CN103693961B - Preparation method of CaCu3Fe2M2O12-type composite perovskite oxide powder - Google Patents
Preparation method of CaCu3Fe2M2O12-type composite perovskite oxide powder Download PDFInfo
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- CN103693961B CN103693961B CN201310702720.8A CN201310702720A CN103693961B CN 103693961 B CN103693961 B CN 103693961B CN 201310702720 A CN201310702720 A CN 201310702720A CN 103693961 B CN103693961 B CN 103693961B
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- 239000000843 powder Substances 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910004247 CaCu Inorganic materials 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000013049 sediment Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000005054 agglomeration Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 230000005303 antiferromagnetism Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a preparation method of CaCu3Fe2M2O12-type composite perovskite oxide powder, wherein M is Nb, Ta or Sb. The method comprises the following steps: adding an M2O5 oxide to a hydrofluoric acid to prepare a transparent solution; slowly adding ammonium hydroxide to prepare a sediment M(OH)5; adding the sediment to a citric acid solution to evenly mix; adding a nitrate with the stoichiometric proportion corresponding to the general formula of the perovskite oxide to distilled water to dissolve; adding the two solutions to a high-pressure kettle according to a certain stoichiometric proportion; and keeping the high-pressure kettle warm at a certain temperature for a period of time, so as to prepare the CaCu3Fe2M2O12-type composite perovskite oxide powder. The powder prepared by the method has the advantages of being high in purity, good in mobility, narrow in particle size distribution, light in particle aggregation degree, complete in crystal development, high in sintering activity and the like, and the preparation method is relatively simple, and low in energy consumption.
Description
Technical field
The present invention relates to a kind of CaCu
3fe
2m
2o
12the hydrothermal preparing process of type composite perofskite oxide powder (M=Nb, Ta, Sb), belongs to technical field of chemical engineering.
Background technology
CaCu
3fe
2m
2o
12type composite perofskite oxide compound is a kind of good semiconductor material, simultaneously it or a kind of very promising ferromagnetic substance, and its inner ionic interaction can have ferromegnetism and antiferromagnetism simultaneously, and has relatively large magnetic moment.But the common methods of this oxide powder of synthetic preparation is high pressure solid sintering technology, due to high-temperature heat treatment, causes reunion and grain growth between powder particulate, easily affects its performance.
Based on the above, similar powder prepared by hydrothermal method has that purity is high, good fluidity, narrow diameter distribution, particle agglomeration mild degree, crystal development is complete, technique is relatively simple and sintering activity advantages of higher [Lanfredi S, Dessemond L, Martins A C Rodrigues. Dense ceramics of NaNbO
3produced from powders prepared by a new chemical route. Journal of the European Ceramic Society, 2000,20 (7): 983-990.].Meanwhile, it is once to complete in liquid phase that hydrothermal method is prepared powder, does not need the crystallization and thermal treatment in later stage, thereby has avoided hard aggregation, the crystal grain of powder grow up voluntarily and easily sneak into the shortcomings such as impurity.
Summary of the invention
The object of this invention is to provide a kind of CaCu
3fe
2m
2o
12the preparation method of type composite perofskite oxide powder, wherein M is a kind of in Nb, Ta and Sb.
Concrete steps are:
(1) by analytically pure M
2o
5it is in 10 ~ 18% hydrofluoric acid that oxide compound joins mass percent concentration, M
2o
5with the ratio of the amount of substance of pure HF be 1:1.2 ~ 5, make clear solution; Described M
2o
5for Nb
2o
5, Sb
2o
5or Ta
2o
5.
(2) in the clear solution making toward step (1), slowly adding excessive mass percent concentration is 1 ~ 8% ammoniacal liquor, makes corresponding throw out M (OH)
5.
(3) the throw out M (OH) step (2) being made
5with distilled water, clean then and dry, join mass percent concentration and be in 5 ~ 20% citric acid solution, mix, make M
5+ionic concn is the solution of 0.1 ~ 1mol/L.
(4) by Ca (NO
3)
2, Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is according to uhligite oxidation general formula CaCu
3fe
2m
2o
12corresponding stoichiometric ratio weighs and joins in distilled water, Ca
2+: Cu
2+: Fe
3+the ratio of amount of substance be 1:3:2, make Fe
3+ionic concn is the solution of 0.1 ~ 1mol/L; Nitrate used is analytical pure.
(5) solution that the solution according to 50 ~ 80% filling ratio, step (3) being made and step (4) make adds in autoclave with respective volume ratio, and volume ratio is determined by the concentration of the two, made M
5+ion and Fe
3+the amount of substance of ion is than being 1:1, and then sealing autoclave, puts into pit furnace or baking oven, with the heat-up rate of 1 ~ 10 degree Celsius of per minute, rises to 120 ~ 240 degrees Celsius, is incubated furnace cooling after 4 ~ 72 hours.
