CN103145201B - A kind of cellular perovskite typed microfibre and preparation method thereof - Google Patents
A kind of cellular perovskite typed microfibre and preparation method thereof Download PDFInfo
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- CN103145201B CN103145201B CN201210511609.6A CN201210511609A CN103145201B CN 103145201 B CN103145201 B CN 103145201B CN 201210511609 A CN201210511609 A CN 201210511609A CN 103145201 B CN103145201 B CN 103145201B
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Abstract
The invention belongs to inorganic micro nanometer fiber Material Field, particularly relate to a kind of cellular perovskite typed microfibre and preparation method thereof.The present invention's wide-aperture cellular perovskite structure micrometer fibers that adopted sol-gel-thermal treatment process to prepare first, technique is simple, easy to operate, raw material sources are extensive, and cost is low, and productive rate is high, adopt cellular porous perovskite structure micrometer fibers prepared by the present invention, have specific surface high, length-to-diameter ratio is large, even aperture distribution, the features such as orientation is consistent, being conducive at catalyzer, sorbent material, is used widely in strainer and microreactor aspect.
Description
Technical field
The invention belongs to inorganic micro nanometer fiber Material Field, particularly relate to a kind of cellular perovskite typed microfibre and preparation method thereof.
Background technology
Perovskite structural material is widely used in catalyzer because of its good thermostability and electrochemical stability, solid oxidized fuel cell, sensor field, porous calcium titanium ore micrometer fibers also has high specific surface except above advantage, Stability Analysis of Structures, excellent gas adsorption desorption and surfactivity, be expected in gas storage and transport, heavy metal ion administer and dye adsorption, the aspect such as aviation and semi-conductor obtains practical application, thus the uhligite fiber of the vesicular structure preparing high-ratio surface has been become to the study hotspot in inorganic materials synthetic technology.
In recent years, relevant uhligite micro nanometer fiber has been reported, as: Yang [J. Solid State Chem., 2005,178:1157 – 1164; Mater. Res. Bull., 2006,41:274 – 281] and the people such as Song [Sensor actuat. B-chem., 2010,147:248 – 254] be that template has obtained nanometer LaNiO with anodised aluminium (AAO) and cotton respectively
3(LaFeO
3) fiber and LaFeO
3tubular fibre; Leng [Mater. Lett., 2010,64:1912 – 1914] and Liu Wei [functional materials, 2007,38:2210 – 2211] has obtained LaFeO respectively by electrostatic spinning
3and LaMnO
3fiber, Wu [Mater. Res. Bull, 2010,45:1330 – 1333] is template with carbon nanotube, has obtained La
0.8ca
0.2mnO
3and LaCo
0.5mn
0.5o
3uhligite nanofiber, and be fixed on optical fiber surface and make its macroscopical diameter at 20 microns; But the perovskite typed micro nanometer fiber smooth surface of above-mentioned preparation, almost atresia or aperture little, specific surface is low; Complex process during template synthesis fiber, cost is high and productive rate is low; Natural polymer kind for Electrospun is few, the preparation of orientation fibers difficulty and high top pressure operation time safety problem, nano-scale fiber are more easily reunited, Stability Analysis of Structures performance is bad.
Summary of the invention
The object of the invention is the deficiency existed for current uhligite filamentary material and preparation method, a kind of cellular perovskite typed microfibre and preparation method thereof is provided, specific fiber surface is high, aperture ratio is large, even pore distribution, and the method technique adopted is simple, and controllability is strong.
Goal of the invention of the present invention is achieved through the following technical solutions:
A kind of cellular perovskite typed microfibre, is characterized in that: molecular formula is La
x a
1
-x fe
y b
1-
y o
3, wherein, A is a kind of in K, Sr, Ca; B is the one in Mn, Co, Ni;
xbe 0.7 ~ 1,
ybe 0 ~ 1; This fiber has cellular network structure or passage, diameter 1 ~ 5 μm, aperture size 50 ~ 320 nm.
