CN102180508A - Preparation method of high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution - Google Patents
Preparation method of high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution Download PDFInfo
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Abstract
The invention relates to a preparation method of a high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution, which can be applied to electrode support bodies of solid oxide fuel batteries. The preparation method of the high-crystallinity order mesoporous GDC solid solution is characterized by comprising the following steps of: (1) selecting raw materials; (2) preparing GDC precursor sol; (3) preparing a polymer solution; (4) pouring the GDC precursor sol into the polymer solution; (5) roasting; (6) when a mixed solution becomes sticky, removing a culture dish cover, and continuing a reaction for 40-60min to obtain a GDC/polyisoprene and polyethylene oxide segmented copolymer hybrid material; (7) calcining the material for 2-3h at 600-700 DEG C under an argon gas atmosphere; and (8) calcining carbon-containing GDC oxide solid solution powder for 2-3h at 400-500 DEG C under an air atmosphere to obtain the high-crystallinity order mesoporous GDC solid solution. The high-crystallinity order mesoporous GDC solid solution has the characteristics of high crystallinity, large specific surface area and regular channel structure.
Description
Technical field
The present invention relates to a kind of preparation method of order mesoporous gadolinium sesquioxide doped cerium oxide sosoloid.This order mesoporous sosoloid can be used for the electrode support of Solid Oxide Fuel Cell.
Background technology
Gadolinium sesquioxide doped cerium oxide (gadolinia doped ceria, GDC) under middle temperature (500～700 ℃) ionic conductivity than the traditional electrolyte oxidation of Solid Oxide Fuel Cell (SOFC) according to stable high 1～2 order of magnitude of zirconium white (YSZ), be in the ideal, the low-temperature solid oxide fuel cell electrolyte.Solid Oxide Fuel Cell in, operation can be widened the range of choice of corresponding each element material greatly under the low temperature, the possibility that reduces to react between the cell device, to help reducing cost, improving the life-span, but in, operation can make the kinetic activity of electrode reduce under the low temperature, thereby have influence on the performance of battery.Therefore, must seek the electrode materials that is complementary with the gadolinium sesquioxide doped cerium oxide electrolyte.Recently, in order to improve the performance of electrode, the combined electrode of a kind of ion and electronics hybrid conductive becomes a main research focus.Ni/GDC composite anode materials for example, Ni has the catalyzed oxidation of fuel and the function of electronic conduction, and GDC is mainly as the supporter of Ni, and has the ionic conduction function.Same, lanthanum manganate (LSM)/GDC also is used as cathode material.The performance of these combined electrodes and gas three phase boundary (TPB) length have very big relation, the long more catalytic rate that has utilization to improve electrode more of TPB length.The TPB of this length can reach by the GDC material that preparation has a uniform sequential pore structure.The pore passage structure of rule can improve dispersed and stable to catalyzer, thereby greatly improve catalytic activity.Therefore how to prepare have bigger serface, focus that regular pore canal structure, the high GDC hole material of stability become research.
Prepare order mesoporous crystallization GDC oxide solid solution and mainly adopt soft, hard template method, soft template method adopts organic segmented copolymer to guide reagent as structure, remove the GDC oxide solid solution that template obtains meso-hole structure by calcining in air, but this method is difficult to obtain high crystalline GDC oxide solid solution, because may cause mesoporous caving at the removing template that goes down of high-temperature very.Hard template method is that the GDC oxide precursor is penetrated in the hard template of ordered mesoporous silicon or charcoal, at high temperature remove template then, can obtain the mesoporous GDC oxide solid solution of high crystalline, and mesoporous being not easy caved in, but this method is time-consuming, and the program complexity is difficult to control, it is also difficult to obtain the ideal hard template, and is difficult to allow the GDC oxide precursor fill all holes.Therefore, it is imperative to explore a kind of preparation method of the order mesoporous GDC oxide solid solution of high crystallization of simple possible.
