CN105540673A - Strontium manganate nanowires and microwires and preparation method thereof - Google Patents
Strontium manganate nanowires and microwires and preparation method thereof Download PDFInfo
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- CN105540673A CN105540673A CN201610085523.XA CN201610085523A CN105540673A CN 105540673 A CN105540673 A CN 105540673A CN 201610085523 A CN201610085523 A CN 201610085523A CN 105540673 A CN105540673 A CN 105540673A
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- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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Abstract
The invention discloses strontium manganate nanowires and microwires and a controllable hydrothermal preparation method thereof. The chemical formula of strontium manganate is SrMn3O(6-x), and lanthanum doping can be performed within certain range; and the regulation of wire size and doping amount can be realized by changing the conditions such as reaction temperature, time and raw material proportioning, wherein the wire diameter is 50nm-5mum, the length is 40-300mum, and the doping amount is 0-0.25% by weight. The system has excellent specific surface area, ion exchangeability and stability as well as unique molecule-grade tunnel space and has an important application value in the fields such as catalysts, secondary battery electrode materials, adsorbents, molecular sieves and sensors. Meanwhile, the unique magnetic and electrical properties are of important application value in terms of magnetic recording and magnetic sensors. The method has the advantages of easiness, low equipment requirements and low energy consumption and can be applied to the strontium manganate preparation as well as one-dimensional system synthesis of other similar multielement materials, for example, nanowires and microwires of barium manganate, calcium manganate and sodium manganate.
Description
Technical field
The present invention relates to the preparation method of a kind of nanometer and micro wire, especially relate to the preparation method of La doped strontium manganate nano wire and micro wire.
Background technology
Strontium manganate has unique asymmetric modulation tunnel structure, MnO
6octahedra chain altogether drift angle, altogether rib is connected to form mesh tunnel topology.The tunnel construction of this uniqueness make strontium manganate have larger specific surface area, more negative charge amount, excellent ion-exchange performance, satisfactory stability and molecule and tunnel space, the structure of this uniqueness makes it be with a wide range of applications in fields such as catalyzer, battery, sorbent material, molecular sieves.Meanwhile, nanostructure Mn oxide has unique magneto-electric behavior, in Magnetic Sensor and magnetic recording device, have potential using value.
At present, scientists has had certain progress in Mn oxide nanometer, the brilliant preparation of micron, but most use high temperature solid state reaction.2009, Appl.Phys.Lett. the 94th phase 182506 pages reports a kind of preparation method of strontium manganate nano belt, under 800 DEG C of high temperature sinterings, prepare gained, the advantage of this method is easy to into phase, but there is shortcomings such as needing high-temperature calcination, energy consumption are high, sample easy-sintering.Cryst.GrowthDes. the 1st phase in 2011 2852 pages reports a kind of ion exchange method based on molten-salt growth method and prepared strontium manganate nano belt under 870 DEG C of high temperature, has prepared calcium manganate, Rosensthiel's green nano belt by identical method simultaneously.The high generation being conducive to thing phase of this method sintering temperature, utilize in reaction fused salt do solvent decrease to a certain extent high temperature solid state reaction sintering shortcoming, but there is agglomeration in sample.High-temperature solid phase reaction method may be used for preparing other Mn oxides or other multi-element compounds.As J.AM.CHEM.SOC. the 129th phase in 2007 15444 pages has prepared at 825 DEG C or 1000 DEG C of sintering the sodium niobate nano rods that length is tens microns.Chem.Mater. the 18th phase in 2006 5530 pages reports high-temperature solid phase reaction method and prepared calcium manganate (CaMn under 1200 DEG C of reactions condition of 12 hours
3o
6), sample has tunnel structure.As can be seen here, synthesis multi-element compounds uses high temperature solid state reaction always, and this method is easy to into phase, but temperature of reaction is high, easy-sintering.
Comparatively speaking, liquid phase method synthesis high-dispersion nano material is a kind of more satisfactory method, and wherein hydrothermal method has outstanding advantage in the materials synthesis such as synthetic metals, sulfide, selenide, oxide compound, achieves tremendous development at present.This method is simple, energy-conservation, equipment requirements is low, and the sample dispersion of preparation is very good.But for the synthesis of multi-component, due to phase-splitting easy in preparation process, use the method to be difficult to realize, relevant report is less, and the preparation of the hydrothermal method of strontium manganate nano wire and micro wire there is no relevant report.
