CN102120183A - Preparation method of cerium-based rare earth binary one-dimensional oxide solid solution - Google Patents
Preparation method of cerium-based rare earth binary one-dimensional oxide solid solution Download PDFInfo
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Abstract
The invention relates to a preparation method of a cerium-based rare earth binary one-dimensional oxide solid solution. A soluble trivalent rare earth salt is used as a precursor, and excessive alkali substances are added as a precipitant; a cerium-based rare earth binary hydroxide solid solution is obtained by hydrothermal process, then the obtained hydroxide is roasted at the temperature of 300-500 DEG C for 3-10 hours so that the oxide solid solution Ce(1-x)RExO(2-x/2) can be obtained, wherein x is the mole fraction of the dopant, and x is more than 0 and less than 1, namely, the amount of the dopant can be optionally changed within the range of 0-100%; RE is a trivalent rare earth element such as Sm, La, Y, Gd and the like. The cerium-based rare earth binary one-dimensional oxide solid solution obtained in the preparation method has the advantages of good homogeneity and simple preparation method; and the oxygen vacancy concentration in the solid solution can be adjusted within a relatively larger concentration range. The cerium-based rare earth binary one-dimensional oxide solid solution obtained in the preparation method can be applied to various types of catalytic reactions, particularly to the catalytic purification process of automobile exhaust.
Description
Technical field
The present invention relates to a kind of preparation method of cerium base rare earth binary one dimension oxide solid solution, prepared solid solution can be used for various catalytic processes such as purifying vehicle exhaust processing.
Background technology
Along with the development of nanometer technology, nano-cerium oxide is widely used as a kind of catalysis material of excellence.This mainly is because cerium can be at Ce
3+And Ce
4+Between carry out Reversible Cycle, and have good oxygen storage capacity (OSC).In fact, the rare earth element ion that utilizes other trivalents mixes to cerium oxide and forms rare earth binary composite oxide solid solution, but realization body oxide CeO
2In oxygen room controlled modulation in a big way, thereby optimize the redox and the catalytic performance of cerium sill.
But, discover that will realize that the rare earth element ion of other trivalents mixes to cerium oxide, the oxide solid solution of preparation even structure also is not easy; Particularly in doping than under the condition with higher, tend to occur the separation of phase.Its main cause be cerium oxide different with other rare earth oxide crystal structures due to.As everyone knows, cerium oxide belongs to face-centered cubic crystal structure, and other rare earth oxides are generally simple cubic or hexagonal crystallographic texture.Because the difference of crystal structure, be doped to other rare earth oxides uniformly in the cerium oxide of face-centered cubic fluorite structure sufficiently high energy must be provided, high-temperature solid phase reaction method is the common method of this type of oxide solid solution of preparation.But high temperature solid-state method needs very high sintering temperature, and often more than micron order, specific area is minimum for the material particle size of acquisition, and is obviously improper as catalyst.Traditional coprecipitation is synthesizing mean effectively, because Ce is a kind of very special element, though trivalent cerium is stable in solution, in case form precipitation, even if also can rapid oxidized formation CeO under the room temperature in air
2Independent phase, and other rare earths often exist with the form of trivalent hydroxide, form single-phase Ce
1-xRe
xO
2-x/2Still need follow-up high-temperature roasting to handle.Therefore be necessary very much to develop a kind of brand-new low temperature synthetic route, with this obtain a kind of even doping, form solid solution adjustable in a big way.
We are devoted to the synthetic and Catalytic Performance of control of rare earth cerium base related compound always recently, we find that the valence state of cerium can be regulated and control as part by selecting suitable inorganic anion in water-heat process, utilize the anionic interaction that has strong coordination ability with trivalent cerium ion, even if under aerobic conditions, also can be easy to obtain the nanoscale Ce (OH) of stable existence in the thermal and hydric environment
3Crystalline phase.As everyone knows, the trivalent hydroxide of other rare earths and Ce (OH)
3Belong to hexagonal crystal system together, the similitude of crystal structure, trivalent rare earth element character and ionic radius makes to form binary composite rare earth hydroxide Ce
1-xRE
x(OH)
3More or less freely, dehydration can obtain corresponding C e at low temperatures subsequently
1-xRE
xO
2-x/2Because intermediate product binary composite rare earth hydroxide is uniform on microstructure, therefore, end product cerium base rare earth binary one dimension oxide solid solution has very high microhomogeneity, and form can be on a large scale in controlled modulation and the separation of phase does not take place.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of cerium base rare earth binary one dimension oxide solid solution, other rare earth element ions by hydrothermal synthesis method doping trivalent in the cerium hydroxide matrix, obtain cerium base rare earth binary one dimension hydroxide solid solution body thus, this hydroxide is carried out roasting can obtain cerium base oxide solid solution.Prepared cerium base rare earth binary one dimension oxide solid solution good uniformity is formed controlled in a big way.