Summary of the invention
The preparation method who the purpose of this invention is to provide the order mesoporous gadolinium sesquioxide doped cerium oxide of a kind of high crystalline sosoloid, degree of crystallinity height, the specific surface area of the order mesoporous gadolinium sesquioxide doped cerium oxide sosoloid of this method preparation are big, and technology is simple.
To achieve these goals, the technical solution used in the present invention is: the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid is characterized in that it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.5-2.5,
Methyl ethyl diketone gadolinium hydrate 0.35-0.45,
Methyl alcohol 20-30,
N, dinethylformamide 0.3-0.5,
Tetrahydrofuran (THF) 3.0-4.0,
Chloroform 5.0-6.0,
Polyisoprene and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, tetrahydrofuran (THF), chloroform, polyisoprene and polyethylene oxide block copolymer, standby;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH
3COCHCOCH
3)
3XH
2O), methyl ethyl diketone gadolinium hydrate (Gd (CH
3COCHCOCH
3)
3XH
2O), methyl alcohol and N, dinethylformamide (adds deionized water or does not add deionized water; When adding deionized water, the shared parts by weight of deionized water are 0.2-0.4), stirring at room 1-2 hour, obtain the GDC precursor sol, stand for standby use;
3) preparation of polymers soln: tetrahydrofuran (THF) and chloroform are mixed, obtain the mixed solvent of tetrahydrofuran (THF) and chloroform; Add polyisoprene and polyethylene oxide block copolymer in the mixed solvent of tetrahydrofuran (THF) and chloroform, 65-70 ℃ of dissolving 1 hour, cool to room temperature obtained polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the culture dish lid, 65-70 ℃ of baking 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the culture dish lid, continue 40-60 minute (gelation reaction) of reaction, obtain GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material;
7) GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 2-3 hour (temperature rise rate is 20-25 ℃/minute) of 600-700 ℃ of calcining;
8) under air atmosphere, 400-500 ℃ of calcining carbonaceous GDC oxide solid solution powder 2-3 hour (temperature rise rate is 20-25 ℃/minute) obtains the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
Raw material in the described step 1) also comprises deionized water, and the shared parts by weight of deionized water are: 0.2-0.4; Deionized water is in step 2) in methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol and N, dinethylformamide stirs together.
Water content x=3-4 in the molecular formula of described methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate;
Described methyl alcohol, N, dinethylformamide, tetrahydrofuran (THF), chloroform are analytical pure, and purity is greater than 98wt%;
Described polyisoprene and polyethylene oxide block copolymer number-average molecular weight are 50.5 * 10
3, molecular weight distribution is 1.05, the weight percentage of polyoxyethylene segments is 15wt%.
Described polyisoprene and polyethylene oxide block copolymer (polymer P I-PEO) be from Canadian Polymer Source, Inc. (Montreal Canada) directly buys,
Http:// www.polymersource.com/
The present invention adopts has the active methyl ethyl diketone cerium of low in hydrolysis, the methyl ethyl diketone gadolinium is as the presoma of sol-gel, adopt amphipathic polyisoprene and polyethylene oxide block copolymer structure guiding reagent as the preparation of GDC oxide compound, mode by self-assembly, the GDC oxide precursor selects swelling in hydrophilic polyoxyethylene segments, remove polymer architecture guiding reagent by two step calcining procesies then, the firm decolorizing carbon that forms in the calcination process can support the wall of mesoporous GDC oxide solid solution effectively, prevent mesoporous the caving in of GDC oxide solid solution when high temperature, therefore adopted present method can obtain the order mesoporous GDC oxide solid solution of high crystalline.
The present invention adopts has the active methyl ethyl diketone cerium of low in hydrolysis hydrate, methyl ethyl diketone gadolinium hydrate is as the presoma of GDC sol-gel, adopt amphipathic polyisoprene and polyethylene oxide block copolymer structure guiding reagent as the preparation of GDC oxide compound, mode by self-assembly, the GDC oxide precursor selects swelling in hydrophilic polyoxyethylene segments, remove polymer architecture guiding reagent by two step calcining procesies then, in the template removal processes under the argon gas atmosphere, polyoxyethylene segments is easy to decompose), but polyisoprene is more stable, it will be converted into firm decolorizing carbon, this original position carbon can support the wall of mesoporous GDC oxide solid solution effectively, prevent mesoporous the caving in of GDC oxide solid solution when high temperature, therefore adopt present method can obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
Compare with existing method, the present invention has following advantage:
1) the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid of the present invention's preparation, with respect to soft template method, the degree of crystallinity height, and have bigger serface, regular pore canal structure (being mesoporous orderly), stability height.
