CN100558640C - Single-crystal perovskite type oxide La 2CuO 4The preparation method of nano and micron rod - Google Patents
Single-crystal perovskite type oxide La 2CuO 4The preparation method of nano and micron rod Download PDFInfo
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- CN100558640C CN100558640C CNB2007101789240A CN200710178924A CN100558640C CN 100558640 C CN100558640 C CN 100558640C CN B2007101789240 A CNB2007101789240 A CN B2007101789240A CN 200710178924 A CN200710178924 A CN 200710178924A CN 100558640 C CN100558640 C CN 100558640C
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Abstract
Single-crystal perovskite type oxide La
2CuO
4The preparation method of nano and micron rod belongs to the nanocatalyst preparation field.Under the condition of hydro-thermal, by the oxide compound of selecting lanthanum nitrate or lanthanum be lanthanum source, control potassium hydroxide be the consumption, hydrothermal temperature of alkali source at 180 ℃-260 ℃ and time 24h-48h, 850 ℃ of calcination temperatures and time 2h-6h, can obtain nano and micron rod shape perovskite-like type oxide compound La
2CuO
4The perovskite-like type oxide compound La that the present invention obtained
2CuO
4Have and receive the bar-shaped pattern of micron-scale and good single crystal structure.This has the perovskite-like type oxide compound La of unique pattern and single crystal structure
2CuO
4Have a good application prospect in fields such as superconducting material, chemical sensor, catalytic cleaning of car tail gas, oxynitride catalysis elimination, catalytic organism oxidations.
Description
Technical field
The present invention relates to a kind of preparation method of single-crystal perovskite type oxide nano and micron rod, relate in particular to and utilize hydrothermal synthesis method to prepare single-crystal perovskite type oxide La
2CuO
4The method of nano and micron rod, it belongs to the nanocatalyst preparation field.
Background technology
Perofskite type oxide (ABO
3) and perovskite-like type oxide compound (A
2BO
4) be the composite oxides of people's extensive concern.At A
2BO
4In the structure, A position ion and 9 oxygen atom ligands, B position ion is positioned at BO
6Octahedral center forms tetragonal structure.This compounds has unique physicochemical property (as ferromegnetism, ferroelectricity, supraconductivity, heat conductance, adsorptivity, oxidation-reduction quality etc.).Since the 1950's, perovskite-like type oxide compound has obtained extensive studies and application at aspects such as catalyzed oxidation, environmental catalysis, shortening, hydrocracking, photochemical catalysis, solid fuel cell and chemical sensors.
The preparation method of perovskite-like type oxide compound has very big influence to its physical and chemical performance (as structure, pattern, size, specific surface area and catalytic activity etc.).The preparation method who generally adopts has citric acid complex method (H.X.Dai, et al., Catal.Lett. at present, 2000,67:183-192), evaporation, decomposition method (S.D.Peter, et al., Appl.Catal.A, 2001,205:147-158), solid reaction process (H.X.Dai, et al., J.Catal., 2001,197:251-266), polyoxyethylene glycol gel method (Z.Zhao, et al., Appl.Catal.B, 1996,8:281-289), polyacrylamide high-molecular gel method (N.Guihanume, etal. .J.Catal., 1997,165:197-204.), diethylene triamine pentacetic acid (DTPA) complexometry (A.Gonzalez, et al., Catal.Today, 1997,33:361-369), critical water hypobaric drying method (G..A.Alexander, et al., Angew.Chem.Int.Ed., 2000,39:2738-2740) etc.But condition complex process, cost that these methods require are higher, and it is irregular that the particle diameter of prepared perovskite-like type oxide compound reaches pattern more greatly, and be polycrystalline structure.There is the shortcoming that is difficult to target product is carried out pattern and grain size control in these methods.Although the hard template technology that grows up in succession in recent years helps realizing largely the control to particle morphology, grain size and distribution thereof, but be subjected to the restriction of the character of template own.Compare with three-dimensional macroparticle, its one dimension nano and micro materials has the physico-chemical property of many uniquenesses, has purposes widely in fields such as material, physics, chemistry.In recent years, the synthetic technology of one dimension nano and micro materials has obtained development rapidly, and people have synthesized many one dimension Nano/micro tubes (line, rod etc.) compound.For example, be hard template with porous polycarbonate film (aperture is 1 μ m, and thickness is 8 μ m), utilize microwave-assisted denitration technology (this heat treatment process directly influences the final pattern of product), can prepare La