This patent, for above problem, by suitably improving hydrothermal temperature, adding the experiment conditions such as suitable mineralizer, develops a kind of hydrothermal synthesis method of simple, convenient, energy-conservation multi-element compounds, has prepared strontium manganate overlong nanowire and micro wire.
Summary of the invention
The present invention overcomes weak point of the prior art, provides a kind of novel processing step preparing strontium manganate nano wire and micro wire simply and easily, and realizes size and doping regulation and control.
Through lot of experiments and analysis, the Hydrothermal Synthesis temperature of strontium manganate is relatively high, the temperature (mostly at 180 ~ 200 DEG C) that conventional hydrothermal building-up reactions is lower is difficult to the thing phase formation condition meeting strontium manganate, the present invention is by adding the mineralizer being conducive to thing and generating mutually, promote the generation of strontium manganate thing phase, and improve hydrothermal temperature, prolongation reaction times, successfully achieve the Hydrothermal Synthesis of strontium manganate.Utilize some the crystal face growth-inhibiting effect of K, Na ion pair in mineralizer, and by adjustment reaction conditions, promote the growth of specific direction crystal face, finally generate one-dimentional structure.
The invention provides a kind of preparation method of strontium manganate, particularly it completes according to the following steps:
1) strontium salt, manganese salt and lanthanum salt is soluble in water by predetermined proportion, and stirring at room temperature is to dissolving completely, forms the aqueous solution.
2) in the above-mentioned aqueous solution, appropriate mineralizer is added, even in stirring at room temperature.
3) precursor liquid that step 2 obtains is put into high temperature water heating kettle, put into air dry oven and react, temperature of reaction is 200 DEG C ~ 300 DEG C, and the reaction times is 1 ~ 3 day.
4) reaction terminates rear furnace cooling, reaction product is taken out, uses ethanol washed with de-ionized water, 80 ~ 100 DEG C of dryings, thus obtains strontium manganate nano wire and micro wire.
5) be strontium manganate with X-ray diffractometer confirmatory reaction product, use sem observation sample topography, determine diameter and the length of line.
As strontium manganate nano wire and micro wire novel preparation method, have relative to the beneficial effect of existing solid reaction process, one, by utilizing hydrothermal method, suitable raising hydrothermal temperature, adds suitable mineralizer, successfully achieves the preparation of strontium manganate nano wire and micro wire, relative to high temperature solid-state method, temperature of reaction is reduced greatly; Its two, overcome hydrothermal method be difficult to adulterate problem, achieve La doped; Its three, preparation method's technique is simple, and link is few, and cost is low, is convenient to large-scale production.
Accompanying drawing explanation
Here is described in further detail optimal way of the present invention by reference to the accompanying drawings.
Fig. 1 is the collection of illustrative plates mixing lanthanum strontium manganate nano wire and micro wire with x-ray diffractometer test.
Fig. 2 is the scanning electron microscope microscope photograph mixing lanthanum strontium manganate nano wire and micro wire.
Fig. 3 is the EDX spectrogram of the La doped strontium manganate obtained by the energy spectrum analysis annex of SEM.
Fig. 4 be after strontium manganate nano wire and micro wire scanning electron microscope microscopic the picture taken the photograph.
Fig. 5 is the EDX spectrogram of the strontium manganate obtained by the energy spectrum analysis annex of SEM.
Embodiment
Embodiment 1:
Strontium salt, manganese salt and lanthanum salt is soluble in water by 0.3: 3: 0.7, and stirring at room temperature is to dissolving completely, forms the aqueous solution.24g mineralizer is added in the above-mentioned aqueous solution, even in stirring at room temperature.The precursor liquid obtained is put into high temperature water heating kettle, puts into air dry oven and react, temperature of reaction is 275 DEG C, and the reaction times is 28 hours.Reaction terminates rear furnace cooling, reaction product is taken out, uses ethanol washed with de-ionized water, 100 DEG C of dryings, and collect sample.Use scanning electronic microscope and X-ray diffractometer to carry out observing to obtained sample and test, according to X-ray diffraction (XRD) (Fig. 1), wherein ordinate zou is relative intensity, X-coordinate is diffraction angle, from each diffraction peak position and relative intensity, the sample of preparation is strontium manganate structure.According to scanning electron microscope (SEM) photo (Fig. 2) and energy spectrum analysis (Fig. 3), illustrate successfully to have prepared and mix lanthanum strontium manganate overlong nanowire and micro wire, its diameter is respectively 50nm ~ 5 μm; Length is 40 ~ 300 μm.