2) the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid of the present invention's preparation, with respect to hard template method, it is simple to have technology, is easy to control.
The order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid of the present invention's preparation can be used for the electrode support of Solid Oxide Fuel Cell.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.554,
Methyl ethyl diketone gadolinium hydrate 0.355,
Methyl alcohol 25.37,
N, dinethylformamide 0.415,
Tetrahydrofuran (THF) 3.0,
Chloroform 5.0,
Polyisoprene and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, tetrahydrofuran (THF), chloroform, polyisoprene and polyethylene oxide block copolymer, standby;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH
3COCHCOCH
3)
3XH
2O, x=3), methyl ethyl diketone gadolinium hydrate (Gd (CH
3COCHCOCH
3)
3XH
2O, x=3), methyl alcohol and N, dinethylformamide (not adding deionized water), stirring at room 1 hour obtains stable GDC precursor sol, stand for standby use;
3) preparation of polymers soln: tetrahydrofuran (THF) and chloroform are mixed, obtain the mixed solvent of tetrahydrofuran (THF) and chloroform; Add polyisoprene and polyethylene oxide block copolymer in the mixed solvent of tetrahydrofuran (THF) and chloroform, 65 ℃ of dissolvings 1 hour, cool to room temperature obtained limpid polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the culture dish lid, 65 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the culture dish lid, continue 40 minutes (gelation reaction) of reaction, obtain GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material;
7) GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 2 hours (temperature rise rate is 20-25 ℃/minute) of 600 ℃ of calcinings;
8) under air atmosphere, 400 ℃ of calcining carbonaceous GDC oxide solid solution powders 2 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 2:
The preparation method is with embodiment 1, only the deionized water that do not add of embodiment 1 increased to and adds deionized water 0.315g.Deionized water is in step 2) in methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol and N, dinethylformamide stirs together.The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 3:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.554,
Methyl ethyl diketone gadolinium hydrate 0.355,
Methyl alcohol 25.37,
N, dinethylformamide 0.415,
Deionized water 0.315,
Tetrahydrofuran (THF) 4.0g,
Chloroform 6.0g,
Polyisoprene and polyethylene oxide block copolymer 0.5g,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, tetrahydrofuran (THF), chloroform, polyisoprene and polyethylene oxide block copolymer, standby;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH
3COCHCOCH
3)
3XH
2O, x=3), methyl ethyl diketone gadolinium hydrate (Gd (CH
3COCHCOCH
3)
3XH
2O, x=3), methyl alcohol, N, dinethylformamide and deionized water, stirring at room 2 hours obtains stable GDC precursor sol, stand for standby use;
3) preparation of polymers soln: tetrahydrofuran (THF) and chloroform are mixed, obtain the mixed solvent of tetrahydrofuran (THF) and chloroform; Add polyisoprene and polyethylene oxide block copolymer in the mixed solvent of tetrahydrofuran (THF) and chloroform, 70 ℃ of dissolvings 1 hour, cool to room temperature obtained limpid polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the culture dish lid, 70 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the culture dish lid, continue 50 minutes (gelation reaction) of reaction, obtain GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material;
7) GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 2 hours (temperature rise rate is 20-25 ℃/minute) of 600 ℃ of calcinings;
8) under air atmosphere, 400 ℃ of calcining carbonaceous GDC oxide solid solution powders 2 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 4:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.554,
Methyl ethyl diketone gadolinium hydrate 0.355,
Methyl alcohol 25.37,
N, dinethylformamide 0.415,
Tetrahydrofuran (THF) 4.0,
Chloroform 6.0,
Polyisoprene and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, tetrahydrofuran (THF), chloroform, polyisoprene and polyethylene oxide block copolymer, standby;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH
3COCHCOCH
3)
3XH
2O, x=4), methyl ethyl diketone gadolinium hydrate (Gd (CH
3COCHCOCH
3)
3XH
2O, x=4), methyl alcohol and N, dinethylformamide (not adding deionized water), stirring at room 1.5 hours obtains stable GDC precursor sol, stand for standby use;