0.325Pr
0.300Ca
0.375MnO
3Nanotube, its external diameter are 800nm, and length is about 4 μ m, thickness of pipe be 150nm (A.G.Leyva, J.Solid State Chem., 2004,177:3949-3953).Adopt hydrothermal synthesis method can prepare single-phase cubic perovskite type oxide compound La
0.5Sr
0.5MnO
3Nano wire and La
0.5Ba
0.5MnO
3Nanometer piece (J.B.Liu, et al., Mater.Res.Bull., 2003,38:817-822; J.J.Urban, et al., Nano.Lett., 2004,4:1547-1550).Yet, also do not adopt hydrothermal synthesis method to prepare the report of monocrystalline one dimension perovskite-like type oxide compound up to now.According to the method that the present invention describes, selects different presomas, by controlling alkali source concentration, hydrothermal temperature and time, calcination temperature and time, can prepare the nano and micron rod shape perovskite-like type oxide compound La of different size size
2CuO
4The background technology of at present relevant this respect especially patent there is no report.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of perovskite-like type oxide compound nano and micron rod, the product that the present invention prepares is the nano and micron rod shape composite oxides of single-crystal perovskite type structure.
The preparation method of a kind of single-crystal perovskite type oxide La2CuO4 nano and micron rod provided by the invention, it is characterized in that: under normal temperature, normal pressure and magnetic agitation condition, with the cupric nitrate is the copper source, oxide compound with lanthanum nitrate or lanthanum is the lanthanum source, with potassium hydroxide is precipitation agent, wherein cupric nitrate: lanthanum nitrate: the amount of substance ratio of potassium hydroxide is: 1: 2: 35.71; Cupric nitrate: lanthanum trioxide: the amount of substance ratio of potassium hydroxide is: 1: 1: 35.71; With concentration is that the potassium hydroxide solution of 17.85mol/L adds in the mixing solutions of being made up of copper source and lanthanum source, form precipitation, after continuing to stir, be transferred to ultrasonic dispersing 0.5h in the ultrasonic cleaner, again it is transferred in the stainless steel cauldron that liner is a tetrafluoroethylene, put in the thermostat container in 180oC-260oC insulation 24h-48h, cooling afterwards, with the products therefrom deionized water wash, suction filtration, dry, put into retort furnace and rise to 400oC and at 400oC insulation 1h from room temperature, continue to be warmed up to 850oC with the temperature rise rate of 3oC/min again and at 850oC insulation 2h-6h with the temperature rise rate of 1oC/min; Obtain nano and micron rod shape perovskite-like type oxide compound La2CuO4 after the grinding.
Adopt hydrothermal method by selecting lanthanum source, alkali source, hydro-thermal time and temperature, calcination time and temperature prepare nano and micron rod shape single-crystal perovskite type oxide does not still have report.
The gained powdered product is characterized with X-ray diffractometer (XRD), environmental scanning electron microscope (ESEM), transmission electron microscope (TEM) and selected area electron diffraction technology such as (SAED).The result shows that adopting the obtained sample of present method is single-crystal perovskite type oxide La
2CuO
4Nano and micron rod.
Description of drawings
For further understanding the present invention, elaborate with embodiment below, and provide accompanying drawing and describe the nano and micron rod shape single-crystal perovskite type oxide La that the present invention obtains
2CuO
4Particle, wherein:
Fig. 1 is for receiving the bar-shaped La of micron monocrystalline
2CuO
4The XRD spectra of sample, wherein curve (a) La
2CuO
4Embodiment 1; (b) La
2CuO
4Embodiment 2; (c) La
2CuO
4Embodiment 3.
Fig. 2 (a), 2 (b) are respectively and receive the bar-shaped La of micron monocrystalline
2CuO
4The ESEM of embodiment 1 sample and TEM photo, wherein the illustration among Fig. 2 (b) is the SAED pattern of this sample.
