal redox property.Laguna etc.（Laguna, Appl. Catal. B: Environ.,
2011, 106, 621）Nanoscale Iron cerium solid solution material is prepared for using microemulsion method, its iron content may be up to 50at.%, and refer to
The oxygen vacancy concentration for going out the catalyst when iron content is 10at.% reaches highest while having highest redox efficiency.
The preparation of nanometer cerium base solid-solution material largely improves the performance of cerium oxide base catalyst, but on
State several method and easily crystalline phase skewness occur in preparation process, cause doping efficiency relatively low, while influenceing catalyst
Overall performance.Therefore, a kind of method for preparing the homogeneous nanometer cerium base solid-solution material of crystalline phase is developed to further optimization cerium
Base catalyst material performance has very important significance.
The content of the invention
In order to overcome the problems of prior art, the present invention to provide a kind of crystalline phase homogeneous high-performance nickel cerium solid solution
Preparation method, the present invention provide high-performance nickel cerium solid solution preparation method, first using organic polymer as structure
Directed agents and ultrasonic assisted technique, nickel cerium solid solution material is prepared using high temperature ageing process；Wherein, by adjusting slaine
The temperature and time of ratio, the temperature of solution, ultrasonically treated time, the species of template and hydro-thermal process, makes to prepare
Nickel cerium solid solution material nanoparticle pile up composition, in flower-shaped or spherical etc., pattern is homogeneous and even structure, and with big ratio
The features such as surface area and height store oxygen amount, oxygen storage capacity reaches 400-600 μm of ol O/g, in environmental catalysis, solid fuel cell, biography
The fields such as sensor have a good application prospect.
The method that the ultrasonic wave added that the present invention is provided prepares nickel cerium solid solution material, concretely comprises the following steps：
（1）Inorganic Cerium source is dissolved in organic solvent dimethyl sulfoxide (DMSO) by a certain percentage with inorganic nickel source, and is added and a certain amount of is had
Machine acid, stirring is to well mixed；Wherein, cerium nickel mol ratio is 99:1–4:1, preferential cerium nickel mol ratio is 50:1–4:1；
（2）A certain amount of organic polymer is added as structure directing agent, and carry out it is ultrasonically treated, make solution be well mixed,
A certain amount of weak aqua ammonia is added afterwards, and is sufficiently stirred for；
（3）By step（2) resulting solution carries out high-temperature process in being transferred to water heating kettle in, afterwards by filtering, washing, dry, roasting
Burning, pickling processes, that is, be obtained nickel cerium solid solution material.
In step（1) in, the Inorganic Cerium source is six water cerous nitrates（Ce(NO3)3·6H2O）Or seven water cerous chlorates
（CeCl3·7H2O）；Inorganic nickel source used is six water nickel nitrates（Ni(NO3)2·6H2O）Or six water nickel chlorides（NiCl2·
6H2O）；The organic acid is formic acid or glycolic.
In step（2) in, the macromolecular structure directed agents are polyvinylpyrrolidone（Molecular weight be 10000-
800000）Or cetyl ammonium bromide；The ultrasonication is that solution is processed using 40kHz frequency ultrasonic waves,
Process time is 0.5-4h, and solution temperature is 30-60 DEG C when ultrasonic.The ammonia concn is 1.5-3wt%.
In step（3) in, during the burin-in process, aging temperature is 120-180 DEG C, and ageing time is 0.5-72h；
The washing process is respectively with distilled water and absolute ethanol washing 2-3 times by gained solid after filtering；The drying process is
Solid after filtering is placed in 80 DEG C of baking ovens and dries 6-8h；The roasting process be by gained solid sample in air atmosphere
It is calcined, sintering temperature is 400-600 DEG C, and heating rate is 2-3 DEG C/min, and roasting time is 3-5h；The acid cleaning process
It is that gained solid is placed in washing by soaking in dust technology, dust technology concentration is 5-15wt%, and soak time is 0.5-6h, afterwards mistake
Filter.
Advantages of the present invention：
（1）Prepared nickel cerium solid solution crystalline phase is homogeneous, and nickel ion doping efficiency is high, and oxygen vacancy concentration is high；
（2）Prepared nickel cerium solid solution crystal particle scale is small, and specific surface area is big；
（3）Prepared nickel cerium solid solution nickel content is relatively low, and metallic nickel doping efficiency is high, and raw material is cheap and easy to get, manufacturing cost compared with
It is low.
Brief description of the drawings
Fig. 1 is the Scanning Electron microscope of gained nickel cerium solid solution in embodiment 1 ~ 3 and comparative example 1（SEM）Photo.