A preparation method for cellular perovskite typed microfibre, is characterized in that preparation process comprises the following steps:
(1) a kind in citric acid and lanthanum nitrate and iron, cobalt, nickel, manganese nitrate is pressed the ratio 0.9-1.1:1 of citric acid and metal ion total mole number, mol ratio between each metal ion is dissolved in deionized water by molecular formula theoretical molar ratio and forms mixing solutions, after stirred at ambient temperature 20-48 h, rotate evaporative removal moisture at 60 ~ 80 DEG C, after obtaining spinning property gel, wire drawing obtains Precursors of Fibers;
Or a kind in a kind in citric acid and lanthanum nitrate and potassium, strontium, calcium carbonate, iron, cobalt, nickel, manganese nitrate pressed the ratio 0.9-1.1:1 of citric acid and metal ion total mole number, mol ratio between each metal ion is dissolved in deionized water by molecular formula theoretical molar ratio and forms mixing solutions, after stirring 20-48 h, rotate evaporative removal moisture at 60 ~ 80 DEG C, after obtaining spinning property gel, wire drawing obtains Precursors of Fibers;
Or citric acid and a kind in a kind in lanthanum nitrate, iron nitrate and potassium, strontium, calcium carbonate, cobalt, nickel, manganese nitrate pressed the ratio 0.9-1.1:1 of citric acid and metal ion total mole number, mol ratio between each metal ion is dissolved in deionized water by molecular formula theoretical molar ratio and forms mixing solutions, after stirring 20-48 h, rotate evaporative removal moisture at 60 ~ 80 DEG C, after obtaining spinning property gel, wire drawing obtains Precursors of Fibers;
(2) Precursors of Fibers is placed in baking oven after dry 24h, to be placed in retort furnace and to rise to 550 ~ 800 DEG C with the temperature rise rate of 1 ~ 5 DEG C/min at 90 ~ 110 DEG C, insulation 2 ~ 6 h, namely obtain cellular perovskite typed microfibre.
The present invention's wide-aperture cellular perovskite structure micrometer fibers that adopted sol-gel-thermal treatment process to prepare first, technique is simple, easy to operate, raw material sources are extensive, and cost is low, and productive rate is high, adopt cellular porous perovskite structure micrometer fibers prepared by the present invention, have specific surface high, length-to-diameter ratio is large, even aperture distribution, the features such as orientation is consistent, being conducive at catalyzer, sorbent material, is used widely in strainer and microreactor aspect.
Accompanying drawing explanation
Fig. 1 is the LaFeO obtained in embodiment 1
3the X-ray diffractogram of fiber;
Fig. 2 is the LaFeO obtained in embodiment 1
3the scanning electron microscope (SEM) photograph of fiber;
Fig. 3 is the LaMnO obtained in embodiment 2
3the X-ray diffractogram of fiber;
Fig. 4 is the LaMnO obtained in embodiment 2
3the scanning electron microscope (SEM) photograph of fiber;
Fig. 5 is the La obtained in embodiment 3
0.9k
0.1fe
0.5mn
0.5o
3the X-ray diffractogram of fiber;
Fig. 6 is the La obtained in embodiment 3
0.9k
0.1fe
0.5mn
0.5o
3the scanning electron microscope (SEM) photograph of fiber.
Embodiment
embodiment 1
(1) by 8.08 g La (NO
3)
39H
2o and 8.6602 g Fe (NO
3)
36H
2o is dissolved in 450 ml deionized waters, after dissolving completely, add 8.4056 g C
6h
8o
7h
2o, continue by this solution at room temperature magnetic agitation 24h form stable colloidal sol, wherein, citric acid and metal ion mol ratio are 1:1.
(2) above-mentioned clear solution is transferred to Rotary Evaporators, evaporative removal moisture content at 70 DEG C, obtains spinning property gel, then gel is gone to spinning-drawing machine be drawn into silk, to be put in baking oven dry 24h at 90 DEG C subsequently.
(3) dried Precursors of Fibers is put in High Temperature Furnaces Heating Apparatus with the temperature rise rate of 3 DEG C/min be raised to 600 DEG C insulation 4 h after cool to room temperature, the microfibre obtained, as shown in Fig. 1,2 scanning electron microscope and X-ray diffraction analysis, is the vesicular structure LaFeO with honeycomb channels
3micrometer fibers, Fibre diameter is 1-3 μm, aperture size 50-180 nm.
embodiment 2
(1) by 8.08 g La (NO
3)
39H
2o and 4.9018 g Mn (NO
3)
24H
2o is dissolved in 450 ml deionized waters, after dissolving completely, add 7.5650g C
6h
8o
7h
2o, continues colloidal sol stable for the at room temperature magnetic agitation formation in 24 hours of this solution; Wherein, citric acid and metal ion mol ratio are 0.9:1.