Fig. 3 (a), 3 (b) are respectively and receive the bar-shaped La of micron monocrystalline
2CuO
4The ESEM of embodiment 2 samples and TEM photo, wherein the illustration among Fig. 3 (b) is the SAED pattern of this sample.
Fig. 4 (a), 4 (b) are respectively and receive the bar-shaped La of micron monocrystalline
2CuO
4The ESEM of embodiment 3 samples and TEM photo, wherein the illustration among Fig. 4 (b) is the SAED pattern of this sample.
Embodiment
Concrete implementation step of the present invention is as follows:
Embodiment 1: under normal temperature, normal pressure and magnetic agitation condition, with 0.02mol La (NO
3)
36H
2O is dissolved in the 10ml deionized water, behind magnetic agitation (500 rev/mins) 15min, adds 0.01mol Cu (NO in above-mentioned solution
3)
23H
2O continues to stir 15min.In addition with 20g KOH dissolving extremely fully in the 20ml deionized water, slowly join in the above-mentioned mixing solutions again, after continuing to stir 0.5h, be transferred in the ultrasonic cleaner, behind the ultrasonic dispersing 0.5h, it is transferred to (80% volume loading level) in the stainless steel cauldron that liner is a tetrafluoroethylene, put in the thermostat container in 260 ℃ of insulation 24h, be cooled to room temperature afterwards, take out, with deionized water wash, suction filtration 4 times, dry (60 ℃, 12h).The gained pressed powder is placed retort furnace, rise to 400 ℃ and from room temperature, continue to be warmed up to 850 ℃ and with 3 ℃/min temperature rise rate again at 850 ℃ of constant temperature 2h at 400 ℃ of insulation 1h with 1 ℃/min temperature rise rate.After grinding, obtaining diameter is that 80～200nm, length are the nano and micron rod shape single-crystal perovskite type oxide La of 2～10 μ m
2CuO
4Particle.
Embodiment 2: under normal temperature, normal pressure and magnetic agitation condition, with 0.02mol La (NO
3)
36H
2O is dissolved in the 10ml deionized water, behind magnetic agitation (500 rev/mins) 15min, adds 0.01mol Cu (NO in above-mentioned solution
3)
23H
2O continues to stir 15min.Take by weighing 20g KOH solid, make it to be dissolved in the 20ml deionized water.This KOH solution is slowly joined in the above-mentioned mixing solutions, magnetic agitation and ultrasonic dispersing are after each half an hour, it is transferred to (80% volume loading level) in the stainless steel cauldron that liner is a tetrafluoroethylene, put in the thermostat container in 260 ℃ of insulation 48h, be cooled to room temperature afterwards, use again deionized water wash, suction filtration 4 times, dry (60 ℃, 12h).The gained pressed powder is placed retort furnace, rise to 400 ℃ and from room temperature, continue to be warmed up to 850 ℃ and with 3 ℃/min temperature rise rate again at 850 ℃ of constant temperature 6h at 400 ℃ of insulation 1h with 1 ℃/min temperature rise rate.After grinding, obtaining diameter is 250～400nm, and length is the nano and micron rod shape single-crystal perovskite type oxide La of 5～10 μ m
2CuO
4Particle.
Embodiment 3: under normal temperature, normal pressure and magnetic agitation condition, with 0.01mol La
2O
3In the 10ml deionized water, behind magnetic agitation (500 rev/mins) 15min, in above-mentioned suspension liquid, add 0.01mol Cu (NO
3)
23H
2O continues to stir 15min.Take by weighing 20g KOH solid, make it to be dissolved in the 20ml deionized water.This KOH solution is slowly joined in the above-mentioned mixing solutions, magnetic agitation and ultrasonic dispersing are after each half an hour, it is transferred to (80% volume loading level) in the stainless steel cauldron that liner is a tetrafluoroethylene, put into again in the thermostat container in 180 ℃ of insulation 24h, be cooled to room temperature afterwards, use again deionized water wash, suction filtration 4 times, dry (60 ℃, 12h).The gained pressed powder is placed retort furnace, rises to 400 ℃ and under this temperature, be incubated 1h from room temperature with 1 ℃/min temperature rise rate, again with 3 ℃/min temperature rise rate continue to be warmed up to 850 ℃ and under this temperature constant temperature 6h.After grinding, obtaining diameter is 80～300nm, and length is the nano and micron rod shape single-crystal perovskite type oxide La of 2～12 μ m
2CuO
4Particle.
