CN100567594C - Cupric oxide with preparation is synthetic spindle body shape of crystal seed and bar-shaped La 2CuO 4Method - Google Patents
Cupric oxide with preparation is synthetic spindle body shape of crystal seed and bar-shaped La 2CuO 4Method Download PDFInfo
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- CN100567594C CN100567594C CNB2007101789255A CN200710178925A CN100567594C CN 100567594 C CN100567594 C CN 100567594C CN B2007101789255 A CNB2007101789255 A CN B2007101789255A CN 200710178925 A CN200710178925 A CN 200710178925A CN 100567594 C CN100567594 C CN 100567594C
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Abstract
Cupric oxide with preparation is synthetic spindle body shape of crystal seed and bar-shaped La
2CuO
4Method belong to the preparation field of nanocatalyst.Be Tong Yuan with the cupric nitrate, be alkali source with sodium hydroxide, adopt hydrothermal synthesis method at first to prepare cashier's micron copper oxide particle; Be Tong Yuan, be the lanthanum source, be alkali source with sodium hydroxide to receive micron cupric oxide again, adopt hydrothermal synthesis method,, can obtain perovskite-like type oxide compound La by 240 ℃ of hydrothermal temperatures of control and time 24h-48h, 850 ℃ of calcination temperatures and time 2h with the lanthanum nitrate
2CuO
4Spindle body shape and bar-shaped micron-particle.The perovskite-like type oxide compound La that the present invention obtained
2CuO
4Have and receive spindle body shape and the bar-shaped pattern and the single crystal structure of (little) meter ruler cun.This has the perovskite-like type oxide compound La of unique pattern and crystal phase 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 the preparation method of a kind of perovskite-like type oxide compound spindle body shape and bar-like single crystal micron-particle, relating in particular to the cupric oxide is that the hydrothermal synthesis method of crystal seed prepares perovskite-like type oxide compound La
2CuO
4The method of spindle body shape and bar-like single crystal micron-particle, it belongs to the preparation field of nanocatalyst.
Background technology
In numerous composite oxides, perofskite type oxide (ABO
3) and perovskite-like type oxide compound (A
2BO
4) receive much concern.Perovskite-like type oxide compound is a kind of stratiform composite oxides, and it is except having and perofskite type oxide ABO
3Outside the similar performance, also have many special performances, as supraconductivity, high-temperature stability, electro permanent magnetic etc.
The present method for preparing perovskite-like type oxide compound that adopts has multiple, for example citric acid complex method (H.X.Dai, et al., Catal.Lett., 2000,67:183-192), solid reaction process (H.X.Dai, et al., J.Catal., 2001,197:251-266), critical water hypobaric drying method (G..A.Alexander, et al., Angew.Chem.Int.Ed., 2000,39:2738-2740) etc.Different preparation methods has very big influence to the physicochemical property such as structure, pattern, size, specific surface area and catalytic performance of products therefrom.But these preparation methods' complex process, condition harshness, cost 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.These methods exist and are difficult to shortcoming that target product pattern and grain size are controlled.People explore and to take different presomas as crystal seed in recent years, preparation perovskite typed and perovskite-like type oxide compound, and the characteristics of this method are to prepare comparatively rule and be the product of single crystal structure of pattern.For example, and Wang etc. (Y.W.Wang, et al., J.phys.chem.B, 2006,110:13831-13840) (diameter is 300～500nm) to be crystal seed, prepares the spherical TiO of single crystal structure by one step hydro thermal method with spherical tio2
2, SrTiO
3And BaTiO
3Fang etc. (B.Fang, et al., Mater.Lett, 2002,52:423-428) with ZnO, NbO and TiO
2Be crystal seed, prepare single crystal perovskite type oxide Pb ((Zn
1/3Nb
2/3)
0.91Ti
0.09) O
3Yet the hydrothermal synthesis method that does not also adopt cupric oxide to make crystal seed is prepared perovskite-like type oxide compound La up to now
2CuO
4The report of monocrystalline micron-particle.
And the method for describing according to the present invention, micron cupric oxide of receiving with specific morphology that selection is prepared is done the copper source, adopt hydrothermal synthesis method, under certain hydrothermal temperature and the condition of time, calcination temperature and time, obtain the spindle body shape and the bar-shaped perovskite-like type oxide compound La of different size size
2CuO
4The monocrystalline micron-particle.The 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 with spindle body shape and bar-shaped perovskite-like type oxide monocrystal micron-particle, the product that the present invention prepares is that the good perovskite-like type composite oxide single crystal of degree of crystallinity is received micron spindle body shape and bar-shaped La
2CuO
4Product.
