CN110182839B - Method for preparing copper oxide nano array by using copper-aluminum oxide film as precursor - Google Patents
Method for preparing copper oxide nano array by using copper-aluminum oxide film as precursor Download PDFInfo
- Publication number
- CN110182839B CN110182839B CN201910471088.8A CN201910471088A CN110182839B CN 110182839 B CN110182839 B CN 110182839B CN 201910471088 A CN201910471088 A CN 201910471088A CN 110182839 B CN110182839 B CN 110182839B
- Authority
- CN
- China
- Prior art keywords
- copper
- oxide film
- aluminum
- precursor
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
A method for preparing a copper oxide nano array by using a copper aluminum oxide film as a precursor relates to a method for preparing a copper oxide nano array. The invention aims to solve the technical problems that the existing copper oxide nano array is complex in preparation process and poor in binding property with a target substrate. The invention comprises the following steps: firstly, preparing a copper-aluminum spinel oxide film; secondly, welding; and thirdly, carrying out hydrothermal reaction. The copper aluminate spinel oxide film prepared by the invention is used as a precursor for synthesizing a CuO nano structure, is convenient to transplant and operate, has stable chemical property in the air and is easy to store; the invention adopts simple soaking and heating processes to prepare the copper-aluminum spinel oxide film, then the copper-aluminum spinel oxide film is stacked with the brazing filler metal and the matrix material and heated, so that the connection of the precursor and the matrix can be realized, the precursor of the copper-aluminum spinel oxide film is welded with the matrix before the hydrothermal reaction, and the CuO nanostructure generated by the reaction of the precursor is well combined with the matrix after the hydrothermal reaction.
Description
Technical Field
The invention relates to a method for preparing a copper oxide nano array.
Background
The copper oxide is a p-type semiconductor material, and the nano copper oxide is composed ofThe scale effect can be used as a bacteriostatic material, and can also be used in the fields of photo-assisted catalysis, electrochemical sensing and the like. The existing methods for preparing the nano copper oxide mainly comprise a sol-gel method, a hydrothermal method, an electrochemical method, a copper matrix heating oxidation method and the like. The nano copper oxide prepared by a chemical method is usually directly or indirectly prepared from copper hydroxide (Cu (OH)2) The CuO is used as a precursor or an intermediate to further obtain the nano CuO, but the CuO prepared by the method is in a free powder shape and cannot be well combined with a target matrix. The CuO obtained by the method is easy to peel off from the substrate due to the larger difference of linear expansion coefficients of the CuO and the substrate, and the CuO structure which is combined with the substrate more stably can be obtained only on an extremely thin copper foil.
Disclosure of Invention
The invention provides a method for preparing a copper oxide nano array by using a copper-aluminum oxide film as a precursor, aiming at solving the technical problems of complex preparation process and poor binding property with a target substrate of the existing copper oxide nano array.
The method for preparing the copper oxide nano array by using the copper-aluminum oxide film as the precursor comprises the following steps:
firstly, preparing a copper-aluminum spinel oxide film: carrying out heat treatment on an Anodic Aluminum Oxide (AAO) film with nano pores, cooling, placing the film in 0.2-0.5 mol/L ethanol solution of dodecylbenzene sulfonic acid for soaking for 4-6 h for hydrophilic modification, taking out the film, naturally drying the film, and placing the film in 1-2 mol/L CuCl2Soaking in the aqueous solution for 10-30 min, taking out, naturally drying in the air, and performing heat treatment again to obtain a copper-aluminum spinel oxide film;
the two heat treatments in the step are the same in process and are carried out in a muffle furnace, the heating temperature is 900-1000 ℃, and the heat preservation time is 5-30 min;
secondly, welding: polishing the base material by using sand paper, then ultrasonically cleaning the base material by using absolute ethyl alcohol for 10-15 min, and naturally drying the base material; stacking the cleaned substrate material, the brazing filler metal and the copper-aluminum spinel oxide film prepared in the first step from bottom to top in sequence, heating, and cooling to room temperature to complete welding of the copper-aluminum spinel oxide film and the substrate;
thirdly, hydrothermal reaction: putting the product welded in the second step into a high-pressure hydrothermal reaction kettle, adding 0.2-0.3 mol/L NaOH aqueous solution to completely immerse the product welded in the second step, heating the product to 190-250 ℃ from room temperature under the condition that the heating rate is 6.5-7 ℃/min, and preserving heat for 30-120 min to enable the copper-aluminum spinel oxide film to react to generate nano copper oxide, taking out the product from the reaction kettle after natural cooling, and cleaning the product with deionized water to obtain a copper oxide nano array; the volume of the 0.2 mol/L-0.3 mol/L NaOH aqueous solution is 45-55% of the volume of the high-pressure hydrothermal reaction kettle.