Embodiment 2:
Strontium salt and manganese salt is soluble in water by 1: 3, and stirring at room temperature is to dissolving completely, forms the aqueous solution.24g mineralizer is added in the above-mentioned aqueous solution, even in stirring at room temperature.Precursor liquid is put into high temperature water heating kettle, put into air dry oven and react, temperature of reaction is 275 DEG C, and the reaction times is 30 hours.Reaction terminates rear furnace cooling, reaction product is taken out, uses ethanol washed with de-ionized water, 100 DEG C of dryings, and collect sample.Use scanning electronic microscope and X-ray diffractometer to carry out observing to obtained sample and test, from the scanning electron microscope obtained (SEM) photo (Fig. 4) and energy spectrum analysis (Fig. 5), successfully prepared strontium manganate overlong nanowire and micro wire, it is 200 ~ 600nm that its diameter is respectively; Length is 15 ~ 100 μm.
Embodiment 3:
Strontium salt, manganese salt and lanthanum salt is soluble in water by 0.3: 3: 0.7, and stirring at room temperature is to dissolving completely, forms the aqueous solution.24g mineralizer is added in the above-mentioned aqueous solution, even in stirring at room temperature.The precursor liquid obtained is put into high temperature water heating kettle, puts into air dry oven and react, temperature of reaction is 275 DEG C, and the reaction times is 28 hours.Reaction terminates rear furnace cooling, reaction product is taken out, uses ethanol washed with de-ionized water, 100 DEG C of dryings, and collect sample.Use scanning electronic microscope and X-ray diffractometer to carry out observing to obtained sample and test, according to X-ray diffraction (XRD) (Fig. 1), wherein ordinate zou is relative intensity, X-coordinate is diffraction angle, from each diffraction peak position and relative intensity, the sample of preparation is strontium manganate structure.According to scanning electron microscope (SEM) photo (Fig. 2) and energy spectrum analysis (Fig. 3), illustrate successfully to have prepared and mix lanthanum strontium manganate overlong nanowire and micro wire, its diameter is respectively 50nm ~ 5 μm; Length is 40 ~ 300 μm.
Embodiment 4:
Strontium salt and manganese salt is soluble in water by 1: 3, and stirring at room temperature is to dissolving completely, forms the aqueous solution.24g mineralizer is added in the above-mentioned aqueous solution, even in stirring at room temperature.Precursor liquid is put into high temperature water heating kettle, put into air dry oven and react, temperature of reaction is 275 DEG C, and the reaction times is 30 hours.Reaction terminates rear furnace cooling, reaction product is taken out, uses ethanol washed with de-ionized water, 100 DEG C of dryings, and collect sample.Use scanning electronic microscope and X-ray diffractometer to carry out observing to obtained sample and test, from the scanning electron microscope obtained (SEM) photo (Fig. 4) and energy spectrum analysis (Fig. 5), successfully prepared strontium manganate overlong nanowire and micro wire, it is 200 ~ 600nm that its diameter is respectively; Length is 15 ~ 100 μm.
Obviously, those skilled in the art can carry out various change and modification to the preparation method of strontium manganate nanometer of the present invention and micro wire and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (9)
1. strontium manganate nano wire and micro wire and a hydrothermal preparing process thereof, is characterized in that:
Lanthanum salt, first by strontium salt, the water-soluble solution of manganese salt, for doping system, is dissolved in the above-mentioned aqueous solution by 1.1 by a certain percentage;
Mineralizer is added again and even in stirring at room temperature in 1.2 solution obtained to step 1.1;
1.3 precursor liquids step 1.2 obtained put into water heating kettle, reactor is put into air dry oven and reacts, temperature of reaction 200 DEG C ~ 300 DEG C, 0.5 ~ 3 day reaction times;
1.4 finally by products therefrom through precipitation, be separated, cleaning, obtained La doped or undope strontium manganate nano wire and micro wire.
