CN102220641B - Synthesis method of monoclinic crystal phase rare-earth iso-oxy-sulfur superfine nanowire and wire-based superstructure - Google Patents
Synthesis method of monoclinic crystal phase rare-earth iso-oxy-sulfur superfine nanowire and wire-based superstructure Download PDFInfo
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Abstract
The invention discloses a synthesis method of monoclinic crystal phase rare-earth iso-oxy-sulfur Ln2OS2 (Ln=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er and Yb) superfine nanowire and nanowire-based superstructure, comprising the following steps of: heating rare-earth metal nitrate solid and thiourea solid to 180-200 DEG C for solid-liquid phase reaction in the mixed solvent consisting of fatty acid, fatty amine and octadecene, and separating out reaction products to prepare target products. The method adopts a solid-liquid phase chemical reaction route and replaces an organic metal compound with rare-earth nitrate solid, thereby controllably synthesizing a series of rare-earth iso-oxy-sulfur superfine nanowires and nano wire-based superstructures with high efficiency. The synthesis method has a simple and safe operation process and universality, and can implement large-scale preparation of the product.
Description
Technical field
The present invention relates to the compound method of the different oxygen sulphur of a kind of rare earth nano material, particularly a kind of different oxygen sulphur of monocline crystalline phase rare earth (Ln of novelty
2OS
2, Ln=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb) and the controllable synthesis method of superfine nano line and nano wire base superstructure.
Background technology
Size and dimension are two important geometrical structure parameters that influence nano material physics, chemical property.In various nanostructures; 1D nano wire (diameter is less than the cylindrical-shaped structure of 100 nanometers) is because confinement of radial height and axial preferred growth; Its density of electronic states is different from 0D; 2D and 3D nanostructure, thereby have the physicochemical property of the uniqueness that is different from other nanostructure, in fields such as electronics, catalysis, sensing and environment degradables the potential application prospect is arranged.
In recent years, synthetic diameter has caused many scientists' interest and concern less than superfine nano line and the nano wire base superstructure of 10 nm.This is because sharply reducing along with nanowire diameter; Its surface atom ratio sharply increases; Density of electronic states generation considerable change; It is more remarkable that surface effects and quantum effect will become, and helps the coupling and the communication of electronics between absorption and the nano wire of alien species, enhanced or new catalysis, sensing and photoelectric properties might occur.
Usually, synthetic main template, liquid-liquid interface synthesis method, chemical Vapor deposition process (CVD) and the liquid-phase catalysis growth method etc. of adopting of nano wire.But, be difficult to synthesize the superfine nano line of diameter less than 10 nanometers with aforesaid method.Thereby, explore new, repeatably, pervasive method synthesizing superfine nano wire and nano wire base superstructure, and the physicochemical property of studying them has great importance.
As one type of important functional material, the different oxysulfide of rare earth has excellent photoluminescent property, and strengthening fields such as screen (RIS), computer X-ray fault imaging (CT), oxygen storage and medical image radiation detection in radiation has the important commercial using value.According to the difference of oxygen sulphur ratio, the different oxysulfide of rare earth can be divided into two big types.One type is the Ln of quadrature crystalline phase
2O
2S (Ln=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb), another kind of is the Ln of monocline crystalline phase
2OS
2At present, though the different oxysulfide nanostructure of rare earth is arranged, the report of superlattice that are assembled into like nanoparticle, nanometer sheet (nanoplate), nanometer sheet and nanometer rod, nano wire etc., products therefrom mainly is the Ln of quadrature crystalline phase
2O
2S.As far as we know, the Ln of monocline crystalline phase
2OS
2Nanostructure also effectively is not synthesized
Its reason possibly be because the ionic radius of O and S is different, and rare earth ion has extremely strong affinity to O, and to the S affinity relatively a little less than, Ln is easy to get in aqueous systems or oxygen-enriched environment
2O
3Or Ln
2O
2S is more difficult to get Ln
2OS
2With respect to Ln
2O
2S, Ln
2OS
2In the S atomic ratio increase, cause its lattice symmetry sharply to reduce.Theoretical according to the Landau Broken Symmetry, Ln
2OS
2Ln might appear being different from
2O
2The physicochemical property of S.