Cupric oxide with preparation provided by the invention is synthetic spindle body shape of crystal seed and bar-shaped La
2CuO
4Method, it is characterized in that: under normal temperature, normal pressure and magnetic agitation condition, make Tong Yuan, make alkali source with cupric nitrate with sodium hydroxide, hydrothermal synthesis method makes receives a micron copper oxide particle, again with it as the copper source, with the lanthanum nitrate is the lanthanum source, is precipitation agent with sodium hydroxide, wherein cupric oxide: lanthanum nitrate: the amount of substance ratio of sodium hydroxide is: 1: 2: 50; With concentration is that the sodium hydroxide solution of 25mol/L joins in the mixing solutions by 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 240 ℃ of insulation 24h-48h, cooling afterwards, with the products therefrom deionized water wash, suction filtration, dry, put in the retort furnace with the temperature rise rate of 1 ℃/min from room temperature rise to 400 ℃ and under this temperature constant temperature 1h, again with the temperature rise rate of 3 ℃/min continue to be warmed up to 850 ℃ and under this temperature constant temperature 2h; Grind at last and obtain receiving micron spindle body shape or bar-shaped perovskite-like type oxide compound La
2CuO
4
At present, also do not adopt the cupric oxide micron-particle for preparing as crystal seed, and then the report of the class calcium titanium type oxide compound of synthetic specific morphology.
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 perovskite-like type oxide compound La
2CuO
4Spindle body shape and bar-like single crystal micron-particle.
Description of drawings
For further understanding the present invention, elaborate with embodiment below, and provide accompanying drawing and describe the perovskite-like type oxide compound La that the present invention obtains
2CuO
4Spindle body shape and bar-like single crystal micron-particle, wherein:
Fig. 1 is La
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 La
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), 3 (c) are respectively La
2CuO
4The TEM photo of the ESEM of embodiment 2 samples and the cupric oxide micron-particle of TEM photo and preparation, wherein the illustration among Fig. 3 (b) is the SAED pattern of this sample, the illustration among 3 (c) is the SAED pattern of the cupric oxide micron-particle of preparation.
Fig. 4 (a), 4 (b), 4 (c) are respectively La
2CuO
4The TEM photo of the ESEM of embodiment 3 samples and the cupric oxide micron-particle of TEM photo and preparation, wherein the illustration among Fig. 4 (b) is the SAED pattern of this sample, the illustration among 4 (c) is the SAED pattern of the cupric oxide micron-particle of preparation.
Embodiment
Concrete implementation step of the present invention is as follows:
Embodiment 1: at first a micron monocrystalline cupric oxide crystal seed is received in preparation.At normal temperature, under normal pressure and the magnetic agitation condition, 0.03mol cupric nitrate and 1.2mol sodium hydroxide are dissolved in respectively in 30ml dehydrated alcohol and the 60ml deionized water, slowly join copper nitrate solution in the sodium hydroxide solution again, behind magnetic agitation (500 rev/mins) 30min, it is transferred in the stainless steel cauldron that liner is a tetrafluoroethylene, place thermostat container in 100 ℃ of insulation 12h, be cooled to room temperature afterwards, use twice of the centrifugal suction filtration of dehydrated alcohol and deionized water more respectively, (60 ℃ of dryings, promptly make the spindle body shape 24h) and receive a micron monocrystalline copper oxide particle, its diameter is 80～350nm, length is 300～900nm.With this as growth perovskite-like type oxide compound La
2CuO
4The crystal seed of micron-particle.
With 0.02mol La (NO
3)
36H
2O is dissolved in the 10ml deionized water, behind magnetic agitation (500 rev/mins) 30min, adds the prepared micron monocrystalline cupric oxide crystal seed of receiving of 0.01mol in above-mentioned solution, continues to stir 15min.Take by weighing 20g NaOH solid, be dissolved in the 20ml deionized water, it is slowly joined in the above-mentioned mixing solutions, continue to stir 1h, and ultrasonic dispersing 0.5h.The gained mixed solution is transferred to (80% volume loading level) in the stainless steel cauldron that liner is a tetrafluoroethylene, put in the thermostat container and carry out hydrothermal treatment consists 24h in 240 ℃, be cooled to room temperature afterwards, use again deionized water wash, suction filtration 4 times, dry (60 ℃, 12h).With the gained powder place retort furnace with the speed of 1 ℃/min from room temperature be raised to 400 ℃ and under this temperature constant temperature 1h, continue to be warmed up to 850 ℃ and keep this temperature calcination 2h with the speed of 3 ℃/min again.After grinding, obtaining diameter is that 600～900nm, length are that 5～18 μ m receive a micron spindle body shape single-crystal perovskite type oxide La for obtaining diameter
2CuO
4Particle, and diameter is that 90～250nm, length are 1～5 μ m nano and micron rod shape single-crystal perovskite type oxide La
2CuO
4Particle.