The design principle of the invention is as follows:
the AAO template selected in the invention is transparent film-shaped, and the chemical component is aluminum oxide (Al)2O3) Amorphous state at normal temperature, and can be converted into eta-Al by heating in air at 900-1000 deg.C2O3Predominantly activated alumina and remains eta-Al after cooling to room temperature2O3This crystalline form. Al (Al)2O3Has various crystal forms, wherein eta-Al2O3The crystal lattice type of the ceramic belongs to alumina functional ceramics, the crystal lattice type is a spinel structure, the ceramic lattice can be connected by using Ag-based brazing filler metal, and the ceramic lattice has higher chemical activity, can react with various oxides to generate composite oxides, and can be stably stored in the air.
The invention firstly heats the AAO film to convert the film into eta-Al2O3Soaking in CuCl2Coating CuCl on the surface of the substrate in aqueous solution2，CuCl2When heated in air, the CuO is firstly changed into the CuO and then reacts with eta-Al2O3The reaction generates copper-aluminum composite spinel oxide as a precursor for generating CuO nano-structure, then the precursor is welded on a substrate material by brazing filler metal, finally the copper-aluminum spinel oxide film is decomposed by hydrothermal reaction to generate CuO with nano-structure, and Cu with good connectivity with the substrate is obtainedAnd (4) O nano-arrays.
The invention has the following beneficial effects:
1. the copper aluminate spinel oxide film prepared by the invention is used as a precursor for synthesizing a CuO nano structure, is convenient to transplant and operate, has stable chemical property in the air and is easy to store;
2. the method is simple and effective in operation, the copper-aluminum spinel oxide film is prepared by adopting simple soaking and heating processes, and then the film, the brazing filler metal and the matrix material are sequentially stacked and heated, so that the connection of the precursor and the matrix can be realized;
3. according to the invention, before the hydrothermal reaction, the precursor of the copper-aluminum spinel oxide film is welded with the matrix, and after the hydrothermal reaction, the CuO nano structure generated by the precursor reaction is well combined with the matrix.
The invention provides a method for preparing a copper oxide nano array by using a copper-aluminum oxide film as a precursor, which is simple and effective to operate, and simultaneously provides a method for connecting the copper oxide nano array with a target substrate, so that the method has a good application prospect.
Drawings
FIG. 1 is an XRD pattern;
FIG. 2 is an SEM image of the copper oxide nanoarray obtained in step three of experiment one;
FIG. 3 is an SEM image of the product obtained in step three of experiment three.