Among the present invention, thermal treatment rare earth nitrate (Ln (NO in solution
3)
3XH
2O and thiocarbamide solid, under relatively mild condition controlledly synthesis the different oxygen sulphur of the rare earth Ln of 12 kinds of monocline crystalline phases
2OS
2(Ln=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb) superfine nano line and nano wire base superstructure.The Ln of monocline crystalline phase
2OS
2Superfine nano line and nano wire base superstructure can be launched stronger white light under near ultraviolet excitation, can be used as ideal solid light source equivalent material in the following lighting technical field.
Summary of the invention
The object of the present invention is to provide the different oxygen sulphur of a kind of monocline crystalline phase rare earth Ln
2OS
2The controllable synthesis method of (Ln=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb) superfine nano line and nano wire base superstructure utilizes solid-liquid phase chemistry reaction scheme, makes Ln
2OS
2Nucleation and growth separately, down auxiliary at structure directing reagent, through control growing environment and growth kinetics process, obtain monocline crystalline phase Ln
2OS
2Superfine nano line and nano wire base superstructure are developed one type of solid light source material new, the emission white light.
The technical scheme that the present invention adopts is following:
The compound method of a kind of monocline crystalline phase rare earth different oxygen sulphur superfine nano line and nano wire base superstructure; It is characterized in that: in the mixed solvent that lipid acid, aliphatic amide and vaccenic acid are formed; Rare-earth metal nitrate solid and thiocarbamide solid heat temperature raising are carried out solid-liquid phase reaction to 180-200 ℃, and reaction product makes object after separating;
The chemical formula of the different oxygen sulphur of described rare earth is Ln
2OS
2, wherein Ln=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er or Yb.
Described method specifically may further comprise the steps:
1), takes by weighing a certain amount of rare-earth metal nitrate solid and thiocarbamide solid, in the reaction kettle of the inner liner polytetrafluoroethylene of adding clean dried;
2), add an amount of lipid acid, aliphatic amide and vaccenic acid, sealed reactor, direct heating or reaction kettle placed baking oven is warming up to 180-200 ℃ with certain temperature rise rate, and under this temperature, kept 10-60 hour, reduces to room temperature naturally;
3), with step 2) the product deposition, spinning, the washing that obtain, vacuum-drying under the room temperature makes monocline crystalline phase rare earth different oxygen sulphur superfine nano line and nano wire base superstructure.
Its molecular formula of described rare-earth metal nitrate is Ln (NO
3)
3XH
2O, wherein thulium Ln is Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er or Yb, x is 0 ~ 6 integer.
Described lipid acid is C6 ~ C22 straight chain fatty acid, preferred C8 ~ C18 straight chain fatty acid; Described aliphatic amide is C6 ~ C22 straight chain armeen, preferred C8 ~ C16 straight chain armeen.
As reaction raw materials; Selectable one proportion relation of described rare-earth metal nitrate solid, thiocarbamide solid, lipid acid, aliphatic amide and its consumption of vaccenic acid does; The rare-earth metal nitrate solid is the 0.2-6.0 gram; Thiocarbamide solid 0.1 – 4.50 grams, the consumption of lipid acid, aliphatic amide and vaccenic acid is respectively 2-10 mL, 2-10 mL and 5-20 mL in the mixed solvent.
The inventive method solid-liquid phase reaction temperature is 180 ℃-200 ℃; Reaction times is 10-60 hour, and the reaction times is preferably 20-30 hour, most preferably is 24 hours.In step 2, temperature rise rate is 3 ℃-8 ℃ of PMs.
In step 3), earlier with normal heptane with step 2) product that obtains disperses, adds absolute ethyl alcohol then and make it sedimentation; Last spinning; Wash 3-5 time with normal heptane/absolute ethyl alcohol mixed solvent, the product that obtains at last 60 ℃ of following vacuum-dryings 4 hours, is used for analyzing and characterizing.
Collect dried product, adopt X-Ray powder diffractometer (XRD) to test its composition and thing mutually; Adopt transmission electron microscope (TEM) to analyze its pattern; Utilize SEAD (SAED) and high-resolution electron microscope (HRTEM) to analyze its crystallization situation.
Can know the different oxygen sulphur of rare earth (Ln through test analysis
2OS
2, Ln=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb) and superfine nano line and nano wire base superstructure be the monocline crystalline phase, has the geometry (wire of rule; Parallel arranged slabbing structure on the two-dimensional space; The spontaneous tissue of sheet structure meeting forms laminate structure or is curled into tubular structure on the three-dimensional space), wherein nanowire length is hundreds of nm, diameter is about 2～3 nm; Near the single cell size, length-to-diameter ratio is about 50-500.