Embodiment 2: micron preparation method of monocrystalline cupric oxide crystal seed that receives is identical with embodiment 1.With 0.02molLa (NO
3)
36H
2O is dissolved in the 10ml deionized water, behind magnetic agitation (500 rev/mins) 15min, adds the prepared micron monocrystalline cupric oxide crystal seed of receiving of 0.01mol in above-mentioned solution, continues to stir 15min.Take by weighing 20g NaOH, be dissolved in the 20ml deionized water, it is slowly joined in the above-mentioned mixing solutions, after continuing to stir 1h, and use ultrasonic dispersing 0.5h.Then it is transferred to (80% volume loading level) in the stainless steel cauldron that liner is a tetrafluoroethylene, put in the thermostat container and carry out hydrothermal treatment consists 48h in 240 ℃, make it be cooled to room temperature afterwards, through deionized water wash, suction filtration 4 times and dry (60 ℃, 12h), place retort furnace with the speed of 1 ℃/min from room temperature be raised to 400 ℃ and under this temperature constant temperature 1h, continue to be warmed up to 850 ℃ and keep this temperature calcination 2h with the speed of 3 ℃/min again.After grinding, obtain diameter and be 500～800nm, length and be 2～10 μ m and receive a micron spindle body shape single-crystal perovskite type oxide La
2CuO
4Particle.
Embodiment 3: at first receive a micron monocrystalline cupric oxide crystal seed.Under normal temperature, normal pressure and magnetic agitation condition, 0.03mol cupric nitrate and 0.6mol sodium hydroxide are dissolved in respectively in 30ml dehydrated alcohol and the 60ml deionized water, slowly join copper nitrate solution in the sodium hydroxide solution again, behind magnetic agitation (500 rev/mins) 30min, it is transferred in the stainless steel cauldron that liner is a tetrafluoroethylene, place thermostat container in 150 ℃ of insulation 12h, be cooled to room temperature afterwards, use respectively again twice of the centrifugal suction filtration of dehydrated alcohol and deionized water, dry (60～80 ℃, 24h).The gained solid is risen to 200 ℃ and be incubated 1h under this temperature with the speed of 1 ℃/min from room temperature, continue to be warmed up to 400 ℃ and under this temperature, be incubated 2h with the speed of 2 ℃/min again, promptly make triangular shape and receive a micron monocrystalline copper oxide particle, its length of side is 0.5～2 μ m.With this as growth perovskite-like type oxide compound La
2CuO
4The crystal seed of micron-particle.
With 0.02mol La (NO
3)
36H
2O is dissolved in the 10ml deionized water, behind magnetic agitation (500 rev/mins) 30min, adds the prepared triangular shape of 0.01mol and receive a micron monocrystalline cupric oxide crystal seed in above-mentioned solution, continues to stir 15min.Take by weighing 20g NaOH solid, be dissolved in the 20ml deionized water, it is slowly joined in the above-mentioned mixing solutions, continue to stir 1h, and ultrasonic dispersing 0.5h.The gained mixed solution is transferred to (80% volume loading level) in the stainless steel cauldron that liner is a tetrafluoroethylene, put in the thermostat container and carry out hydrothermal treatment consists 48h in 240 ℃, be cooled to room temperature afterwards, use again deionized water wash, suction filtration 4 times, dry (60 ℃, 12h).With the gained powder place retort furnace with the speed of 1 ℃/min from room temperature be raised to 400 ℃ and under this temperature constant temperature 1h, continue to be warmed up to 850 ℃ and keep this temperature calcination 2h with the speed of 3 ℃/min again.After grinding, obtaining diameter is that 200～600nm, length are 5～10 μ m nano and micron rod shape single-crystal perovskite type oxide La
2CuO
4Particle.