3) preparation of polymers soln: tetrahydrofuran (THF) and chloroform are mixed, obtain the mixed solvent of tetrahydrofuran (THF) and chloroform; Add polyisoprene and polyethylene oxide block copolymer in the mixed solvent of tetrahydrofuran (THF) and chloroform, 68 ℃ of dissolvings 1 hour, cool to room temperature obtained limpid polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the culture dish lid, 68 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the culture dish lid, continue 60 minutes (gelation reaction) of reaction, obtain GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material;
7) GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 2.5 hours (temperature rise rate is 20-25 ℃/minute) of 700 ℃ of calcinings;
8) under air atmosphere, 500 ℃ of calcining carbonaceous GDC oxide solid solution powders 2.5 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 5:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.554,
Methyl ethyl diketone gadolinium hydrate 0.355,
Methyl alcohol 25.37,
N, dinethylformamide 0.415,
Tetrahydrofuran (THF) 3.0,
Chloroform 5.0,
Polyisoprene and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, tetrahydrofuran (THF), chloroform, polyisoprene and polyethylene oxide block copolymer, standby;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH
3COCHCOCH
3)
3XH
2O, x=4), methyl ethyl diketone gadolinium hydrate (Gd (CH
3COCHCOCH
3)
3XH
2O, x=4), methyl alcohol and N, dinethylformamide (not adding deionized water), stirring at room 2 hours obtains stable GDC precursor sol, stand for standby use;
3) preparation of polymers soln: tetrahydrofuran (THF) and chloroform are mixed, obtain the mixed solvent of tetrahydrofuran (THF) and chloroform; Add polyisoprene and polyethylene oxide block copolymer in the mixed solvent of tetrahydrofuran (THF) and chloroform, 70 ℃ of dissolvings 1 hour, cool to room temperature obtained limpid polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the culture dish lid, 70 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the culture dish lid, continue 50 minutes (gelation reaction) of reaction, obtain GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material;
7) GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 3 hours (temperature rise rate is 20-25 ℃/minute) of 700 ℃ of calcinings;
8) under air atmosphere, 500 ℃ of calcining carbonaceous GDC oxide solid solution powders 3 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 6:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.5,
Methyl ethyl diketone gadolinium hydrate 0.35,
Methyl alcohol 20,
N, dinethylformamide 0.3,
Deionized water 0.2,
Tetrahydrofuran (THF) 3.0,
Chloroform 5.0,
Polyisoprene and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, tetrahydrofuran (THF), chloroform, polyisoprene and polyethylene oxide block copolymer, standby;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH
3COCHCOCH
3)
3XH
2O, x=3), methyl ethyl diketone gadolinium hydrate (Gd (CH
3COCHCOCH
3)
3XH
2O, x=3), methyl alcohol and N, dinethylformamide adds deionized water, and stirring at room 1 hour obtains the GDC precursor sol, stand for standby use;
3) preparation of polymers soln: tetrahydrofuran (THF) and chloroform are mixed, obtain the mixed solvent of tetrahydrofuran (THF) and chloroform; Add polyisoprene and polyethylene oxide block copolymer in the mixed solvent of tetrahydrofuran (THF) and chloroform, 65 ℃ of dissolvings 1 hour, cool to room temperature obtained polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the culture dish lid, 65 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the culture dish lid, continue 40 minutes (gelation reaction) of reaction, obtain GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material;
7) GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 2 hours (temperature rise rate is 20-25 ℃/minute) of 600 ℃ of calcinings;
8) under air atmosphere, 400 ℃ of calcining carbonaceous GDC oxide solid solution powders 2 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 7:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 2.5,
Methyl ethyl diketone gadolinium hydrate 0.45,
Methyl alcohol 30,
N, dinethylformamide 0.5,
Deionized water 0.4,
Tetrahydrofuran (THF) 4.0,
Chloroform 6.0,
Polyisoprene and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, tetrahydrofuran (THF), chloroform, polyisoprene and polyethylene oxide block copolymer, standby;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH
3COCHCOCH
3)
3XH
2O, x=4), methyl ethyl diketone gadolinium hydrate (Gd (CH
3COCHCOCH
3)
3XH
2O, x=4), methyl alcohol and N, dinethylformamide adds deionized water, and stirring at room 2 hours obtains the GDC precursor sol, stand for standby use;
3) preparation of polymers soln: tetrahydrofuran (THF) and chloroform are mixed, obtain the mixed solvent of tetrahydrofuran (THF) and chloroform; Add polyisoprene and polyethylene oxide block copolymer in the mixed solvent of tetrahydrofuran (THF) and chloroform, 70 ℃ of dissolvings 1 hour, cool to room temperature obtained polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the culture dish lid, 70 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the culture dish lid, continue 60 minutes (gelation reaction) of reaction, obtain GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material;
7) GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 3 hours (temperature rise rate is 20-25 ℃/minute) of 700 ℃ of calcinings;
8) under air atmosphere, 500 ℃ of calcining carbonaceous GDC oxide solid solution powders 3 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Table 1, the The performance test results of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid
The order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that table 1 explanation embodiment of the invention 1-7 obtains has that degree of crystallinity height, specific surface area are big, the characteristics of regular pore canal structure (be mesoporous in order).
Each raw material that the present invention is cited, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (5)
1. the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid is characterized in that it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.5-2.5,
Methyl ethyl diketone gadolinium hydrate 0.35-0.45,
Methyl alcohol 20-30,
N, dinethylformamide 0.3-0.5,
Tetrahydrofuran (THF) 3.0-4.0,
Chloroform 5.0-6.0,
Polyisoprene and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, tetrahydrofuran (THF), chloroform, polyisoprene and polyethylene oxide block copolymer, standby;
2) preparation of GDC precursor sol: add methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol and N in the there-necked flask of induction stirring is housed, dinethylformamide stirring at room 1-2 hour, obtains the GDC precursor sol, stand for standby use;
3) preparation of polymers soln: tetrahydrofuran (THF) and chloroform are mixed, obtain the mixed solvent of tetrahydrofuran (THF) and chloroform; Add polyisoprene and polyethylene oxide block copolymer in the mixed solvent of tetrahydrofuran (THF) and chloroform, 65-70 ℃ of dissolving 1 hour, cool to room temperature obtained polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the culture dish lid, 65-70 ℃ of baking 24 hours down;
6) when mixing solutions becomes thickness, remove the culture dish lid, continue reaction 40-60 minute, obtain GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material;
7) GDC/ polyisoprene and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 600-700 ℃ of calcining 2-3 hour;
8) under air atmosphere, calcined carbonaceous GDC oxide solid solution powder 2-3 hour, and obtained the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid for 400-500 ℃.
2. the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of crystalline according to claim 1 sosoloid, it is characterized in that: the raw material in the described step 1) also comprises deionized water, the shared parts by weight of deionized water are: 0.2-0.4; Deionized water is in step 2) in methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol and N, dinethylformamide stirs together.
3. the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of crystalline according to claim 1 sosoloid is characterized in that: the water content x=3-4 in the molecular formula of described methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate;
4. the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of crystalline according to claim 1 sosoloid is characterized in that: described methyl alcohol, N, and dinethylformamide, tetrahydrofuran (THF), chloroform are analytical pure, and purity is greater than 98wt%;
5. the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of crystalline according to claim 1 sosoloid, it is characterized in that: described polyisoprene and polyethylene oxide block copolymer number-average molecular weight are 50.5 * 10
3, molecular weight distribution is 1.05, the weight percentage of polyoxyethylene segments is 15wt%.
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