Technical scheme of the present invention is as follows:
A kind of cerium base rare earth binary one dimension oxide solid solution that forms by cerium and other trivalent rare earth element, its developed by molecule formula Ce
1-xRE
xO
2-x/2, wherein, 0＜x＜1 (molar fraction), RE is trivalent rare earth element such as Sm, La, Y, Gd.
Provided by the present invention is the preparation method of the above-mentioned cerium base rare earth binary one dimension oxide solid solution of preparation, and this method is carried out as follows:
(1) getting the cerous salt of solubility and other rare earth trivalent salt is dissolved in by a certain percentage and forms mixed solution in the suitable quantity of water.
(2) excessive alkaline substance solution is poured in the above-mentioned mixed solution fast, and constantly stirred, continue again to stir about 5 minutes until generating purple or white depositions.
(3) above-mentioned sediment and solution thereof are transferred in the reactor, be put in the insulating box and carry out hydro-thermal reaction 10～24h in 100～240 ℃, obtain sediment-hydrothermal product, with hydrothermal product with washed with de-ionized water after, be drying to obtain cerium base rare earth binary one dimension hydroxide solid solution body.
(4) above-mentioned cerium base rare earth binary one dimension hydroxide solid solution body can be obtained cerium base rare earth binary one dimension solid solution, oxide at 300-500 ℃ of following roasting 3-10h.
Solubility cerous salt described in the present invention can be in cerous chlorate, cerous sulfate or the cerous oxalate any; Described other rare earth elements can be for any in the trivalent rare earth element such as Sm, La, Y, Gd; Other rare earth trivalent salt of described solubility can be in hydrochloride or the sulfate any; The concentration of cerium salt and other rare-earth salts is 0.01～1.0mol/L.
Described alkaline matter can be in NaOH, potassium hydroxide or the ammoniacal liquor any, and concentration is at 1～5mol/L.
Described preparation method, the temperature range that heats in insulating box are 100～240 ℃, and be 10～24h heat time heating time.
Described preparation method, the sintering temperature scope of hydroxide is 300-500 ℃, the time is 3-10h.
The binary one dimension cerium based solid solution homogeneity that the inventive method prepares is good, the preparation method is simple, ratio by regulation and control cerium salt and trivalent rare earth salt is the composition of adjustable solid solution, and it is adjustable in big concentration range that LR laser raman characterizes the oxygen room that shows in the solid solution.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1, example 2 gained cerium base rare earth binary one dimension hydroxide: the doping of a:Y element is 10%; The doping of b:Y element is 90%.
Fig. 2 is the XRD figure spectrum of embodiment 1, example 2 gained cerium base rare earth binary one dimensional-oxide: the doping of A:Y element is 10%; The doping of B:Y element is 90%.
Fig. 3 is Electronic Speculum (TEM) figure of embodiment 1 gained hydroxide, and the doping of Y element is 10%.
Fig. 4 is Electronic Speculum (TEM) figure of embodiment 2 gained hydroxide, and the doping of Y element is 90%.
The specific embodiment
Material source: any obtaining that cerium ion can be from cerous chlorate, cerous sulfate or cerous oxalate; Rare earth element can be Sm, La, and Y, any in the trivalent rare earth element such as Gd, rare earth element ion can be from any the obtaining solubility trivalent rare earth salt chlorate or the sulfate.
Described alkaline matter can be in NaOH, potassium hydroxide or the ammoniacal liquor any.
Above-mentioned raw materials is the commercial goods.