Detailed Description
The first embodiment is as follows: the embodiment is a method for preparing a copper oxide nano array by using a copper-aluminum oxide film as a precursor, which comprises the following steps:
firstly, preparing a copper-aluminum spinel oxide film: the anodic aluminum oxide film with the nano pores is subjected to heat treatment, is placed in 0.2-0.5 mol/L ethanol solution of dodecylbenzene sulfonic acid for soaking for 4-6 h for hydrophilic modification after being cooled, is taken out and naturally dried, and is then placed in 1-2 mol/L CuCl2Soaking in the aqueous solution for 10-30 min, taking out, naturally drying in the air, and performing heat treatment again to obtain a copper-aluminum spinel oxide film;
the two heat treatments in the step are the same in process and are carried out in a muffle furnace, the heating temperature is 900-1000 ℃, and the heat preservation time is 5-30 min;
secondly, welding: polishing the base material by using sand paper, then ultrasonically cleaning the base material by using absolute ethyl alcohol for 10-15 min, and naturally drying the base material; stacking the cleaned substrate material, the brazing filler metal and the copper-aluminum spinel oxide film prepared in the first step from bottom to top in sequence, heating, and cooling to room temperature to complete welding of the copper-aluminum spinel oxide film and the substrate;
thirdly, hydrothermal reaction: putting the product welded in the second step into a high-pressure hydrothermal reaction kettle, adding 0.2-0.3 mol/L NaOH aqueous solution to completely immerse the product welded in the second step, heating the product to 190-250 ℃ from room temperature under the condition that the heating rate is 6.5-7 ℃/min, and preserving heat for 30-120 min to enable the copper-aluminum spinel oxide film to react to generate nano copper oxide, taking out the product from the reaction kettle after natural cooling, and cleaning the product with deionized water to obtain a copper oxide nano array; the volume of the 0.2 mol/L-0.3 mol/L NaOH aqueous solution is 45-55% of the volume of the high-pressure hydrothermal reaction kettle.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the CuCl mentioned in the step one2The concentration of the aqueous solution was 1.5 mol/L. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the base material in the second step is a high-temperature stable ceramic material, in particular Al2O3BSCF, BCFN or BCFZ. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the base material in the second step is a metal material with high melting point and stable chemical property, specifically Pt, Crofer22APU, AISI310S or AISI 314. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: this embodiment differs from the third and fourth embodiments in that: in the second step, simple substance Ag is used as brazing filler metal, and the process of heating and cooling to room temperature in the second step comprises the following steps: heating the substrate to 970-1000 ℃ from room temperature in a muffle furnace at a heating rate of 10-15 ℃/min, preserving the heat for 15-45 min, cooling the substrate to room temperature at a cooling rate of 5-10 ℃/min, and connecting the substrate and the copper-aluminum spinel oxide film. The other is the same as the third and fourth embodiments.
The sixth specific implementation mode: the first difference between the present embodiment and the specific embodiment is: the matrix material in the second step is a material which is easily oxidized at high temperature in the air, and is particularly a Ti, Nb, Ni or carbon material. The rest is the same as the first embodiment.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: in the second step, AgCuTi is used as brazing filler metal, and the process of heating and cooling to room temperature in the second step is as follows: heating to 780-850 ℃ from room temperature at the heating rate of 10-15 ℃/min under the vacuum condition in a vacuum furnace, preserving the heat for 15-45 min under the vacuum condition, then cooling to room temperature under the conditions of vacuum and cooling rate of 5-10 ℃/min, and connecting the substrate and the copper-aluminum spinel oxide film. The rest is the same as the sixth embodiment.
The specific implementation mode is eight: the present embodiment differs from the first to seventh embodiments in that: the anodic aluminum oxide film with the nano-pores in the step one is of a two-pass structure, the thickness is 30-60 mu m, and the pore diameter is 40-100 nm. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the first difference between the present embodiment and the specific embodiment is: polishing the Pt foil by using sand paper, then ultrasonically cleaning the Pt foil by using absolute ethyl alcohol for 10-15 min, and naturally drying the Pt foil; and (3) sequentially stacking four samples of the Ag brazing filler metal sheet, the copper-aluminum spinel oxide film prepared in the first step, the Ag brazing filler metal sheet and the Pt foil from top to bottom, placing the four samples in a muffle furnace for heating, raising the temperature from room temperature to 970 ℃ under the condition that the temperature rise rate is 10 ℃/min, preserving the temperature for 30min, and cooling to room temperature to weld the copper-aluminum spinel oxide film and the Pt foil together. The rest is the same as the first embodiment.