Claims (1)
1, a kind of cupric oxide with preparation is synthetic spindle body shape of crystal seed and bar-shaped La
2CuO
4Method, it is characterized in that: under normal temperature, normal pressure and magnetic agitation condition, make Tong Yuan, make alkali source with cupric nitrate with sodium hydroxide, hydrothermal synthesis method makes receives a micron copper oxide particle, again with it as the copper source, with the lanthanum nitrate is the lanthanum source, is precipitation agent with sodium hydroxide, wherein cupric oxide: lanthanum nitrate: the amount of substance ratio of sodium hydroxide is: 1: 2: 50; With concentration is that the sodium hydroxide solution of 25mol/L joins in the mixing solutions by 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 240 ℃ of insulation 24h-48h, cooling afterwards, with the products therefrom deionized water wash, suction filtration, dry, put in the retort furnace with the temperature rise rate of 1 ℃/min from room temperature rise to 400 ℃ and under this temperature constant temperature 1h, again with the temperature rise rate of 3 ℃/min continue to be warmed up to 850 ℃ and under this temperature constant temperature 2h; Grind at last and obtain receiving micron spindle body shape or bar-shaped perovskite-like type oxide compound La
2CuO
4
Wherein said hydrothermal synthesis method makes, and to receive the scheme of micron copper oxide particle one of following two kinds: under normal temperature, normal pressure and magnetic agitation condition, 0.03mol cupric nitrate and 0.6mol sodium hydroxide are dissolved in respectively in 30ml dehydrated alcohol and the 60ml deionized water, again copper nitrate solution is joined in the sodium hydroxide solution, behind the magnetic agitation 30min, it is transferred in the stainless steel cauldron that liner is a tetrafluoroethylene, place thermostat container in 150 ℃ of insulation 12h, be cooled to room temperature afterwards, use twice of the centrifugal suction filtration of dehydrated alcohol and deionized water, drying more respectively; The gained solid is risen to 200 ℃ and be incubated 1h under this temperature with the speed of 1 ℃/min from room temperature, continue to be warmed up to 400 ℃ and under this temperature, be incubated 2h with the speed of 2 ℃/min again, promptly make triangular shape and receive a micron monocrystalline copper oxide particle; With this as growth perovskite-like type oxide compound La
2CuO
4The crystal seed of micron-particle;
Perhaps at normal temperature, under normal pressure and the magnetic agitation condition, 0.03mol cupric nitrate and 1.2mol sodium hydroxide are dissolved in respectively in 30ml dehydrated alcohol and the 60ml deionized water, again copper nitrate solution is joined in the sodium hydroxide solution, behind the magnetic agitation 30min, it is transferred in the stainless steel cauldron that liner is a tetrafluoroethylene, place thermostat container in 100 ℃ of insulation 12h, be cooled to room temperature afterwards, use twice of the centrifugal suction filtration of dehydrated alcohol and deionized water more respectively, through 60 ℃, promptly make the spindle body shape after the 24h drying and receive a micron monocrystalline copper oxide particle, its diameter is 80～350nm, length is 300～900nm; With this as growth perovskite-like type oxide compound La
2CuO
4The crystal seed of micron-particle.
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| CN102408122A (en) * | 2011-11-23 | 2012-04-11 | 陕西科技大学 | Co-precipitation method for preparing lanthanum cuprate (La2CuO4) powder |
| CN102515242B (en) * | 2011-11-23 | 2013-08-07 | 陕西科技大学 | Method for preparing lanthanum cuprate (La2CuO4) by sol-gel process |
| CN103194787A (en) * | 2013-04-15 | 2013-07-10 | 东北师范大学 | Preparation method of polyacid based tubular monocrystal microreactor |
| CN103498189B (en) * | 2013-09-22 | 2016-11-16 | 北京工业大学 | One-dimensional single crystal LaFeO3nanometer rods and preparation |
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Non-Patent Citations (4)
| Title |
|---|
| A New Series of Magnetic Rare Earth Cuprates:RCu2O4(R=La,Nd,Sm,and Eu). Steven W.keller等.Journal of the American Chemical Society. 2002 |
| A New Series of Magnetic Rare Earth Cuprates:RCu2O4(R=La,Nd,Sm,and Eu). Steven W.keller等.Journal of the American Chemical Society. 2002 * |
| 纳米氧化铋和复核氧化物铜酸镧的制备及表征. 陈建龙.硕士学位论文. 2004 |
| 纳米氧化铋和复核氧化物铜酸镧的制备及表征. 陈建龙.硕士学位论文. 2004 * |
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