CN104193397B - Perovskite structure porous Ba 0.5sr 0.5co 0.8fe 0.2o 3-δmaterial and preparation method thereof - Google Patents
Perovskite structure porous Ba 0.5sr 0.5co 0.8fe 0.2o 3-δmaterial and preparation method thereof Download PDFInfo
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- CN104193397B CN104193397B CN201410428960.8A CN201410428960A CN104193397B CN 104193397 B CN104193397 B CN 104193397B CN 201410428960 A CN201410428960 A CN 201410428960A CN 104193397 B CN104193397 B CN 104193397B
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Abstract
The invention provides a kind of perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3- δmaterial and preparation method thereof, described method comprises: 1) preparation is containing Ba
2+, Sr
2+, Co
2+, Fe
3+mixed aqueous solution; 2) in mixed aqueous solution, add complexing agent and structural stabilizing agent, and mix, obtain clear solution or colloidal sol; 3) in clear solution or colloidal sol, add carbon ball, and stirring makes carbon ball dispersed, obtains suspension liquid; 4) heating lower stirring suspension liquid volatilizes wherein solvent and obtains xerogel; 5) xerogel is heat-treated at 900 ~ 1000 DEG C.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to a kind of perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial and preparation method thereof.
Background technology
There is perovskite structure ABO
3material-the Ba of type
0.5sr
0.5co
0.8fe
0.2o
3-δ, namely A position is Ba
0.5sr
0.5, B position is Co
0.8fe
0.2, be a kind of conventional fuel battery negative pole electrocatalyst materials, be widely used in the positive electrode material of the Solid Oxide Fuel Cell of 400 ~ 800 DEG C.In recent years, particularly within 2011, be published in research work on Science for representative with the YangSH of Massachusetts Polytechnics and point out, this Ba
0.5sr
0.5co
0.8fe
0.2o
3-δhigh oxygen catalytic reduction activity (ORR) can be showed at normal temperatures; The research work of the people such as EmilianaFabbri in 2014 further demonstrate that this phenomenon, and this result of study has just been published on ACSCatalysis.This is Ba
0.5sr
0.5co
0.8fe
0.2o
3-δapplication in the cathode material of low-temperature fuel cell opens Yishanmen.
But, adopt conventional sol-gel method (Sol-Gel) to prepare the Ba with perovskite structure
0.5sr
0.5co
0.8fe
0.2o
3-δ, often need synthesize at the temperature of>=1000 DEG C, obtain the general lower (≤10m of specific surface area of powder body material
2/ g).The catalyst powder material with high-specific surface area exposes more catalytic activity point, also will be conducive to and promote the carrying out of catalyzed reaction.Thus, this field is in the urgent need to a kind of low temperature synthesis specific area Ba
0.5sr
0.5co
0.8fe
0.2o
3-δthe method of material.
Summary of the invention
The present invention is intended to overcome existing Ba
0.5sr
0.5co
0.8fe
0.2o
3-δthe defect of material in performance and preparation method, the invention provides a kind of perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial and preparation method thereof.
The invention provides a kind of perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δthe preparation method of material, described method comprises:
1) preparation meets chemical formula Ba
0.5sr
0.5co
0.8fe
0.2o
3-δmiddle between Ba, Sr, Co, Fe mol ratio, containing Ba
2+, Sr
2+, Co
2+, Fe
3+mixed aqueous solution;
2) to step 1) add complexing agent and structural stabilizing agent in the mixed aqueous solution prepared, and mix, obtain clear solution or colloidal sol;
3) to step 2) add carbon ball in the clear solution prepared or colloidal sol, and stir and make carbon ball dispersed, obtain suspension liquid;
4) the lower whipping step 3 of heating) in the suspension liquid of preparation volatilize wherein solvent and obtain xerogel;
5) by step 4) xerogel prepared heat-treats, removes carbon ball, obtain described perovskite structure porous Ba at 900 ~ 1000 DEG C
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial.
Preferably, step 1) in, with Ba (NO
3)
2, Sr (NO
3)
2, Co (NO
3)
26H
2o, Fe (NO
3)
39H
2o is raw material.