Optic test shows, the Ln of the monocline crystalline phase of the inventive method preparation
2OS
2Superfine nano line and nano wire base superstructure can be launched stronger white light under near ultraviolet excitation.
Advantage of the present invention is: adopt simple solid-liquid phase chemistry route; Rare earth nitrate solid with cheap has substituted expensive organometallic compound; Substituted noxious solvent commonly used with eco-friendly solvent; Under lower temperature,, efficiently controllably synthesized the different oxygen sulphur of serial rare-earth (Ln through the control reaction parameter
2OS
2, Ln=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb) and superfine nano line and nano wire base superstructure.Superfine nano line that the inventive method makes and nano wire base superstructure material have good luminescent properties, under near ultraviolet excitation, can launch stronger white light, can be used as following illumination and use the solid light source candidate material.In addition, compound method operating process of the present invention simply, safely, have a universality well, and can the mass preparation product, established solid basis for this type material moves towards to use.
The different oxygen sulphur of monocline crystalline phase rare earth of the present invention (Ln
2OS
2) the extensive controlledly synthesis of superfine nano line and nano wire base superstructure; Not only expanded the composition of whole superfine nano line family; In basic scientific research, have significant values, and great strategic importance is arranged for reasonable, the efficient development and application of China's rare earth resources.
Description of drawings
Fig. 1 is according to embodiment 1 synthetic Y
2OS
2The X-Ray powder diagram of superfine nano line and superstructure thereof shows 12 obvious diffraction peaks among the figure, can belong to be monocline crystalline phase Y
2OS
2(011), (111), (21-2), (021), (211), (121), (300), (22-1), (12-1), (131), the diffraction of (21-3) and (322) crystal face.
Fig. 2 b and Fig. 2 a are according to embodiment 1 synthetic Y
2OS
2The TEM figure of superfine nano line and superstructure thereof; The pattern that has confirmed products therefrom is one dimension (1D) linear structure; Length is hundreds of nm; Diameter is about 2～3 nm, and length-to-diameter ratio is about 50-500, and the spontaneous tissue of described under certain condition superfine nano line structure forms 2D sheet structure or 3D laminate structure.
Fig. 2 c is according to embodiment 1 synthetic Y
2OS
2The HRTEM figure of superfine nano line has further confirmed gained Y
2OS
2Has the one dimension linear structure; By the crystallographic property and the direction of growth that HRTEM can further observe nano wire, be 0.29 nm through the spacing of measuring single nano-wire, corresponding to monocline crystalline phase Y
2OS
2(211) crystal face.And the spacing at the thin position of nanowire diameter is 0.27 nm, corresponding to Y
2OS
2(300) crystal face.
Fig. 2 d is according to embodiment 1 synthetic Y
2OS
2The SAED of superfine nano line, through calculating, the crystal face that diffraction ring is corresponding is (011), (300) and (322).
Fig. 3 a, Fig. 4 a, Fig. 5 a, Fig. 6 a, Fig. 7 a are according to 2,3,4,5,6 synthetic Gd of embodiment
2OS
2, Dy
2OS
2, Ho
2OS
2, Er
2OS
2And Yb
2OS
2The X-Ray powder diagram of superfine nano line has confirmed synthetic Gd
2OS
2, Dy
2OS
2, Ho
2OS
2, Er
2OS
2And Yb
2OS
2Nano wire purity is high, crystallization is better, and all is the oblique crystal phase structure.
Fig. 3 b, Fig. 4 b, Fig. 5 b, Fig. 6 b, Fig. 7 b are according to 2,3,4,5,6 synthetic Gd of embodiment
2OS
2, Dy
2OS
2, Ho
2OS
2, Er
2OS
2And Yb
2OS
2The TEM figure of superfine nano line, the pattern of products therefrom is the one dimension linear structure, and length is hundreds of nm, and diameter is about 2～3 nm, and length-to-diameter ratio is about 50-500, and parallel arranged becomes the 2D sheet structure.
Embodiment
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with embodiment, but is limited claim.