The invention was verified with the following tests:
test one: the test is a method for preparing a copper oxide nano array by using a copper-aluminum oxide film as a precursor, and is specifically carried out according to the following steps:
firstly, preparing a copper-aluminum spinel oxide film: carrying out heat treatment on the anodic aluminum oxide film with the nano holes, cooling, placing the film in 0.2mol/L ethanol solution of dodecylbenzene sulfonic acid for soaking for 4 hours for hydrophilic modification, taking out the film, naturally airing the film, and placing the film in 1.5mol/L CuCl2Soaking in the water solution for 15min, taking out, naturally drying in the air, and performing heat treatment again to obtain a copper-aluminum spinel oxide film;
the two heat treatments in the step are the same in process and are carried out in a muffle furnace, the heating temperature is 970 ℃, and the heat preservation time is 30 min; the anodic aluminum oxide film with the nano-pores is of a bi-pass structure, the thickness is 50 mu m, and the pore diameter is 60 nm-80 nm;
secondly, welding: polishing a Pt foil serving as a base material by using sand paper, then ultrasonically cleaning the Pt foil by using absolute ethyl alcohol for 10-15 min, and naturally drying the Pt foil; stacking the cleaned Pt foil, the cleaned Ag solder and the copper-aluminum spinel oxide film prepared in the first step together from bottom to top in sequence, heating the Pt foil, the Ag solder and the copper-aluminum spinel oxide film from room temperature to 970 ℃ in a muffle furnace at a heating rate of 15 ℃/min, preserving heat for 30min, and then cooling the Pt foil, the Ag solder and the copper-aluminum spinel oxide film to room temperature under the condition that the cooling rate is 10 ℃/min to finish welding the substrate and the copper-aluminum spinel oxide film;
thirdly, hydrothermal reaction: putting the product welded in the second step into a high-pressure hydrothermal reaction kettle, adding 0.2mol/L NaOH aqueous solution to completely immerse the product welded in the second step, heating the product from room temperature to 250 ℃ under the condition that the heating rate is 6.5 ℃/min, preserving the temperature for 60min to enable the copper-aluminum spinel oxide film to react to generate nano copper oxide, naturally cooling the nano copper oxide, taking the nano copper oxide out of the reaction kettle, and cleaning the nano copper oxide with deionized water to obtain a copper oxide nano array; the volume of the 0.2mol/L NaOH aqueous solution is 50 percent of the volume of the high-pressure hydrothermal reaction kettle.
FIG. 1 is an XRD pattern, where A is a number of nanocrystals in experiment oneThe anodic alumina film with the micropores in the first test is a sample of the anodic alumina film with the micropores in the first test after the heating temperature is 970 ℃ and the heat preservation time is 30min, and the figure shows that the amorphous anodic alumina film can be converted into crystalline eta-Al after being heated in the air at 970 DEG C2O3. Curve D is the thin film of copper aluminum spinel oxide obtained at step one of test one.
And (2) test II: adding CuCl2The sample after the holding time of 30min at a heating temperature of 500 ℃ in air was subjected to XRD test, and as shown by curve C in FIG. 1, it was identified as CuO.
Fig. 2 is an SEM image of the copper oxide nanoarray obtained in the third step of the first test, and it can be seen that the CuO nanoarray prepared in the first test is sheet-shaped, has a large length in the z-direction, and is connected to the substrate.
And (3) test III: this test differs from the test one in that: polishing the Pt foil by using sand paper, then ultrasonically cleaning the Pt foil by using absolute ethyl alcohol for 10-15 min, and naturally drying the Pt foil; and (3) sequentially stacking four samples of the Ag brazing filler metal sheet, the copper-aluminum spinel oxide film prepared in the first step, the Ag brazing filler metal sheet and the Pt foil from top to bottom, placing the four samples in a muffle furnace for heating, raising the temperature from room temperature to 970 ℃ under the condition that the temperature rise rate is 10 ℃/min, preserving the temperature for 30min, and cooling to room temperature to weld the copper-aluminum spinel oxide film and the Pt foil together. The rest is the same as test one.
Fig. 3 is an SEM image of the product obtained in the third step of the third experiment, where the region 1 is Ag and the region 2 is CuO, and the entire structure is seen to be sandwiched, and the CuO nanoarray connects the upper and lower Ag portions together.