2. strontium manganate nano wire according to claim 1 and micro wire and preparation method thereof, is characterized in that the one in the optional lanthanum nitrate of lanthanum salt used, Lanthanum trichloride, lanthanum acetate.
3. strontium manganate nano wire according to claim 1 and micro wire and preparation method thereof, is characterized in that the one in the optional strontium nitrate of strontium salt used, strontium chloride, strontium acetate.
4. strontium manganate nano wire according to claim 1 and micro wire and preparation method thereof, is characterized in that the one in the optional manganous nitrate of manganese salt used, chloric acid manganese, manganese acetate.
5. strontium manganate nano wire according to claim 1 and micro wire and preparation method thereof, is characterized in that solvent for use is the one in deionized water, dehydrated alcohol.
6. strontium manganate nano wire according to claim 1 and micro wire and preparation method thereof, is characterized in that the optional potassium hydroxide of mineralizer used, sodium hydroxide, potassium hydroxide solution, sodium hydroxide solution.
7. strontium manganate nano wire according to claim 1 and micro wire and preparation method thereof, is characterized in that hydrothermal temperature is 200 ~ 300 DEG C, preferred 250-280 DEG C.
8. the La doped strontium manganate nano wire of strontium manganate nano wire according to claim 1 and micro wire and preparation method thereof preparation, comprises micro wire, it is characterized in that:
Described in 8.1, La doped strontium manganate nanowire diameter is 50 ~ 500nm, and length is 20 ~ 200 μm;
Described in 8.2, La doped strontium manganate micro wire diameter is 1 ~ 5 μm, and length is 40 ~ 300 μm.
9. the La doped prepared according to the arbitrary claim of claim 1 ~ 9 or undope strontium manganate nano wire and micro wire, doping is 0 ~ 0.25wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694089A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | One-dimensional nano line VPI-8 molecular sieve and its synthetic method |
| CN110416559A (en) * | 2018-04-26 | 2019-11-05 | 天津大学 | A kind of support type calcium manganese oxide composite material and its preparation method and application |
| CN110767898A (en) * | 2019-09-30 | 2020-02-07 | 合肥国轩高科动力能源有限公司 | Manganese-based nanowire bundle and preparation method and application thereof |
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| CN1357492A (en) * | 2000-12-14 | 2002-07-10 | 中国科学技术大学 | Amorphous La1-xSrxMnO3-5 compound and its prepn |
| CN1974886A (en) * | 2006-11-10 | 2007-06-06 | 北京工业大学 | Prepn process of nanometer rod and micron block of monocrystalline perovskite type oxide La1-xSrxMnO3 |
| KR20150115260A (en) * | 2014-04-03 | 2015-10-14 | (재)울산테크노파크 | Syntheses of transition metal-doped lasrmno_3 nanopowders by hydrothermal method for interconnect of solid oxide fuel cell |
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Patent Citations (3)
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| CN1357492A (en) * | 2000-12-14 | 2002-07-10 | 中国科学技术大学 | Amorphous La1-xSrxMnO3-5 compound and its prepn |
| CN1974886A (en) * | 2006-11-10 | 2007-06-06 | 北京工业大学 | Prepn process of nanometer rod and micron block of monocrystalline perovskite type oxide La1-xSrxMnO3 |
| KR20150115260A (en) * | 2014-04-03 | 2015-10-14 | (재)울산테크노파크 | Syntheses of transition metal-doped lasrmno_3 nanopowders by hydrothermal method for interconnect of solid oxide fuel cell |
Non-Patent Citations (1)
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| FEI TENG: "Hydrothermal synthesis and their catalytic properties of manganite nanowires", 《SOLID STATE SCIENCES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694089A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | One-dimensional nano line VPI-8 molecular sieve and its synthetic method |
| CN110416559A (en) * | 2018-04-26 | 2019-11-05 | 天津大学 | A kind of support type calcium manganese oxide composite material and its preparation method and application |
| CN110767898A (en) * | 2019-09-30 | 2020-02-07 | 合肥国轩高科动力能源有限公司 | Manganese-based nanowire bundle and preparation method and application thereof |
| CN110767898B (en) * | 2019-09-30 | 2022-06-07 | 合肥国轩高科动力能源有限公司 | Manganese-based nanowire bundle and preparation method and application thereof |
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