Embodiment 1
A clean dried, have in the teflon-lined reaction kettle (volume is 50 mL), add 0.20～6. 0g Y (NO
3)
36 H
2O solid, 0.10～4.50g thiocarbamide solid, 2～10 mL oleic acid (Aldrich; 90%), 2～10 mL amino dodecanes (Alfa Aesar, 98%) and 5～20 mL vaccenic acids (Alfa Aesar, 90%); Sealed reactor is transferred to it in baking oven; Speed with 4 ℃/min rises to 180 ℃ from room temperature, react 24 h after, be cooled to room temperature naturally.Obtain the jelly of light brown shape, add normal heptane, low-grade fever adds ethanol sedimentation again, and spinning goes out solid.Use normal heptane/absolute ethyl alcohol mixed solvent (volume ratio is 2/1) washing gained initial product then, obtain deposition after the spinning.Repeated washing 3-5 time obtains the oyster solid phase prod, will wash good product at last at 60 ℃ of following vacuum-drying 4 h.
Collect dried product, adopt X-Ray powder diffractometer (XRD) to test its composition and thing mutually, the result shows, products therefrom is the Y of pure oblique crystal phase structure
2OS
2(Fig. 1).Observe, analyze its pattern and structure (Fig. 2 a-Fig. 2 d) with transmission electron microscope (TEM), SEAD (SAED) and high-resolution electron microscope (HRTEM), show gained Y
2OS
2Pattern be the one dimension linear structure, length is hundreds of nm, diameter is about 2～3nm, length-to-diameter ratio is about 50-500, parallel arranged becomes the 2D sheet structure.
Embodiment 2
A clean dried, have in the teflon-lined reaction kettle (volume is 50 mL), add 0.2～6.0 g Gd (NO
3)
36 H
2O solid, 0.10～4.50g thiocarbamide solid, 2～10 mL oleic acid, 2～10 mL amino dodecanes and 5～20 mL vaccenic acids; Sealed reactor is transferred to it in baking oven; Speed with 4 ℃/min rises to 180 ℃ from room temperature; After reacting 24 h, be cooled to room temperature naturally, obtain the jelly of light brown shape.Add normal heptane, low-grade fever adds ethanol again, and spinning goes out solid.Use normal heptane/absolute ethyl alcohol mixed solvent (volume ratio is 2/1) washing gained head product then, obtain deposition after the spinning.Repeated washing 3-5 time obtains the oyster solid phase prod, will wash good product at last at 60 ℃ of following vacuum-drying 4 h.。
Collect dried product, adopt X-Ray powder diffractometer (XRD) to test its composition and thing mutually, show that products therefrom is the Gd of pure oblique crystal phase structure
2OS
2(Fig. 3 a).Observe its pattern and structure (Fig. 3 b) with transmission electron microscope (TEM).The result shows, gained Gd
2OS
2Pattern be the one dimension linear structure, length is hundreds of nm, diameter is about 2～3 nm, length-to-diameter ratio is about 50-500, parallel arranged becomes the 2D sheet structure.
Embodiment 3
A clean dried, have in the teflon-lined reaction kettle (volume is 50 mL), add 0.2～6.0 g Dy (NO
3)
36 H
2O solid, 0.10～4.50g thiocarbamide solid, 2～10 mL oleic acid, 2～10 mL amino dodecanes and 5～20 mL vaccenic acids; Sealed reactor is transferred to it in baking oven; Speed with 4 ℃/min rises to 200 ℃ from room temperature, react 24 h after, be cooled to room temperature naturally.Obtain the jelly of light brown shape.Add normal heptane, low-grade fever adds ethanol again, and spinning goes out solid.Use normal heptane/absolute ethyl alcohol mixed solvent (volume ratio is 2/1) washing products therefrom then, obtain deposition after the spinning.Repeated washing operation 3-5 time obtains the oyster solid phase prod, will wash good product at last at 60 ℃ of following vacuum-drying 4 h.
Collect dried product, adopt X-Ray powder diffractometer (XRD) to test its composition and thing mutually, the result shows that products therefrom is the Dy of pure oblique crystal phase structure
2OS
2(Fig. 4 a).Observe its pattern and structure (Fig. 4 b) with transmission electron microscope (TEM), the result shows gained Dy
2OS
2Pattern be the one dimension linear structure, length is hundreds of nm, diameter is about 2～3 nm, length-to-diameter ratio is about 50-500, parallel arranged becomes the 2D sheet structure.