Embodiment 1:
Claim CeCl
37H
2O 1.0g, YCl
3XH
2O 0.06g is dissolved in the 10ml deionized water, obtains solution 1.Other takes by weighing NaOH 6g, is dissolved in the 30ml deionized water, obtains solution 2.Solution 2 is joined rapidly in the solution 1, and constantly stir until generating flocculate, continue to stir 5 minutes, then it is transferred to and puts into 120 ℃ of following heated at constant temperature 12h of insulating box in the reactor, the sediment that obtains is dry after with washed with de-ionized water can to obtain the cerium hydroxide nano rod that Y element mixes, and this nanometer rods can be obtained the cerium base rare earth binary one dimension solid solution, oxide of 10%Y element doping at 450 ℃ of roasting 6h.
Fig. 1 (a) is the XRD figure of the cerium hydroxide nano rod of above-mentioned Y element doping.
Fig. 2 (A) is the XRD figure of the cerium base rare earth binary one dimension solid solution, oxide of above-mentioned Y element doping.
Fig. 3 is the TEM figure of the cerium hydroxide nano rod that mixes of above-mentioned Y element, and the solid solution, oxide pattern that is obtained behind 450 ℃ of roasting 6h is consistent with hydroxide.
Embodiment 2:
Claim CeCl
37H
2O 0.2g, YCl
3XH
2O 1.0g is dissolved in the 10ml deionized water, obtains solution 1.Other takes by weighing NaOH 6g, is dissolved in the 30ml deionized water, obtains solution 2.Solution 2 is joined rapidly in the solution 1, and constantly stir until generating flocculate, continue to stir 5 minutes, then it is transferred to and puts into 120 ℃ of following heated at constant temperature 12h of insulating box in the reactor, the sediment that obtains is dry after with washed with de-ionized water can to obtain the cerium hydroxide nano rod that Y element mixes, and this nanometer rods can be obtained the cerium base rare earth binary one dimension solid solution, oxide of 90%Y element doping at 450 ℃ of roasting 6h.
Fig. 1 (b) is the XRD figure of the cerium hydroxide nano rod of above-mentioned Y element doping.
Fig. 2 (B) is the XRD figure of the cerium base rare earth binary one dimension solid solution, oxide of above-mentioned Y element doping.
Fig. 4 is the TEM figure of the cerium hydroxide nano rod that mixes of above-mentioned Y element, and the solid solution, oxide pattern that is obtained behind 450 ℃ of roasting 6h is consistent with hydroxide.
Embodiment 3:
Claim CeCl
37H
2O 1.0g, GdCl
36H
2O 1.0g is dissolved in the 10ml deionized water, obtains solution 1.Other takes by weighing NaOH 6g, is dissolved in the 30ml deionized water, obtains solution 2.Solution 2 is joined rapidly in the solution 1, and constantly stir until generating flocculate, continue to stir 5 minutes, then it is transferred to and puts into 120 ℃ of following heated at constant temperature 12h of insulating box in the reactor, the sediment that obtains with washed with de-ionized water after the dry cerium hydroxide nano rod that can obtain the Gd element doping, this nanometer rods can be obtained the cerium base rare earth binary one dimension solid solution, oxide of 50%Gd element doping at 450 ℃ of roasting 6h.
Embodiment 4:
Claim CeCl
37H
2O 1.0g, SmCl
3XH
2O 0.7g is dissolved in the 10ml deionized water, obtains solution 1.Other takes by weighing NaOH 6g, is dissolved in the 30ml deionized water, obtains solution 2.Solution 2 is joined rapidly in the solution 1, and constantly stir until generating flocculate, continue to stir 5 minutes, then it is transferred to and puts into 120 ℃ of following heated at constant temperature 12h of insulating box in the reactor, the sediment that obtains with washed with de-ionized water after the dry cerium hydroxide nano rod that can obtain the Sm element doping, this nanometer rods can be obtained the cerium base rare earth binary one dimension solid solution, oxide of 50%Sm element doping at 450 ℃ of roasting 6h.
Embodiment 5:
Claim CeCl
37H
2O 1.0g, LaCl
37H
2O 1.0g is dissolved in the 10ml deionized water, obtains solution 1.Other takes by weighing NaOH 6g, is dissolved in the 30ml deionized water, obtains solution 2.Solution 2 is joined rapidly in the solution 1, and constantly stir until generating flocculate, continue to stir 5 minutes, then it is transferred to and puts into 120 ℃ of following heated at constant temperature 12h of insulating box in the reactor, the sediment that obtains with washed with de-ionized water after the dry cerium hydroxide nano rod that can obtain the La element doping, this nanometer rods can be obtained the cerium base rare earth binary one dimension solid solution, oxide of 50%La element doping at 450 ℃ of roasting 6h.