Fig. 2 is the oxygen storage capacity test result of gained nickel cerium solid solution in embodiment 1 ~ 3 and comparative example 1.
Specific embodiment
To be described in further detail for the present invention by example below, but therefore it not limited.
Embodiment 1
By 0.181g cerium chloride seven-hydrates and the water nickel chlorides of 0.029g six（Mol ratio is 4:1）It is added to and contains 40ml dimethyl sulfoxide (DMSO)s
Beaker in, and add 1.0ml formic acid, after stirring 30min, beaker is put into frequency in 40kHz supersonic cleaning machines, while slow
It is slow to add 1.0g polyvinylpyrrolidones（Molecular weight is 10000）, it is 30 DEG C to set ultrasonic temperature, starts ultrasonically treated, treatment
Time is 0.5h.4ml concentration is added for the weak aqua ammonia of 1.5wt% and is stirred, solution is transferred to outfit polytetrafluoroethylene (PTFE) afterwards
High-temperature process is carried out in the water heating kettle of liner, treatment temperature is 120 DEG C, and process time is 0.5h.After high-temperature process terminates, filtering
Solution, and 6-8h is dried at 80 DEG C afterwards, then by solid 400 with distilled water and absolute ethanol washing solid 3 times respectively
Roasting 5h, 2 DEG C/min of heating rate are carried out under DEG C air atmosphere.Gained solid is processed in being soaked in the dilute nitric acid solution of 5wt%
0.5h, by the filtering of above-mentioned identical, washing, dry, roasting process, obtains final product nickel cerium solid solution material（It is designated as
NiCeOn-1）, its pattern is as shown in figure 1, its oxygen storage capacity is as shown in Figure 2.
Embodiment 2
By the water cerous nitrates of 2.321g six and the water nickel nitrates of 0.016g six（Mol ratio is 99:1）It is added to sub- containing 100ml dimethyl
In the beaker of sulfone, and 3.0ml glycolics are added, after stirring 30min, beaker is put into frequency in 40kHz supersonic cleaning machines, together
When be slowly added to 4.0g cetyl ammonium bromides, it is 60 DEG C to set ultrasonic temperature, starts ultrasonically treated, and process time is 4h.Plus
Enter 8ml concentration for the weak aqua ammonia of 3wt% and stir, solution is transferred to is equipped with the water heating kettle of polytetrafluoroethyllining lining afterwards
High-temperature process is carried out, treatment temperature is 180 DEG C, and process time is 72h.After high-temperature process terminates, filtering solution, and respectively with steaming
Distilled water and absolute ethanol washing solid 3 times, dry 6-8h at 80 DEG C afterwards, then enter solid under 600 DEG C of air atmospheres
Row roasting 3h, 3 DEG C/min of heating rate.Gained solid processes 0.5h in being soaked in the dilute nitric acid solution of 15wt%, by above-mentioned
Identical filtering, washing, dry, roasting process, obtain final product nickel cerium solid solution material（It is designated as NiCeOn-2）, its pattern
As shown in figure 1, its oxygen storage capacity is as shown in Figure 2.
Embodiment 3
By 0.181g cerium chloride seven-hydrates and the water nickel chlorides of 0.013g six（Mol ratio is 9:1）It is added to and contains 34ml dimethyl sulfoxide (DMSO)s
Beaker in, and add 1.0ml formic acid, after stirring 30min, beaker is put into frequency in 40kHz supersonic cleaning machines, while slow
It is slow to add 1.0g polyvinylpyrrolidones（Molecular weight 30000）, it is 30 DEG C to set ultrasonic temperature, and beginning is ultrasonically treated, during treatment
Between be 1h.2ml concentration is added for the weak aqua ammonia of 2wt% and is stirred, solution is transferred to be equipped with polytetrafluoroethyllining lining afterwards
High-temperature process is carried out in water heating kettle, treatment temperature is 160 DEG C, and process time is 4h.After high-temperature process terminates, filtering solution, and
Respectively with distilled water and absolute ethanol washing solid 3 times, 6-8h is dried at 80 DEG C afterwards, then by solid in 450 DEG C of air
Roasting 4h, 2 DEG C/min of heating rate are carried out under atmosphere.Gained solid processes 2h in being soaked in the dilute nitric acid solution of 10wt%, in warp
Above-mentioned identical filtering, washing, dry, roasting process are crossed, final product nickel cerium solid solution material is obtained（It is designated as NiCeOn-3）,
Its pattern is as shown in figure 1, its oxygen storage capacity is as shown in Figure 2.