(2) above-mentioned clear solution is transferred to Rotary Evaporators, evaporative removal moisture at 60 DEG C, obtains spinning property gel, then gel is gone to spinning-drawing machine be drawn into silk, to be put in baking oven dry 24h at 110 DEG C subsequently.
(3) dried Precursors of Fibers is put in High Temperature Furnaces Heating Apparatus with the temperature rise rate of 3 DEG C/min be raised to 700 DEG C insulation 6 h after cool to room temperature, the microfibre obtained, as shown in Fig. 3,4 scanning electron microscope and X-ray diffraction analysis, is the vesicular structure LaMnO with honeycomb channels
3micrometer fibers, Fibre diameter is 2-4 μm, aperture size 80-220 nm.
embodiment 3
(1) by 7.272 g La (NO
3)
39H
2o and 4.3301 g Fe (NO
3)
36H
2o is dissolved in 450 ml deionized waters, after dissolving completely, add 8.4056 g C
6h
8o
7h
2o makes it abundant dissolving, then adds 2.4509g Mn (NO
3)
24H
2o, adds 0.1382 g KCO again after Keep agitation 2h
3, continue colloidal sol stable for the at room temperature magnetic agitation formation in 24 hours of this solution, wherein, citric acid and metal ion mol ratio are 1:1.
(2) above-mentioned clear solution is transferred to Rotary Evaporators, evaporative removal moisture at 70 DEG C, obtains spinning property gel, then gel is gone to spinning-drawing machine be drawn into silk, to be put in baking oven dry 24h at 100 DEG C subsequently.
(3) dried Precursors of Fibers is put in High Temperature Furnaces Heating Apparatus with the temperature rise rate of 3 DEG C/min be raised to 650 DEG C insulation 6 h after cool to room temperature, the microfibre obtained, as shown in Fig. 5,6 scanning electron microscope and X-ray diffraction analysis, is the vesicular structure La with honeycomb channels
0.9k
0.1fe
0.5mn
0.5o
3micrometer fibers, Fibre diameter is 2-5 μm, aperture size 120-280nm.
embodiment 4
(1) by 6.464 g La (NO
3)
39H
2o and 8.6602 g Fe (NO
3)
36H
2o is dissolved in 450 ml deionized waters, after dissolving completely, add 8.4056 g C
6h
8o
7h
2o continues to stir 2h, then adds 0.5905g Sr (NO
3)
34H
2o, then obtain comparatively stable colloidal sol in stirred at ambient temperature 20h, wherein citric acid and metal ion mol ratio are 1:1.
(2) above-mentioned clear solution is transferred to Rotary Evaporators, evaporative removal moisture at 80 DEG C, obtains spinning property gel, then gel is gone to spinning-drawing machine be drawn into silk, to be put in baking oven dry 24h at 90 DEG C subsequently.
(3) dried Precursors of Fibers is put in High Temperature Furnaces Heating Apparatus with the temperature rise rate of 3 DEG C/min be raised to 600 DEG C insulation 4 h after cool to room temperature, obtain the La of cellular structures
0.5sr
0.5feO
3micrometer fibers, diameter 1-4 μm, aperture size 50-150 nm.
embodiment 5
(1) by 6.064 g La (NO
3)
39H
2o, 6.9282 g Fe (NO
3)
36H
2o, 0.9746g Ca (NO
3)
24H
2o and 1.1641g Co (NO
3)
36H
2o is dissolved in 450 ml deionized waters, adds 9.2462g C after fully dissolving
6h
8o
7h
2o makes it abundant dissolving, stirs and forms stable colloidal sol after 20 hours; Wherein, citric acid and metal ion mol ratio are 1.1:1.
(2) above-mentioned clear solution is transferred to Rotary Evaporators, evaporative removal moisture at 80 DEG C, obtains spinning property gel, then gel is gone to spinning-drawing machine be drawn into silk, to be put in baking oven dry 24h at 100 DEG C subsequently.
(3) dried Precursors of Fibers is put into after being raised to 800 DEG C of insulation 6 h with the temperature rise rate of 3 DEG C/min in High Temperature Furnaces Heating Apparatus and cools, obtain the La of the polynuclear plane of porous
0.7ca
0.3fe
0.8co
0.2o
3micrometer fibers, diameter 2-5 μm, aperture size 80-220 nm.