Embodiment 4
A clean dried, have in the teflon-lined reaction kettle (volume is 50 mL), add 0.2～6.0 g Ho (NO
3)
36 H
2O solid, 0.10～4.50g thiocarbamide solid, 2～10 mL oleic acid, 2～10 mL amino dodecanes and 5～20 mL vaccenic acids; Sealed reactor is transferred to it in baking oven; Speed with 6 ℃/min rises to 180 ℃ from room temperature, react 24 h after, be cooled to room temperature naturally.Obtain the jelly of light brown shape, add normal heptane, low-grade fever adds ethanol again, and spinning goes out solid.Use normal heptane/absolute ethyl alcohol mixed solvent (volume ratio is 2/1) washing gained head product then, obtain deposition after the spinning.Repeated washing 3-5 time obtains the oyster solid phase prod, will wash good product at last at 60 ℃ of following vacuum-drying 4 h.
Collect dried product, adopt X-Ray powder diffractometer (XRD) to test its composition and thing mutually, the result shows, products therefrom is the Ho of pure oblique crystal phase structure
2OS
2(Fig. 5 a).Observe its pattern and structure (Fig. 5 b) with transmission electron microscope (TEM), the result shows, gained Ho
2OS
2Pattern be the one dimension linear structure, length is hundreds of nm, diameter is about 2～3 nm, length-to-diameter ratio is about 50-500, parallel arranged becomes the 2D sheet structure.
A clean dried, have in the teflon-lined reaction kettle (volume is 50 mL), add 0.20～6.0 g Er (NO
3)
36 H
2O solid, 0.10～4.50g thiocarbamide solid, 2～10 mL oleic acid, 2～10 mL amino dodecanes and 5～20 mL vaccenic acids; Sealed reactor is transferred to it in baking oven; Speed with 4 ℃/min rises to 185 ℃ from room temperature, react 24 h after, be cooled to room temperature naturally.Obtain the jelly of light brown shape.Add normal heptane, low-grade fever adds ethanol again, and spinning goes out solid.Use normal heptane/absolute ethyl alcohol mixed solvent (volume ratio is 2/1) washing products therefrom then, obtain deposition after the spinning.Repeated washing 3-5 time obtains the oyster solid phase prod, will wash good product at last at 60 ℃ of following vacuum-drying 4 h.
Collect dried product, adopt X-Ray powder diffractometer (XRD) to test its composition and thing mutually, the result shows that products therefrom is the Er of pure oblique crystal phase structure
2OS
2(Fig. 6 a).Observe its pattern and structure (Fig. 6 b) with transmission electron microscope (TEM), the result shows gained Er
2OS
2Pattern be the one dimension linear structure, length is hundreds of nm, diameter is about 2～3 nm, length-to-diameter ratio is about 50-500, parallel arranged becomes the 2D sheet structure.
Embodiment 6
A clean dried, have in the teflon-lined reaction kettle (volume is 50 mL), add 0.20～6.0 g Yb (NO
3)
36 H
2O solid, 0.10～4.50g thiocarbamide solid, 2～10 mL oleic acid, 2～10 mL amino dodecanes and 5～20 mL vaccenic acids; Sealed reactor is transferred to it in baking oven; Speed with 6 ℃/min rises to 195 ℃ from room temperature, react 24 h after, be cooled to room temperature naturally.Obtain the jelly of light brown shape.Add normal heptane, low-grade fever adds ethanol again, and spinning goes out solid.Use normal heptane/absolute ethyl alcohol mixed solvent (volume ratio is 2/1) washing gained head product then, obtain deposition after the spinning.Repeated washing 3-5 time obtains the oyster solid phase prod, will wash good product at last at 60 ℃ of following vacuum-drying 4 h.
Collect dried product, adopt X-Ray powder diffractometer (XRD) to test its composition and thing mutually, the result shows that products therefrom is the Yb of pure oblique crystal phase structure
2OS
2(Fig. 7 a).Observe its pattern and structure (Fig. 7 b) with transmission electron microscope (TEM), the result shows gained Yb
2OS
2Pattern be the one dimension linear structure, length is hundreds of nm, diameter is about 2～3 nm, length-to-diameter ratio is about 50-500, parallel arranged becomes the 2D sheet structure.
Embodiment 7-12
According to the method identical, adopt the nitrate salt of La, Ce, Pr, Nd, Sm, Eu to substitute Y (NO with embodiment 1
3)
36 H
2The O solid, other condition is identical with embodiment 1, makes the different oxygen sulphur of the rare earth superfine nano line and the nano wire base superstructure of oblique crystal phase structure respectively.