Claims (9)
1. A method for preparing a copper oxide nano array by using a copper-aluminum oxide film as a precursor is characterized by comprising the following steps of:
firstly, preparing a copper-aluminum spinel oxide film: the anodic alumina film with nano-pores is subjected to heat treatment, and is placed in 0.2 mol/L-0.5 mol/L dodecyl benzene sulfonic acid after being cooledSoaking in alcohol solution of acid for 4-6 hr for hydrophilic modification, taking out, air drying, and adding into 1-2 mol/L CuCl2Soaking in the aqueous solution for 10-30 min, taking out, naturally drying in the air, and performing heat treatment again to obtain a copper-aluminum spinel oxide film;
the two heat treatments in the step are the same in process and are carried out in a muffle furnace, the heating temperature is 900-1000 ℃, and the heat preservation time is 5-30 min;
secondly, welding: polishing the base material by using sand paper, then ultrasonically cleaning the base material by using absolute ethyl alcohol for 10-15 min, and naturally drying the base material; stacking the cleaned substrate material, the brazing filler metal and the copper-aluminum spinel oxide film prepared in the first step from bottom to top in sequence, heating, and cooling to room temperature to complete welding of the copper-aluminum spinel oxide film and the substrate;
thirdly, hydrothermal reaction: putting the product welded in the second step into a high-pressure hydrothermal reaction kettle, adding 0.2-0.3 mol/L NaOH aqueous solution to completely immerse the product welded in the second step, heating the product to 190-250 ℃ from room temperature under the condition that the heating rate is 6.5-7 ℃/min, and preserving heat for 30-120 min to enable the copper-aluminum spinel oxide film to react to generate nano copper oxide, taking out the product from the reaction kettle after natural cooling, and cleaning the product with deionized water to obtain a copper oxide nano array; the volume of the 0.2 mol/L-0.3 mol/L NaOH aqueous solution is 45-55% of the volume of the high-pressure hydrothermal reaction kettle.
2. The method of claim 1, wherein the CuCl is introduced in step one2The concentration of the aqueous solution was 1.5 mol/L.
3. The method for preparing copper oxide nanoarrays using copper aluminum oxide thin film as precursor as claimed in claim 1, wherein the base material in step two is a high temperature stable ceramic material, specifically Al2O3BSCF, BCFN or BCFZ.
4. The method for preparing copper oxide nanoarrays using copper aluminum oxide thin film as precursor according to claim 1, wherein the base material in the second step is a metal material with high melting point and stable chemical property, specifically Pt, Crofer22APU, AISI310S or AISI 314.
5. The method for preparing the copper oxide nano array by using the copper aluminum oxide film as the precursor as claimed in claim 3 or 4, wherein the simple substance Ag is used as the brazing filler metal in the second step, and the process of heating and cooling to room temperature in the second step comprises the following steps: heating the substrate to 970-1000 ℃ from room temperature in a muffle furnace at a heating rate of 10-15 ℃/min, preserving the heat for 15-45 min, cooling the substrate to room temperature at a cooling rate of 5-10 ℃/min, and connecting the substrate and the copper-aluminum spinel oxide film.
6. The method for preparing copper oxide nanoarrays using copper aluminum oxide thin film as precursor as claimed in claim 1, wherein the base material in step two is a material which is easily oxidized at high temperature in air, specifically Ti, Nb, Ni or carbon material.
7. The method for preparing the copper oxide nano array by using the copper aluminum oxide film as the precursor as claimed in claim 6, wherein AgCuTi is used as the brazing filler metal in the second step, and the process of heating and cooling to room temperature in the second step comprises the following steps: heating from room temperature to 780-850 ℃ at the heating rate of 10-15 ℃/min in a vacuum furnace, preserving the heat for 15-45 min in the vacuum condition, cooling to room temperature under the conditions of vacuum and cooling rate of 5-10 ℃/min, and connecting the substrate and the copper-aluminum spinel oxide film.
8. The method for preparing copper oxide nanoarrays using copper aluminum oxide thin film as precursor as claimed in claim 1, wherein the anodic aluminum oxide thin film with nanopores in step one is a double pass structure with a thickness of 30 μm to 60 μm and a pore size of 40nm to 100 nm.