Claims (1)
1, a kind of single-crystal perovskite type oxide La
2CuO
4The preparation method of nano and micron rod, it is characterized in that: under normal temperature, normal pressure and magnetic agitation condition, being the copper source with the cupric nitrate, is the lanthanum source with the oxide compound of lanthanum nitrate or lanthanum, with potassium hydroxide is precipitation agent, wherein cupric nitrate: lanthanum nitrate: the amount of substance ratio of potassium hydroxide is: 1: 2: 35.71; Cupric nitrate: lanthanum trioxide: the amount of substance ratio of potassium hydroxide is: 1: 1: 35.71; With concentration is that the potassium hydroxide solution of 17.85mol/L adds in the mixing solutions of being made up of copper source and lanthanum source, form precipitation, after continuing to stir, be transferred to ultrasonic dispersing 0.5h in the ultrasonic cleaner, again it is transferred in the stainless steel cauldron that liner is a tetrafluoroethylene, put in the thermostat container in 180 ℃-260 ℃ insulation 24h-48h, cooling afterwards, with the products therefrom deionized water wash, suction filtration, dry, put into retort furnace and rise to 400 ℃ and from room temperature, continue to be warmed up to 850 ℃ and with the temperature rise rate of 3 ℃/min again at 850 ℃ of insulation 2h-6h at 400 ℃ of insulation 1h with the temperature rise rate of 1 ℃/min; Obtain nano and micron rod shape perovskite-like type oxide compound La after the grinding
2CuO
4
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| CN101798103B (en) * | 2010-01-29 | 2011-12-21 | 北京工业大学 | Method for preparing colloid crystal template of orthorhombic La2CuO4 with three-dimensional macro-porous structure |
| CN102398915B (en) * | 2011-11-23 | 2013-10-09 | 陕西科技大学 | Method for preparing lanthanum cuprate (La2CuO4) powder by means of microwave-hydrothermal method |
| CN102515242B (en) * | 2011-11-23 | 2013-08-07 | 陕西科技大学 | Method for preparing lanthanum cuprate (La2CuO4) by sol-gel process |
| CN102491401A (en) * | 2011-11-23 | 2012-06-13 | 陕西科技大学 | Method for preparing lanthanum cuprate nanometer crystal through combination of sol-gel and microwave hydrothermal synthesis |
| CN102392304B (en) * | 2011-11-23 | 2013-12-25 | 陕西科技大学 | Preparation method of La2CuO4 film |
| CN102583497A (en) * | 2011-11-23 | 2012-07-18 | 陕西科技大学 | Method adopting sol-gel to prepare high-temperature superconductivity parent-phase material, i.e. La2CuO4 powder |
| CN104505522B (en) * | 2014-12-31 | 2017-05-03 | 东莞市迈科科技有限公司 | Hydrothermal preparation method of lanthanum-nickel composite oxide catalyst for lithium air battery |
| CN104624195A (en) * | 2015-01-19 | 2015-05-20 | 陕西科技大学 | Method for preparing Sm2O3/CuO nano composite through sol-gel process |
| CN107857289B (en) * | 2017-11-13 | 2019-04-12 | 东北大学 | A kind of preparation method of copper acid lanthanum nano adsorption material |
| CN109796037A (en) * | 2019-01-23 | 2019-05-24 | 陕西理工大学 | A kind of La of nanostructure2CuO4Catalyst material and its preparation method and application |
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| A New Series of Magnetic Rare EarthCuprates:RCu2O4(R=La,Nd,Sm,and Eu). Steven W.keller, et al.Journal of The American Chemical Society,Vol.116 No.18. 2002 |
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