Above-mentioned example shows, adopt described hydrothermal synthesis method,, can obtain the binary one dimension solid solution that different rare earth elements mix in varing proportions based on cerium oxide by the kind and the concentration of simple regulation and control rare earth element and rare-earth salts, the preparation method is simple, uniform doping.
Claims (4)
1. cerium base rare earth binary one dimension oxide solid solution is characterized in that: this solid solution is the oxide solid solution that cerium and other rare earth elements form, and its crystal form is one-dimensional rod-like or tubulose, and its developed by molecule formula is Ce
1-xRE
xO
2-x/2, wherein, 0＜x＜1 (molar fraction), RE is trivalent rare earth element such as Sm, La, Y, Gd.
2. one kind prepares the method for cerium base rare earth binary one dimension oxide solid solution according to claim 1, and it is characterized in that: this method is carried out as follows:
(1) getting the cerous salt of solubility and other rare earth trivalent salt is dissolved in by a certain percentage and forms mixed solution in the suitable quantity of water.
(2) excessive NaOH or potassium hydroxide or ammonia spirit are poured in the above-mentioned mixed solution fast, and constantly stirred, continue again to stir about 5 minutes until generating purple or white depositions.
(3) above-mentioned sediment and solution thereof are transferred in the reactor, be put in the insulating box and carry out hydro-thermal reaction 10～24h in 100～240 ℃, obtain sediment-hydrothermal product, with hydrothermal product with washed with de-ionized water after, be drying to obtain cerium base rare earth binary one dimension hydroxide solid solution body.
(4) above-mentioned cerium base rare earth binary one dimension hydroxide solid solution body can be obtained cerium base rare earth binary one dimension solid solution, oxide at 300-500 ℃ of following roasting 3-10h.
3. preparation method according to claim 2 is characterized in that, described solubility cerous salt is cerous chlorate, cerous oxalate or cerous sulfate.
4. preparation method according to claim 2 is characterized in that, described other rare earth elements are trivalent rare earth element such as Sm, La, Y, Gd, and described soluble rare-earth salt is hydrochloride or sulfate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583495A (en) * | 2012-02-23 | 2012-07-18 | 清华大学 | Preparation method of rare earth metal ion doping cerium oxide nanometer material |
| WO2017216653A1 (en) * | 2016-06-17 | 2017-12-21 | Sabic Global Technologies B.V. | Mixed cerium-lanthanum oxide catalysts and systems for oxidative halogenation of an alkane |
| CN110165269A (en) * | 2019-05-28 | 2019-08-23 | 盐城市新能源化学储能与动力电源研究中心 | A kind of solid oxide fuel cell composite electrolyte and preparation method thereof |
| CN111569892A (en) * | 2020-05-29 | 2020-08-25 | 包头稀土研究院 | Cerium-based solid solutions, process for their preparation and their use |
-
2010
- 2010-01-07 CN CN 201010000176 patent/CN102120183A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583495A (en) * | 2012-02-23 | 2012-07-18 | 清华大学 | Preparation method of rare earth metal ion doping cerium oxide nanometer material |
| CN102583495B (en) * | 2012-02-23 | 2014-08-06 | 清华大学 | Preparation method of rare earth metal ion doping cerium oxide nanometer material |
| WO2017216653A1 (en) * | 2016-06-17 | 2017-12-21 | Sabic Global Technologies B.V. | Mixed cerium-lanthanum oxide catalysts and systems for oxidative halogenation of an alkane |
| CN110165269A (en) * | 2019-05-28 | 2019-08-23 | 盐城市新能源化学储能与动力电源研究中心 | A kind of solid oxide fuel cell composite electrolyte and preparation method thereof |
| CN110165269B (en) * | 2019-05-28 | 2022-06-24 | 盐城市新能源化学储能与动力电源研究中心 | Solid oxide fuel cell composite electrolyte and preparation method thereof |
| CN111569892A (en) * | 2020-05-29 | 2020-08-25 | 包头稀土研究院 | Cerium-based solid solutions, process for their preparation and their use |
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Application publication date: 20110713 |