Comparative example 1
The comparative example is prepared using coprecipitation.By 1.81g cerium chloride seven-hydrates and the water nickel chlorides of 0.13g six（Mol ratio is 9:1）
It is added in the beaker containing 50ml distilled water, fully after dissolving, rapidly joins the ammoniacal liquor that concentration is 25wt%, adjusts pH value of solution
It is worth 10 or so, beaker is put into 50 DEG C of water-bath and continues to stir 1h, the hydro-thermal with polytetrafluoroethyllining lining is transferred to afterwards
In kettle at 120 DEG C high-temperature process 4h.After high-temperature process terminates, Temperature fall, and filtered, washed, dried and be calcined
Journey（Processing method is with embodiment 3）, obtain the nickel cerium solid solution material of coprecipitation preparation（It is designated as NiCeOn-CP）.
Claims (4)
1. a kind of method that ultrasonic wave added prepares nickel cerium solid solution material, it is characterised in that concretely comprise the following steps：
（1）Inorganic Cerium source is dissolved in organic solvent dimethyl sulfoxide (DMSO) with inorganic nickel source, and adds organic acid, stirring is equal to mixing
It is even；Wherein, cerium nickel mol ratio is 99:1–4:1；
（2）Organic polymer is added as structure directing agent, and carry out it is ultrasonically treated, make solution be well mixed, add afterwards
Weak aqua ammonia, and be sufficiently stirred for；
（3）By step（2) resulting solution carries out high temperature ageing treatment in being transferred to water heating kettle in, afterwards by filtering, washing, do
Dry, roasting, pickling and after baking treatment, that is, be obtained nickel cerium solid solution material.
2. method according to claim 1, it is characterised in that step（1) in, the Inorganic Cerium source be six water cerous nitrates or
Seven water cerous chlorates；Inorganic nickel source used is six water nickel nitrates or six water nickel chlorides；The organic acid is formic acid or glycolic；Institute
Organic solvent is stated for dimethyl sulfoxide (DMSO).
3. method according to claim 1, it is characterised in that step（2) in, the macromolecular structure directed agents are molecule
Measure the polyvinylpyrrolidone or cetyl ammonium bromide for 10000-800000；It is described it is ultrasonically treated be using 40kHz frequencies
Ultrasonic wave is processed solution, and process time is 0.5-4h, and solution temperature is 30-60 DEG C when ultrasonic；The ammonia concn is
1.5–3wt%。
4. method according to claim 1, it is characterised in that step（3) in, the high temperature ageing processing procedure is aging
Temperature is 120-180 DEG C, and ageing time is 0.5-72h；The washing is that gained solid after filtering is used into distilled water and nothing respectively
Water-ethanol is washed 2-3 times；The drying is that the solid after filtering is placed in 80 DEG C of baking ovens to dry 6-8h；The roasting is by institute
Obtain solid to be calcined in air atmosphere, sintering temperature is 400-600 DEG C, heating rate is 2-3 DEG C/min, roasting time
It is 3-5h；The pickling is that roasting gained solid is placed in into washing by soaking in dust technology, and dust technology concentration is 5-15wt%, immersion
Time is 0.5-6h, is filtered afterwards.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114665109A (en) * | 2022-03-18 | 2022-06-24 | 清华大学 | Electrode material of solid oxide fuel cell or electrolytic cell, and preparation method and application thereof |
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| CN1791554A (en) * | 2003-05-21 | 2006-06-21 | 韩华石油化学株式会社 | Metal oxide solid solution, preparation and use thereof |
| CN106058241A (en) * | 2016-07-21 | 2016-10-26 | 天津巴莫科技股份有限公司 | Ce1-xZrxO2 nano solid solution homogenate modified lithium ion battery anode material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1791554A (en) * | 2003-05-21 | 2006-06-21 | 韩华石油化学株式会社 | Metal oxide solid solution, preparation and use thereof |
| CN106058241A (en) * | 2016-07-21 | 2016-10-26 | 天津巴莫科技股份有限公司 | Ce1-xZrxO2 nano solid solution homogenate modified lithium ion battery anode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘鑫: ""复合氧化物(1-x)CeO2•xNiO的制备、表征及其催化性能的研究"", 《万方学位论文数据库》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114665109A (en) * | 2022-03-18 | 2022-06-24 | 清华大学 | Electrode material of solid oxide fuel cell or electrolytic cell, and preparation method and application thereof |
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