9. A method for preparing a copper oxide nano array by using a copper-aluminum oxide film as a precursor is characterized by comprising the following steps of:
firstly, preparing a copper-aluminum spinel oxide film: the anodic aluminum oxide film with the nano pores is subjected to heat treatment, is placed in 0.2-0.5 mol/L ethanol solution of dodecylbenzene sulfonic acid for soaking for 4-6 h for hydrophilic modification after being cooled, is taken out and naturally dried, and is then placed in 1-2 mol/L CuCl2Soaking in the aqueous solution for 10-30 min, taking out, naturally drying in the air, and performing heat treatment again to obtain a copper-aluminum spinel oxide film;
the two heat treatments in the step are the same in process and are carried out in a muffle furnace, the heating temperature is 900-1000 ℃, and the heat preservation time is 5-30 min;
secondly, welding: polishing the Pt foil by using sand paper, then ultrasonically cleaning the Pt foil by using absolute ethyl alcohol for 10-15 min, and naturally drying the Pt foil; sequentially stacking four samples of the Ag brazing filler metal sheet, the copper-aluminum spinel oxide film prepared in the first step, the Ag brazing filler metal sheet and the Pt foil from top to bottom, placing the four samples in a muffle furnace for heating, raising the temperature from room temperature to 970 ℃ under the condition that the temperature rise rate is 10 ℃/min, preserving the temperature for 30min, and cooling to room temperature to complete the welding of the copper-aluminum spinel oxide film and the Pt foil;
thirdly, hydrothermal reaction: putting the product welded in the second step into a high-pressure hydrothermal reaction kettle, adding 0.2-0.3 mol/L NaOH aqueous solution to completely immerse the product welded in the second step, heating the product to 190-250 ℃ from room temperature under the condition that the heating rate is 6.5-7 ℃/min, and preserving heat for 30-120 min to enable the copper-aluminum spinel oxide film to react to generate nano copper oxide, taking out the product from the reaction kettle after natural cooling, and cleaning the product with deionized water to obtain a copper oxide nano array; the volume of the 0.2 mol/L-0.3 mol/L NaOH aqueous solution is 45-55% of the volume of the high-pressure hydrothermal reaction kettle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910471088.8A CN110182839B (en) | 2019-05-31 | 2019-05-31 | Method for preparing copper oxide nano array by using copper-aluminum oxide film as precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910471088.8A CN110182839B (en) | 2019-05-31 | 2019-05-31 | Method for preparing copper oxide nano array by using copper-aluminum oxide film as precursor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110182839A CN110182839A (en) | 2019-08-30 |
| CN110182839B true CN110182839B (en) | 2021-07-06 |
Family
ID=67719505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910471088.8A Active CN110182839B (en) | 2019-05-31 | 2019-05-31 | Method for preparing copper oxide nano array by using copper-aluminum oxide film as precursor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110182839B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115465881B (en) * | 2022-08-09 | 2023-09-01 | 河北科技大学 | Synthesis method of electron-rich n-CuO material rich in oxygen vacancies |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1625628A2 (en) * | 2003-05-21 | 2006-02-15 | Hahn-Meitner-Institut Berlin GmbH | METHOD FOR PRODUCING TRANSPARENT P-CONDUCTIVE CuAlO2 |
| CN101391901A (en) * | 2008-11-07 | 2009-03-25 | 哈尔滨工业大学 | Brazing method Al2O3 ceramic and metallic material |
| CN101890498A (en) * | 2010-06-24 | 2010-11-24 | 昆明理工大学 | Preparation method of CuAlO2 target |
| CN102560362A (en) * | 2012-03-08 | 2012-07-11 | 杭州电子科技大学 | Method for preparing p-type CuAlO2 transparent conductive film |
| KR20130056663A (en) * | 2011-11-22 | 2013-05-30 | 한국과학기술연구원 | A counter electrodes for dye-sensitized solar cells and preparation method thereof |
| CN103523815A (en) * | 2013-10-29 | 2014-01-22 | 西南民族大学 | Preparing method of CuAlO2 powder adaptable to solar cell |
| CN104005015A (en) * | 2014-06-12 | 2014-08-27 | 哈尔滨工业大学 | Method for conducting in-situ growth of alpha-Fe2O3 nano arrays on surface of steel |
-
2019
- 2019-05-31 CN CN201910471088.8A patent/CN110182839B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1625628A2 (en) * | 2003-05-21 | 2006-02-15 | Hahn-Meitner-Institut Berlin GmbH | METHOD FOR PRODUCING TRANSPARENT P-CONDUCTIVE CuAlO2 |