Claims (3)
1. a cellular perovskite typed microfibre, is characterized in that: molecular formula is La
x a
1
-x fe
y b
1-
y o
3, wherein, A is the one in K, Sr, Ca; B is the one in Mn, Co, Ni;
xbe 0.7 ~ 1,
ybe 0 ~ 1; This fiber has cellular network structure or passage, diameter 1 ~ 5 μm, aperture size 50 ~ 320 nm.
2. the preparation method of a kind of cellular perovskite typed microfibre as claimed in claim 1, is characterized in that preparation process comprises the following steps:
(1) a kind in citric acid, lanthanum nitrate and iron, cobalt, nickel, manganese nitrate is pressed the ratio 0.9-1.1:1 of citric acid and metal ion total mole number, mol ratio between each metal ion is dissolved in deionized water by molecular formula theoretical molar ratio and forms mixing solutions, after stirred at ambient temperature 20-48 h, rotate evaporative removal moisture at 60 ~ 80 DEG C, after obtaining spinning property gel, wire drawing obtains Precursors of Fibers;
Or by citric acid, lanthanum nitrate, 1 kind in a kind in potassium, strontium, calcium carbonate and iron, cobalt, nickel, the manganese nitrate ratio 0.9-1.1:1 pressing citric acid and metal ion total mole number, mol ratio between each metal ion is dissolved in deionized water by molecular formula theoretical molar ratio and forms mixing solutions, after stirring 20-48 h, rotate evaporative removal moisture at 60 ~ 80 DEG C, after obtaining spinning property gel, wire drawing obtains Precursors of Fibers;
Or by citric acid, lanthanum nitrate, iron nitrate, 1 kind in a kind in potassium, strontium, calcium carbonate and cobalt, nickel, the manganese nitrate ratio 0.9-1.1:1 pressing citric acid and metal ion total mole number, mol ratio between each metal ion is dissolved in deionized water by molecular formula theoretical molar ratio and forms mixing solutions, after stirring 20-48 h, rotate evaporative removal moisture at 60 ~ 80 DEG C, after obtaining spinning property gel, wire drawing obtains Precursors of Fibers;
(2) Precursors of Fibers is placed in baking oven drying to be placed on retort furnace and to rise to 550 ~ 800 DEG C with the temperature rise rate of 1 ~ 5 DEG C/min, insulation 2 ~ 6 h, namely obtain cellular perovskite typed microfibre.
3. the preparation method of a kind of cellular perovskite typed microfibre as claimed in claim 2, is characterized in that: the drying conditions described in step 2 is dry 24h at 90 ~ 110 DEG C.
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| CN104746176B (en) * | 2015-04-20 | 2017-01-04 | 黑龙江大学 | CaTiO3: Eu3+/ TiO2the preparation method of composite fibre |
| CN106040249B (en) * | 2016-06-20 | 2019-07-23 | 西安交通大学 | A kind of Perovskite Catalytic persulfate and its preparation method and application |
| CN106582666B (en) * | 2016-12-21 | 2019-08-13 | 大连理工大学 | Gamma-valerolactone hydrogenation catalyst, preparation method and the method for being used to prepare 1,4- pentanediol and 2- methyltetrahydrofuran |
| CN110759457A (en) * | 2019-10-30 | 2020-02-07 | 武汉大学 | Method for removing organic pollutants in water based on perovskite oxide |
| CN113808856A (en) * | 2021-08-13 | 2021-12-17 | 常州大学 | Honeycomb-shaped LaMnO3Preparation method of super capacitor |
| CN116212854A (en) * | 2023-01-09 | 2023-06-06 | 武汉纺织大学 | La (La) 1-x K x MnO 3 Perovskite preparation method and application thereof in preparing aldehyde by selectively oxidizing organic alcohol with molecular oxygen |
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| CN101036888A (en) * | 2007-04-26 | 2007-09-19 | 天津大学 | Perovskite fiber boy compound oxide catalyst for treating automobile's waste gas, and method for preparing same |
| CN101235558A (en) * | 2008-03-12 | 2008-08-06 | 长春理工大学 | Method for preparing perovskite-type rare earth composite oxide porous hollow nano fiber |
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