Preferably, step 1) in, in mixed aqueous solution, Ba
2+volumetric molar concentration be 0.05 ~ 0.1mol/L.
Preferably, step 2) described in complexing agent and the volumetric molar concentration of structural stabilizing agent in mixing solutions be the 0.5-4 of metal ion volumetric molar concentration sum doubly.
Preferably, step 3) the middle carbon ball used, carry out alkaline purification before the use, leach, dry by carbon ball in basic solution after soaking, the diameter of carbon ball is 0.5-8 μm.
Preferably, step 5) in, the heat treated time is 4 ~ 6 hours.
Again, the invention provides perovskite structure porous Ba prepared by a kind of aforesaid method
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial, described perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial consist of Ba
0.5sr
0.5co
0.8fe
0.2o
3-δ, aperture size is 0.5 ~ 8 μm, and specific surface area is 58 ~ 100m
2/ g.
Beneficial effect of the present invention:
(1) carbon ball is adopted to be mould material, at formation perovskite structure Ba
0.5sr
0.5co
0.8fe
0.2o
3-δwhile, burn carbon template and form vesicular structure;
(2) the perovskite structure Ba for preparing of the method
0.5sr
0.5co
0.8fe
0.2o
3-δspecific surface area be greatly improved;
(3) the method is simple, and preparation condition is gentle, and calcining temperature is low, saves the energy.
Accompanying drawing explanation
Fig. 1 shows the perovskite structure porous Ba prepared in an embodiment of the invention
0.5sr
0.5co
0.8fe
0.2o
3-δxRD figure;
Fig. 2 shows the perovskite structure porous Ba prepared in an embodiment of the invention
0.5sr
0.5co
0.8fe
0.2o
3-δxRD figure;
Fig. 3 shows the perovskite structure porous Ba prepared in an embodiment of the invention
0.5sr
0.5co
0.8fe
0.2o
3-δfE-SEM photo;
Fig. 4 shows the perovskite structure porous Ba prepared in an embodiment of the invention
0.5sr
0.5co
0.8fe
0.2o
3-δfE-SEM photo.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The invention provides one and simply prepare perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δthe method of material.The method take diameter as the carbon ball of micron order (0.5 ~ 8 μm) is template, with citric acid or EDTA for complexing agent and structural stabilizing agent, with metal nitrate soluble in water for precursor, as metal nitrate salt ion (Ba
2+, Sr
2+, Co
2+, Fe
3+) when forming uniform solution or colloidal sol, add carbon ball template, form metal ion uniform ring and be around in xerogel around carbon ball, the thermal treatment of 900 ~ 1000 DEG C under air atmosphere, while burning carbon ball template, reactive metal oxide original position forms Ba
0.5sr
0.5co
0.8fe
0.2o
3-δ, obtain the porous Ba of perovskite structure
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial.Size and the Ba of resulting materials pore structure is controlled respectively by the height of the diameter and calcining temperature that simply regulate and control carbon ball template
0.5sr
0.5co
0.8fe
0.2o
3-δthe purity of phase.Obtained perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δspecific surface area (the 58-100m of material
2/ g), hole is of a size of 0.5 ~ 8 μm.Present method preparation process is simple, mild condition, easy handling, and while perovskite structure is formed, remove carbon template, power saving saves time.The method belongs to inorganic nano material synthesis field.
By controlling the diameter of carbon ball to regulate and control described Ba
0.5sr
0.5co
0.8fe
0.2o
3-δthe aperture in material duct, aperture size is 0.5 ~ 8 μm, and specific surface area is 58 ~ 100m
2/ g.
The diameter of described carbon ball is 0.5 ~ 8 μm.
The volumetric molar concentration of described complexing agent and structural stabilizing agent is 0.5 ~ 4 times of ionizable metal salt volumetric molar concentration.
Described metal-salt precursor is nitrate soluble in water.
Described metal nitrate is Ba (NO
3)
2, Sr (NO
3)
2, Co (NO
3)
26H
2o, Fe (NO
3)
39H
2o.