| CN101391901A (en) * | 2008-11-07 | 2009-03-25 | 哈尔滨工业大学 | Brazing method Al2O3 ceramic and metallic material |
| CN101890498A (en) * | 2010-06-24 | 2010-11-24 | 昆明理工大学 | Preparation method of CuAlO2 target |
| KR20130056663A (en) * | 2011-11-22 | 2013-05-30 | 한국과학기술연구원 | A counter electrodes for dye-sensitized solar cells and preparation method thereof |
| CN102560362A (en) * | 2012-03-08 | 2012-07-11 | 杭州电子科技大学 | Method for preparing p-type CuAlO2 transparent conductive film |
| CN103523815A (en) * | 2013-10-29 | 2014-01-22 | 西南民族大学 | Preparing method of CuAlO2 powder adaptable to solar cell |
| CN104005015A (en) * | 2014-06-12 | 2014-08-27 | 哈尔滨工业大学 | Method for conducting in-situ growth of alpha-Fe2O3 nano arrays on surface of steel |
Non-Patent Citations (4)
| Title |
|---|
| Evolution behavior of Al2O3 nanoparticles reinforcements during reactive air brazing and its role in improving the joint strength;Xiaoqing Si;《Materials and Design》;20170702;第132卷;全文 * |
| Reactive air brazing of YSZ ceramic with novel Al2O3 nanoparticles reinforced Ag-CuO-Al2O3 composite filler: Microstructure and joint properties;Xiaoqing Si;《Materials and Design》;20161028;第114卷;全文 * |
| Time-effective synthesis of rhombohedral CuAlO2 from mesoporous alumina substrate;Ali Saffar Shamshirgar;《Materials & Design》;20180605;第147卷;全文 * |
| 陶瓷空气反应钎焊研究综述;李淳;《精密成形工程》;20180131;第10卷(第1期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110182839A (en) | 2019-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105714353B (en) | A kind of method in high-entropy alloy Surface Creation Nano tube of composite oxides array | |
| CN103360080B (en) | Method for preparation of ceramic nanofiltration membrane by improved sol-gel technique | |
| JP4216803B2 (en) | Submicron electrolyte thin films formed on nanoporous substrates by oxidation of metal films | |
| CN108075139B (en) | Ordered membrane electrode based on metal oxide nanobelt and preparation and application thereof | |
| CN110182839B (en) | Method for preparing copper oxide nano array by using copper-aluminum oxide film as precursor | |
| CN105964151A (en) | Preparation method and use of graphene composite film with interlayer MOFs | |
| CN101302118A (en) | Preparation of silicon nanowire array | |
| CN110038436B (en) | Preparation method of titanium dioxide/graphene oxide/polyethylene glycol composite ceramic nanofiltration membrane | |
| CN106086768B (en) | The preparation method of copper-based bed load nanostructure copper cobalt manganese composite oxide material | |
| WO2023134092A1 (en) | Preparation method for multilayer ceramic membrane having oxide thin layer, and application | |
| CN105845945B (en) | A kind of middle low-temperature protonic conductor solid oxide cell combination electrode and preparation | |
| CN109012187B (en) | Method for in-situ growth of layered double-metal oxide nanofiltration membrane | |
| CN103938130A (en) | Preparation method of nanometer porous nickel block | |
| CN103490076B (en) | Method for preparing acicular metal Ni on inner surface of porous substrate at high temperature | |
| CN105251374A (en) | Preparation method of nanoscale surface defect crystal seed induced SAPO-34 molecular sieve membrane | |
| CN108033479A (en) | A kind of needle-shaped Kocide SD with super-hydrophobicity and preparation method thereof | |
| CN101319388B (en) | Preparation method of multicenter zinc aluminate nanometer pipe | |
| JPWO2009102009A1 (en) | Film-like free-standing metal thin film for hydrogen separation and method for producing the same | |
| CN107879371B (en) | Method for in-situ growth of needle-shaped copper hydroxide on surface of copper-based material | |
| CN107974671B (en) | A kind of preparation method of photo catalytic reduction graphene oxide composite membrane | |
| CN102061439B (en) | Method for preparing biaxial NiO (200) coating conductor buffer layers by medium-temperature surface oxidation epitaxy | |
| CN104630771B (en) | A kind of method for preparing porous oxide film in metal carrier surface | |
| CN101200126B (en) | Thermal-barrier coating and method for making same | |
| CN108018531B (en) | Method for preparing nano porous metal material | |
| CN107354479B (en) | A kind of anode preparation method suitable for high-temperature electrochemistry hydrogen pump |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |