CN101445272A - Method for preparing CuCrO2*flaky nanocrystalline material - Google Patents
Method for preparing CuCrO2*flaky nanocrystalline material Download PDFInfo
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- CN101445272A CN101445272A CNA200810246218XA CN200810246218A CN101445272A CN 101445272 A CN101445272 A CN 101445272A CN A200810246218X A CNA200810246218X A CN A200810246218XA CN 200810246218 A CN200810246218 A CN 200810246218A CN 101445272 A CN101445272 A CN 101445272A
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Abstract
The invention discloses a method for preparing CuCrO2*flaky nanocrystalline material with copper and iron ore structure. The method comprises the following steps: firstly, the cuprous oxide and the chromic nitrate are weighed according to the 1:0.8-1.25 mol ratio of the copper and the chromium, then the chromic nitrate is added in the aqueous solution of sodium hydroxide to be stirred until fully dissolved, and then the cuprous oxide and a certain amount of polyhexandiol are added to the former solution to be stirred for 30 min to obtain precursor solution; secondly, the precursor solution is transferred to an autoclave with inner liner made of polytetrafluoroethylene, the autoclave is put in a baking oven, the temperature in the baking oven is retained between 210-230 degrees, and the duration time is 48 hours; and thirdly, the solution in the autoclave is taken out to be added with deionized water and acetone for cleaning, the powder obtained after centrifugal separation is dried at the 80 degrees, and then the CuCrO2*flaky nanocrystalline with copper and iron ore structure is obtained. The prepared nanocrystalline material with the copper and iron ore structure has important significance on the application in various fields, because the invention of the CuCrO2 nanometer material with the copper and iron ore structure is not provided so far.
Description
Technical field:
The present invention relates to a kind of CuCrO of delafossite structure
2The preparation of flaky nanocrystalline material and goods.
Background technology:
Delafossite type oxide compound ABO
2(A=Ag
+, Cu
+, Pd
+, and Pt
+B=Al, Fe, Co, Ga, Rh, Cr, In, T1 ...) be a class novel semiconductor material, have A layer and BO by close-packed hexagonal
6The rib octahedral layer replaces the laminate structure of stacking altogether, and it is that monovalent cation B position is a Tricationic that this structure has well been kept the A position.Different positively charged ions is in conjunction with the Application Areas that has determined it, and the A position is Cu
+And Ag
+(d
10Ions) help improving its optical transparence, and Pd
+And Pt
+(d
9Ions) help improving its electroconductibility.Delafossite type oxide compound ABO
2Be generally P-type semiconductor, its current carrier hole derives from that material departs from stoicheiometry and the cationvacancy or the oxygen excess that produce.The delafossite sill is at catalyzer, luminescent material, and solar cell, there is wide application in ozone sensor and P-aspects such as type transparent semiconductor material, receives much attention in recent years.Studies show that at present: delafossite section bar material is as the N type transparent conductive material of its specific conductivity of P type transparent conductive material much smaller than widespread use at present; Delafossite section bar material CuAlO2 at room temperature also can't satisfy the needs of application to the sensitivity of ozone response; Performances such as rare magnetic of adulterated delafossite material and thermoelectricity yet do not reach the requirement of application.And these researchs mainly are at polycrystalline bulk and thin-film material, have only the research of the relevant nanometer delafossite of minute quantity material.And the refinement of nano material crystal grain makes the surface electronic structure of crystal grain and crystal mechanism that variation take place, and has produced the not available effect of a series of block materials, the mechanical property that has caused material, electric property, optical property, magnetic, the change of dielectricity and even thermomechanical property.So with the delafossite material nanoization and study its character, have good practicability for solve the problem that the delafossite material exists in application, significant for it in the application in each field.Have only the research about nanometer delafossite material of minute quantity at present, and mainly concentrate on CuAlO
2, do not have report about other nanometer delafossite materials.Therefore preparing nanometer delafossite material has important meaning for its application in each field, but does not up to the present also have the invention of the nano material of relevant delafossite structure.
Summary of the invention
It is simple to the objective of the invention is to propose a kind of technology, with environmental compatible, and the copper chromium oxygen CuCrO of the delafossite structure that energy consumption is low
2The preparation method of flaky nanocrystalline material.
The CuCrO of delafossite structure
2The preparation method of flaky nanocrystalline material, its feature: finish according to following steps:
(a) be 1:0.8-1.25 weighing Red copper oxide and chromium nitrate by the mol ratio of copper and chromium after, chromium nitrate is joined in the aqueous solution of 1.0-2.5M sodium hydroxide, being stirred to chromium nitrate dissolves fully, subsequently, be that the poly-hexylene glycol of 0.6-0.9M joins to stir in the solution of front and obtained precursor solution in 20-60 minute with Red copper oxide and surfactant concentration;
(b) top precursor solution is transferred to (compactedness of solution is 60%-70% in its still) in the autoclave that liner is a tetrafluoroethylene, after the sealing autoclave is put into baking oven, temperature in the baking oven remains on 210-230 ℃, and the time length is to naturally cool to room temperature after 36-60 hour;
(c) solution that takes out in the still adds deionized water and acetone cleaning, and the powder that obtains after the centrifugation is being dried, thereby makes the copper chromium oxygen flaky nanocrystalline material of delafossite structure.
The CuCrO of described delafossite structure
2The preparation method of flaky nanocrystalline material is characterized in that precursor solution is placed enclosed autoclave, and wherein the compactedness of autoclave is 70%, and temperature of reaction is 210-230 ℃, and the time length is 48 hours.
The CuCrO of described delafossite structure
2The preparation method of flaky nanocrystalline material is characterized in that the mol ratio of copper and chromium is 1:1 in Red copper oxide and the chromium nitrate.
Beneficial effect with respect to prior art is, one, and preparation technology is simple, uses water as solvent, and is free from environmental pollution, and reaction is carried out at low temperatures, makes production cost be reduced significantly, makes it be easy to large-scale industrial production; Its two, make the CuCrO of delafossite structure
2The polycrystalline phase becomes mutually even, and does not contain dephasign; Its three, to the CuCrO of the delafossite structure that repeatedly makes
2Polycrystalline material uses field emission scanning electron microscope, x-ray diffractometer, x-ray photoelectron spectroscopy analyser, high resolution transmission electron microscopy and incidental selected area electron diffraction analyser respectively, from the stereoscan photograph that obtains as can be known, the powder of polycrystalline material is a flaky nanocrystalline, and the particle size distribution scope does not have any coacervate at 30-90nm.By X-ray diffracting spectrum as can be known, polycrystalline material is the 3R-CuCrO of delafossite structure
2The polycrystalline phase becomes mutually even, does not contain its halfwidth of dephasign and obviously broadens and have the feature of typical nano structural material.By x-ray photoelectron spectroscopy figure as can be known, polycrystalline material is elementary composition by monovalence copper, tervalent chromium and three kinds of oxygen.By the micro-spectrum of high resolution projection electron and selected area electron diffraction figure as can be known this flaky nanocrystalline be monocrystalline.
Description of drawings:
Fig. 1 is the CuCrO to the delafossite structure that makes
2The powder x-ray diffraction of nano material (XRD) spectrum, X-coordinate is a diffraction angle among the figure, ordinate zou is a relative intensity.Peak position and halfwidth by XRD figure can see that this material is the CuCrO of delafossite structure
2And has a feature of typical nano structural material.
Fig. 2 is the CuCrO to the delafossite structure that makes
2Polycrystalline material uses the XPS figure that obtains after the test of X-ray energy spectrum (XPS) analyser, and the X-coordinate among the figure is that energy, ordinate zou are relative intensity.This XPS figure explanation, polycrystalline material by copper be monovalence, chromium is trivalent; Understand that further this material is the CuCrO of pure phase
2
Fig. 3 is the CuCrO to the delafossite structure that makes
2Polycrystalline material use LEO-1530 type field emission scanning electron microscope (SEM) observation take the photograph the SEM photo.Can see that from picture the particulate pattern is flaky, its size of particles is less than 100 nanometers.
Fig. 4 is the CuCrO to the delafossite structure that makes
2Material uses the diffractogram that obtains after the incidental selected area electron diffraction analyser test of JEM 2010 type high resolution transmission electron microscopies, this electron-diffraction diagram explanation, and single small pieces are monocrystalline.
Embodiment
At first buy chromium nitrate, Red copper oxide, sodium hydroxid, poly-hexylene glycol, then from market
Embodiment 1: finish preparation according to the following steps order:
(a) be 1:0.8-1.25 weighing Red copper oxide and chromium nitrate by the mol ratio of copper and chromium after, chromium nitrate is joined in the aqueous solution of sodium hydroxide, being stirred to chromium nitrate dissolves fully, wherein the content of sodium hydroxide is 1.0M, subsequently, Red copper oxide and a certain amount of poly-hexylene glycol (concentration is 0.8M) are joined stir in the solution of front and obtain precursor solution half an hour.
(b) in being transferred to, top precursor solution turns in one's mind in the autoclave for tetrafluoroethylene, the compactedness of solution is 60%-70% in its still, after the sealing autoclave is put into baking oven, the temperature in the baking oven remains on the 210-230 degree, and the time length is to naturally cool to room temperature after 36-60 hour.
(c) solution that takes out in the still adds deionized water and acetone cleaning, and the powder that obtains after the centrifugation is spent oven dry 80, thereby makes the copper chromium oxygen flaky nanocrystalline of delafossite structure.
Embodiment 2: finish preparation according to the following steps order:
(a) be 1:0.8-1.25 weighing Red copper oxide and chromium nitrate by the mol ratio of copper and chromium after, chromium nitrate is joined in the aqueous solution of sodium hydroxide, being stirred to chromium nitrate dissolves fully, wherein the content of sodium hydroxide is 1.5M, subsequently, Red copper oxide and a certain amount of poly-hexylene glycol (concentration is 0.8M) are joined stir in the solution of front and obtain precursor solution half an hour.
(b) in being transferred to, top precursor solution turns in one's mind in the autoclave for tetrafluoroethylene, the compactedness of solution is 60%-70% in its still, after the sealing autoclave is put into baking oven, the temperature in the baking oven remains on the 210-230 degree, and the time length is to naturally cool to room temperature after 36-60 hour.
(c) solution that takes out in the still adds deionized water and acetone cleaning, and the powder that obtains after the centrifugation is spent oven dry 80, thereby makes the copper chromium oxygen flaky nanocrystalline of delafossite structure.
Embodiment 3: finish preparation according to the following steps order:
(a) be 1:0.8-1.25 weighing Red copper oxide and chromium nitrate by the mol ratio of copper and chromium after, chromium nitrate is joined in the aqueous solution of sodium hydroxide, being stirred to chromium nitrate dissolves fully, wherein the content of sodium hydroxide is 2.5M, subsequently, Red copper oxide and a certain amount of poly-hexylene glycol (concentration is 0.8M) are joined stir in the solution of front and obtain precursor solution half an hour.
(b) top precursor solution is transferred in the autoclave that liner is a tetrafluoroethylene, the compactedness of solution is 60%-70% in its still, after the sealing autoclave is put into baking oven, the temperature in the baking oven remains on the 210-230 degree, and the time length is to naturally cool to room temperature after 36-60 hour.
(c) solution that takes out in the still adds deionized water and acetone cleaning, and the powder that obtains after the centrifugation is spent oven dry 80, thereby makes the copper chromium oxygen flaky nanocrystalline of delafossite structure.
Obviously, those skilled in the art can be to the CuCrO of delafossite structure of the present invention
2The preparation method of flaky nanocrystalline material and the material of preparation thereof carry out various changes and modification and do not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (3)
1, CuCrO
2The preparation method of flaky nanocrystalline material, its feature: finish according to following steps:
(a) be 1:0.8-1.25 weighing Red copper oxide and chromium nitrate by the mol ratio of copper and chromium after, chromium nitrate is joined in the aqueous solution of 1.0-2.5M sodium hydroxide, being stirred to chromium nitrate dissolves fully, subsequently, be that the poly-hexylene glycol of 0.6-0.9M joins to stir in the solution of front and obtained precursor solution in 20-60 minute with Red copper oxide and surfactant concentration;
(b) top precursor solution is transferred in the autoclave that liner is a tetrafluoroethylene, after the sealing autoclave is put into baking oven, the temperature in the baking oven remains on 210-230 ℃, and the time length is to naturally cool to room temperature after 36-60 hour;
(c) solution that takes out in the still adds deionized water and acetone cleaning, and the powder that obtains after the centrifugation is being dried, thereby makes the copper chromium oxygen flaky nanocrystalline material of delafossite structure.
2, CuCrO according to claim 1
2The preparation method of flaky nanocrystalline material is characterized in that precursor solution is placed enclosed autoclave, and wherein the compactedness of autoclave is 70%, and temperature of reaction is 210-230 ℃, and the time length is 48 hours.
3, CuCrO according to claim 1
2The preparation method of flaky nanocrystalline material is characterized in that the mol ratio of copper and chromium is 1:1 in Red copper oxide and the chromium nitrate.
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|---|---|---|---|
| CNA200810246218XA CN101445272A (en) | 2008-12-30 | 2008-12-30 | Method for preparing CuCrO2*flaky nanocrystalline material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112310287A (en) * | 2020-10-15 | 2021-02-02 | 上海工程技术大学 | Preparation method of high-stability inorganic hole transport film capable of being produced in large scale |
| CN112456557A (en) * | 2020-11-26 | 2021-03-09 | 北京化工大学 | Method for preparing copper-based delafossite-type oxide material |
-
2008
- 2008-12-30 CN CNA200810246218XA patent/CN101445272A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| SHU ZHOU ET AL.: "Hydrothermal synthesis and characterization of CuCrO2 laminar nanocrystals", 《JOURNAL OFCRYSTALGROWTH》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112310287A (en) * | 2020-10-15 | 2021-02-02 | 上海工程技术大学 | Preparation method of high-stability inorganic hole transport film capable of being produced in large scale |
| CN112456557A (en) * | 2020-11-26 | 2021-03-09 | 北京化工大学 | Method for preparing copper-based delafossite-type oxide material |
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Application publication date: 20090603 |