Heat treated temperature is 900 ~ 1000 DEG C.The described heat treated time is 4 ~ 6 hours.
The invention provides one and prepare perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δmethod, adopt carbon ball to be template, select suitable complexing agent and structural stabilizing agent to make ionizable metal salt be looped around the surface of carbon ball uniformly, at thermal treatment synthesis Ba
0.5sr
0.5co
0.8fe
0.2o
3-δwhile remove carbon ball, thus obtain the porous Ba of perovskite structure
0.5sr
0.5co
0.8fe
0.2o
3-δ, also substantially increase the specific surface area of this material, this has no report in the world.
In the present invention, perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δa specific solution of material is as follows:
(1) according to the preparation of document (Carbon39 (2001) 2211 – 2214) hydrothermal method or directly commercially the carbon ball (0.5 ~ 8 μm) of different diameter as mould material;
(2) this carbon ball material is soaked in 1h in the NaOH or ammonia soln that concentration is 0.05M, filter be placed in 60 ~ 100 DEG C of baking ovens dry 2 ~ 8h hour for subsequent use;
(3) be mBa (NO by metal nitrate according to volumetric molar concentration
3)
2: mSr (NO
3)
2: mCo (NO
3)
26H
2o:mFe (NO
3)
39H
2the ratio of O=0.5:0.5:0.8:0.2 is dissolved in 100 ~ 200ml deionized water, adds citric acid or EDTA that volumetric molar concentration is ionizable metal salt 0.5 ~ 4 times after stirring, and continues the solution that stirring 1 ~ 3h forms homogeneous transparent;
(4) clear solution in (2) is added 5 times to the carbon ball material of metal-salt mole number, after continuing to stir 2h, under gained suspension liquid stirs at 150 ~ 300 DEG C, the moisture that volatilizees gradually forms xerogel;
(5) by after the xerogel grinding that obtains in step (3), be placed in 900 ~ 1000 DEG C of thermal treatment 4 ~ 6h under retort furnace air atmosphere, obtain the porous Ba of perovskite structure
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial.
Advantage of the present invention is as follows:
(1) carbon ball is adopted to be mould material, at formation perovskite structure Ba
0.5sr
0.5co
0.8fe
0.2o
3-δwhile, burn carbon template and form vesicular structure;
(2) the perovskite structure Ba for preparing of the method
0.5sr
0.5co
0.8fe
0.2o
3-δspecific surface area be greatly improved;
(3) the method is simple, and preparation condition is gentle, and calcining temperature is low, saves the energy.
Below some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following processing parameter are also only exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1
According to technique scheme of the present invention and technical process, first preparing diameter according to document is that the carbon ball of 8 μm is as mould material, then this carbon ball material being soaked in concentration is 1h in the NaOH solution of 0.05M, through filter be placed in 60 DEG C of baking ovens dry 8h hour for subsequent use.Be mBa (NO by metal nitrate according to volumetric molar concentration
3)
2: mSr (NO
3)
2: mCo (NO
3)
26H
2o:mFe (NO
3)
39H
2the ratio of O=0.5:0.5:0.8:0.2, the i.e. Ba (NO of 1.31g
3)
2, the Sr (NO of 1.1g
3)
2, the Co (NO of 2.328g
3)
26H
2fe (the NO of O, 0.81g
3)
39H
2o, is dissolved in 200ml deionized water, adds the citric acid 8.4g that volumetric molar concentration is ionizable metal salt about 2 times after stirring, and continues to stir the solution that 3h forms homogeneous transparent.Afterwards, add 5 times to the carbon ball material 1.2g of metal-salt mole number, after continuing to stir 2h, under gained suspension liquid stirs at 300 DEG C, the moisture that volatilizees gradually forms xerogel.Xerogel, after grinding, is placed in the lower 900 DEG C of thermal treatment 6h of retort furnace air atmosphere, obtains the porous Ba of perovskite structure
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial;
The specific surface area of prepared material is: 58m
2/ g (table 1), aperture size is ~ 8 μm, as shown in the SEM photo of A in Fig. 3.
Embodiment 2
According to (with embodiment 1) described in technical process, first preparing diameter according to document is that the carbon ball of 6 μm is as mould material, and gained xerogel, after grinding, is placed in the lower 900 DEG C of thermal treatment 5h of retort furnace air atmosphere, other operational conditions are same with embodiment 1.The structure obtaining material is the Ba of perovskite typed
0.5sr
0.5co
0.8fe
0.2o
3-δ, as shown in the black spectral line in Fig. 1 XRD figure spectrum (900 DEG C/5h), specific surface area is 72m
2/ g (table 1), aperture size is ~ 5.5 μm, as shown in the SEM photo of B in Fig. 3.
Embodiment 3
According to (with embodiment 1) described in technical process, first preparing diameter according to document is that the carbon ball of 5 μm is as mould material, and gained xerogel is after grinding, and be placed in the lower 1000 DEG C of thermal treatment 5h of retort furnace air atmosphere, other operational conditions are with embodiment 1.The structure obtaining material is the Ba of perovskite typed
0.5sr
0.5co
0.8fe
0.2o
3-δ, and the purity of Perovskite Phase increases, and can find out from the red spectral line (1000 DEG C/5h) Fig. 1 XRD figure spectrum, specific surface area is 78m
2/ g (table 1), aperture size is ~ 5 μm, as shown in the SEM photo of C in Fig. 3.
Embodiment 4
According to technique scheme of the present invention and technical process, first preparing diameter according to document is that the carbon ball of 2 μm is as mould material, then this carbon ball material being soaked in concentration is 1h in the ammonia soln of 0.05M, through filter be placed in 100 DEG C of baking ovens dry 2h hour for subsequent use.Be mBa (NO by metal nitrate according to volumetric molar concentration
3)
2: mSr (NO
3)
2: mCo (NO
3)
26H
2o:mFe (NO
3)
39H
2the ratio of O=0.5:0.5:0.8:0.2, the i.e. Ba (NO of 2.62g
3)
2, the Sr (NO of 2.2g
3)
2, the Co (NO of 4.656g
3)
26H
2fe (the NO of O, 1.62g
3)
39H
2o, is dissolved in 100ml deionized water, adds the EDTA8.4g that volumetric molar concentration is ionizable metal salt about 0.7 times after stirring, and continues to stir the solution that 1h forms homogeneous transparent.Afterwards, add 5 times to the carbon ball material 2.4g of metal-salt mole number, after continuing to stir 2h, under gained suspension liquid stirs at 150 DEG C, the moisture that volatilizees gradually forms xerogel.Xerogel, after grinding, is placed in the lower 1000 DEG C of thermal treatment 4h of retort furnace air atmosphere, obtains the porous Ba of perovskite structure
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial;
The specific surface area of prepared material is: 80m
2/ g (table 1), aperture size is ~ 2 μm, as shown in the SEM photo of D in Fig. 3.
Embodiment 5
According to (with embodiment 4) described in technical process, first preparing diameter according to document is that the carbon ball of 0.5 μm is as mould material, gained xerogel, after grinding, is placed in the lower 900 DEG C of thermal treatment 5h of retort furnace air atmosphere, obtains the porous Ba of perovskite structure
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial;
The specific surface area of prepared material is: 100m
2/ g (table 1), aperture size is ~ 0.5 μm, as shown in the SEM photo of A in Fig. 4.
Comparative example 1
According to (with embodiment 1) described in technical process, do not add carbon ball, other operations are with embodiment 1, and prepared material is also perovskite structure, and as shown in the XRD figure spectrum in Fig. 2, but specific surface area is lower, only has 9.5m
2/ g (table 1).
Comparative example 2
According to (with embodiment 4) described in technical process, do not add carbon ball, other operations are with embodiment 4, and prepared material does not contain vesicular structure, as shown in the SEM photo of B in Fig. 4.
Perovskite structure porous Ba prepared by table 1
0.5sr
0.5co
0.8fe
0.2o
3-δthe specific surface area of material
| Sample | BET specific surface area/m 2.g -1 |
| 8 μm of CS-BSCF (example 1) | 58 |
| 6 μm of CS-BSCF (example 2) | 72 |
| 5 μm of CS-BSCF (example 3) | 78 |
| 2 μm of CS-BSCF (example 4) | 80 |
| 0.5 μm of CS-BSCF (example 5) | 100 |
| BSCF (comparative example 1) | 9.5 |
Claims (8)
1. a perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δthe preparation method of material, is characterized in that, described method comprises:
1) preparation meets chemical formula Ba
0.5sr
0.5co
0.8fe
0.2o
3-δmiddle between Ba, Sr, Co, Fe mol ratio, containing Ba
2+, Sr
2+, Co
2+, Fe
3+mixed aqueous solution;
2) add complexing agent and structural stabilizing agent in the mixed aqueous solution prepared to step 1), and mix, obtain clear solution or colloidal sol;
3) to step 2) add carbon ball in the clear solution prepared or colloidal sol, and stir and make carbon ball dispersed, obtain suspension liquid;
4) the lower whipping step 3 of heating) in the suspension liquid of preparation volatilize wherein solvent and obtain xerogel;
5) xerogel step 4) prepared is heat-treated at 900 ~ 1000 DEG C, removes carbon ball, obtains described perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial.
2. preparation method according to claim 1, is characterized in that, in step 1), with Ba (NO
3)
2, Sr (NO
3)
2, Co (NO
3)
26H
2o, Fe (NO
3)
39H
2o is raw material.
3. preparation method according to claim 1 and 2, is characterized in that, in step 1), in mixed aqueous solution, and Ba
2+volumetric molar concentration be 0.05 ~ 0.1mol/L.
4., according to described preparation method arbitrary in claim 1-3, it is characterized in that, step 2) in the complexing agent that uses and structural stabilizing agent be citric acid and/or EDTA.
5., according to described preparation method arbitrary in claim 1-4, it is characterized in that, step 2) described in complexing agent and the volumetric molar concentration of structural stabilizing agent in mixing solutions be the 0.5-4 of metal ion volumetric molar concentration sum doubly.
6., according to described preparation method arbitrary in claim 1-5, it is characterized in that the carbon ball used in step 3) leaches after being soaked in basic solution by carbon ball before the use, dries, the diameter of carbon ball is 0.5-8 μm.
7., according to described preparation method arbitrary in claim 1-6, it is characterized in that, in step 5), the heat treated time is 4 ~ 6 hours.
8. the perovskite structure porous Ba that in a claim 1-7 prepared by arbitrary described method
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial, is characterized in that, described perovskite structure porous Ba
0.5sr
0.5co
0.8fe
0.2o
3-δmaterial consist of Ba
0.5sr
0.5co
0.8fe
0.2o
3-δ, aperture size is 0.5 ~ 8 μm, and specific surface area is 58 ~ 100m
2/ g.
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| CN104923083B (en) * | 2015-06-04 | 2017-03-22 | 上海穗杉实业有限公司 | Stainless steel doped perovskite ceramic two-phase composite hollow fiber oxygen-permeating membrane and preparation method thereof |
| CN106582659A (en) * | 2016-11-08 | 2017-04-26 | 华东理工大学 | Mixed ion-electron conductor oxide/diatomite composite soot combustion catalyst and preparation method thereof |
| CN108117086A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of preparation method of oxygen absorbent |
| CN108114688A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of oxygen absorbent for oxygen coalescence |
| CN113996310B (en) * | 2021-10-22 | 2023-01-31 | 武汉工程大学 | Porous multi-doped perovskite catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728081A (en) * | 2009-12-03 | 2010-06-09 | 宁波大学 | Dye-sensitized nanocrystalline titanium dioxide photo anode and preparation method and application |
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| CN101728081A (en) * | 2009-12-03 | 2010-06-09 | 宁波大学 | Dye-sensitized nanocrystalline titanium dioxide photo anode and preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Ba0.5Sr0.5Co0.8Fe0.2O3-δ-Sm0.5Sr0.5CoO3-δ 复合阴极材料的性能研究;朱文霞 等;《黑龙江八一农垦大学学报》;20130228;第25卷(第1期);第79页1.1阴极粉体的制备 * |
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