(6) taking out and open through the cooling autoclave of step (5), products therefrom in autoclave is poured out, used deionized water filtration washing repeatedly, until washings becomes neutrality, make CaCu
3fe
2m
2o
12type composite perofskite oxide powder, wherein M is a kind of in Nb, Ta and Sb.
The present invention prepares powder and has that purity is high, good fluidity, narrow diameter distribution, particle agglomeration mild degree, crystal development is complete and sintering activity advantages of higher, and do not need the crystallization and thermal treatment in later stage, thereby avoided hard aggregation, the crystal grain of powder grow up voluntarily and easily sneak into the shortcomings such as impurity, preparation method of the present invention is relatively simple simultaneously, energy expenditure is lower, compares and improves significantly and improve with High Temperature High Pressure solid phase synthesis process.
Accompanying drawing explanation
Fig. 1 is the composite perofskite oxide compound CaCu that the embodiment of the present invention 1 makes
3fe
2nb
2o
12xRD figure spectrum.
Fig. 2 is the composite perofskite oxide compound CaCu that the embodiment of the present invention 2 makes
3fe
2sb
2o
12xRD figure spectrum.
Embodiment
embodiment 1:
(1) by analytically pure Nb
2o
5join mass percent concentration and be in 10% hydrofluoric acid, Nb
2o
5with the ratio of the amount of substance of pure HF be 1:1.2, make clear solution.
(2) in the clear solution making toward step (1), slowly adding excessive mass percent concentration is 1% ammoniacal liquor, makes corresponding throw out Nb (OH)
5.
(3) the throw out Nb (OH) step (2) being made
5with distilled water, clean then and dry, join mass percent concentration and be in 5% citric acid solution, mix, make Nb
5+ionic concn is the solution of 0.1mol/L.
(4) by Ca (NO
3)
2, Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is according to perovskite oxide general formula CaCu
3fe
2m
2o
12corresponding stoichiometric ratio weighs and joins in distilled water, Ca
2+: Cu
2+: Fe
3+the ratio of amount of substance be 1:3:2, make Fe
3+ionic concn is the solution of 0.1mol/L; Described nitrate is analytical pure.
(5) solution that the solution according to 80% filling ratio, step (3) being made and step (4) make adds in autoclave with volume ratio 1:1, makes Nb
5+ion and Fe
3+the amount of substance of ion is than being 1:1, and then sealing autoclave, puts into pit furnace, with the heat-up rate of 1 degree Celsius of per minute, rises to 120 degrees Celsius, is incubated furnace cooling after 72 hours.
(6) taking out and open through the cooling autoclave of step (5), products therefrom in autoclave is poured out, used deionized water filtration washing repeatedly, until washings becomes neutrality, make CaCu
3fe
2nb
2o
12type composite perofskite oxide powder.
embodiment 2:
(1) by analytically pure Sb
2o
5join mass percent concentration and be in 15% hydrofluoric acid, Sb
2o
5with the ratio of the amount of substance of pure HF be 1:3, make clear solution.
(2) in the clear solution making toward step (1), slowly adding excessive mass percent concentration is 5% ammoniacal liquor, makes corresponding throw out Sb (OH)
5.
(3) the throw out Sb (OH) step (2) being made
5with distilled water, clean then and dry, join mass percent concentration and be in 10% citric acid solution, mix, make Sb
5+ionic concn is the solution of 0.5mol/L.
(4) by Ca (NO
3)
2, Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is according to perovskite oxide general formula CaCu
3fe
2m
2o
12corresponding stoichiometric ratio weighs and joins in distilled water, Ca
2+: Cu
2+: Fe
3+the ratio of amount of substance be 1:3:2, make Fe
3+ionic concn is the solution of 0.5mol/L; Described nitrate is analytical pure.
(5) solution that the solution according to 65% filling ratio, step (3) being made and step (4) make adds in autoclave with volume ratio 1:1, makes Sb
5+ion and Fe
3+the amount of substance of ion is than being 1:1, and then sealing autoclave, puts into baking oven, with the heat-up rate of 5 degrees Celsius of per minutes, rises to 180 degrees Celsius, is incubated furnace cooling after 40 hours.
(6) taking out and open through the cooling autoclave of step (5), products therefrom in autoclave is poured out, used deionized water filtration washing repeatedly, until washings becomes neutrality, make CaCu
3fe
2sb
2o
12type composite perofskite oxide powder.
embodiment 3:
(1) by analytically pure Ta
2o
5join mass percent concentration and be in 18% hydrofluoric acid, Ta
2o
5with the ratio of the amount of substance of pure HF be 1:5, make clear solution.
(2) in the clear solution making toward step (1), slowly adding excessive mass percent concentration is 8% ammoniacal liquor, makes corresponding throw out Ta (OH)
5.
(3) the throw out Ta (OH) step (2) being made
5with distilled water, clean then and dry, join mass percent concentration and be in 20% citric acid solution, mix, make Ta
5+ionic concn is the solution of 1mol/L.
(4) by Ca (NO
3)
2, Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is according to perovskite oxide general formula CaCu
3fe
2m
2o
12corresponding stoichiometric ratio weighs and joins in distilled water, Ca
2+: Cu
2+: Fe
3+the ratio of amount of substance be 1:3:2, make Fe
3+ionic concn is the solution of 1mol/L; Described nitrate is analytical pure.
(5) solution that the solution according to 50% filling ratio, step (3) being made and step (4) make adds in autoclave with volume ratio 1:1, makes Ta
5+ion and Fe
3+the amount of substance of ion is than being 1:1, and then sealing autoclave, puts into pit furnace, with the heat-up rate of 10 degrees Celsius of per minutes, rises to 240 degrees Celsius, is incubated furnace cooling after 4 hours.
(6) taking out and open through the cooling autoclave of step (5), products therefrom in autoclave is poured out, used deionized water filtration washing repeatedly, until washings becomes neutrality, make CaCu
3fe
2ta
2o
12type composite perofskite oxide powder.
Claims (1)
1. a CaCu
3fe
2m
2o
12the preparation method of type composite perofskite oxide powder, is characterized in that concrete steps are:
(1) by analytically pure M
2o
5it is in 10 ~ 18% hydrofluoric acid that oxide compound joins mass percent concentration, M
2o
5with the ratio of the amount of substance of pure HF be 1:1.2 ~ 5, make clear solution; Described M
2o
5for Nb
2o
5, Sb
2o
5or Ta
2o
5;
(2) in the clear solution making toward step (1), slowly adding excessive mass percent concentration is 1 ~ 8% ammoniacal liquor, makes corresponding throw out M (OH)
5;
(3) the throw out M (OH) step (2) being made
5with distilled water, clean then and dry, join mass percent concentration and be in 5 ~ 20% citric acid solution, mix, make M
5+ionic concn is the solution of 0.1 ~ 1mol/L;
(4) by Ca (NO
3)
2, Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is according to uhligite oxidation general formula CaCu
3fe
2m
2o
12corresponding stoichiometric ratio weighs and joins in distilled water, Ca
2+: Cu
2+: Fe
3+the ratio of amount of substance be 1:3:2, make Fe
3+ionic concn is the solution of 0.1 ~ 1mol/L; Nitrate used is analytical pure;
(5) solution that the solution according to 50 ~ 80% filling ratio, step (3) being made and step (4) make adds in autoclave with respective volume ratio, and volume ratio is determined by the concentration of the two, made M
5+ion and Fe
3+the amount of substance of ion is than being 1:1, and then sealing autoclave, puts into pit furnace or baking oven, with the heat-up rate of 1 ~ 10 degree Celsius of per minute, rises to 120 ~ 240 degrees Celsius, is incubated furnace cooling after 4 ~ 72 hours;
(6) taking out and open through the cooling autoclave of step (5), products therefrom in autoclave is poured out, used deionized water filtration washing repeatedly, until washings becomes neutrality, make CaCu
3fe
2m
2o
12type composite perofskite oxide powder, wherein M is a kind of in Nb, Ta and Sb.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310702720.8A CN103693961B (en) | 2013-12-19 | 2013-12-19 | Preparation method of CaCu3Fe2M2O12-type composite perovskite oxide powder |
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| CN103693961B true CN103693961B (en) | 2014-11-26 |
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| CN115074747B (en) * | 2021-03-12 | 2023-08-08 | 中国科学院物理研究所 | Quadruple perovskite oxide, preparation method and application thereof, and method for electrolyzing water |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041465A (en) * | 2007-04-23 | 2007-09-26 | 山东大学 | Method for preparation of niobic acid zinc nano material |
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2013
- 2013-12-19 CN CN201310702720.8A patent/CN103693961B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041465A (en) * | 2007-04-23 | 2007-09-26 | 山东大学 | Method for preparation of niobic acid zinc nano material |
Non-Patent Citations (1)
| Title |
|---|
| Hongping Xiang et.al..Ferrimagnetic and semiconducting CaCu3Fe2Sb2O12 by first principles.《Computational Materials Science》.2009,第46卷307-309. * |
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