Embodiment 13, and with embodiment 1, difference is that the lipid acid that is adopted is sad, and aliphatic amide is a cetylamine.
Embodiment 14, and with embodiment 2, difference is that the lipid acid that is adopted is palmitinic acid, and aliphatic amide is a tetradecy lamine.
Embodiment 15, and with embodiment 3, difference is that the lipid acid that is adopted is LAURIC ACID 99 MIN, and aliphatic amide is ten amine.
Embodiment 16, and with embodiment 4, difference is that the aliphatic amide that is adopted is an octylame.
Claims (7)
1. the compound method of monocline crystalline phase rare earth different oxygen sulphur superfine nano line and nano wire base superstructure; It is characterized in that: in the mixed solvent that lipid acid, aliphatic amide and vaccenic acid are formed; Rare-earth metal nitrate solid and thiocarbamide solid heat temperature raising are carried out solid-liquid phase reaction to 180-200 ℃, and reaction product makes object after separating;
Described method may further comprise the steps:
(1) takes by weighing 0.2-6.0 gram rare-earth metal nitrate solid and 0.1 –, 4.50 gram thiocarbamide solids, in the reaction kettle of the inner liner polytetrafluoroethylene of adding clean dried;
(2) add 2-10 mL lipid acid, 2-10 mL aliphatic amide and 5-20 mL vaccenic acid; Sealed reactor, direct heating or reaction kettle placed baking oven is warming up to 180-200 ℃ with 3 ℃ of-8 ℃ of speed of PM; And under this temperature, kept 10-60 hour, reduce to room temperature naturally;
(3) with step 2) the product deposition, spinning, the washing that obtain, vacuum-drying under the room temperature makes monocline crystalline phase rare earth different oxygen sulphur superfine nano line and nano wire base superstructure;
The chemical formula of the different oxygen sulphur of described rare earth is Ln
2OS
2, wherein Ln=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er or Yb.
2. the compound method of rare earth according to claim 1 different oxygen sulphur superfine nano line and nano wire base superstructure is characterized in that its molecular formula of described rare-earth metal nitrate is Ln (NO
3)
3XH
2O, wherein thulium Ln is Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er or Yb, x is 0 ~ 6 integer.
3. the compound method of superfine nano line according to claim 1 and nano wire base superstructure is characterized in that: described lipid acid is C6 ~ C22 straight chain fatty acid, and described aliphatic amide is C6 ~ C22 straight chain armeen.
4. the compound method of superfine nano line according to claim 3 and nano wire base superstructure is characterized in that: described lipid acid is C8 ~ C18 straight chain fatty acid, and described aliphatic amide is C8 ~ C16 straight chain armeen.
5. the compound method of rare earth according to claim 1 different oxygen sulphur superfine nano line and nano wire base superstructure; It is characterized in that: in the described step (3); Earlier with normal heptane with step 2) product that obtains disperses, adds absolute ethyl alcohol then and make it sedimentation, last spinning; With normal heptane/absolute ethyl alcohol mixed solvent washing 3-5 time, with the product that obtains at last 60 ℃ of following vacuum-dryings.
6. the compound method of rare earth according to claim 1 different oxygen sulphur superfine nano line and nano wire base superstructure; It is characterized in that the different oxygen sulphur of described rare earth is linear structure; Or nano wire parallel arranged slabbing structure on the two-dimensional space, or the sheet structure self-organization forms laminate structure or tubular structure on the three-dimensional space.
7. the compound method of rare earth according to claim 6 different oxygen sulphur superfine nano line and nano wire base superstructure is characterized in that: described nanowire diameter is 2～3 nm, and length-to-diameter ratio is 50-500.
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| CN1424257A (en) * | 2003-01-10 | 2003-06-18 | 清华大学 | Rare earth hydroxide nano tubes and synthesis of serial rare earth compounds nano tubes |
| CN1631522A (en) * | 2004-11-19 | 2005-06-29 | 清华大学 | Binary composite mesopore oxide material making cerium as base and its preparation |
| CN101982418A (en) * | 2010-10-29 | 2011-03-02 | 北京化工大学 | Preparation method of perovskite LnCrO3 and LnAlO3 nanomaterials |
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