CN115869967B - Foam copper catalyst with trans-scale pore diameter structure and preparation method thereof - Google Patents
Foam copper catalyst with trans-scale pore diameter structure and preparation method thereof Download PDFInfo
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Abstract
The application discloses a foam copper catalyst with a trans-scale pore diameter structure and a preparation method thereof, and belongs to the technical field of electrochemistry and composite materials. The foam copper catalyst consists of a porous silver framework and a metal copper layer coated on the porous silver framework. The preparation method of the foam copper catalyst comprises the following steps: (1) Placing the porous silver skeleton into electroplating solution containing copper salt for electrodeposition copper plating to obtain a porous copper skeleton; (2) And (3) carrying out oxidation treatment and then reduction treatment on the porous copper skeleton to obtain the foam copper catalyst. The foam copper with the cross-scale aperture structure has the advantages of large specific surface area, high conversion efficiency, good cycle stability and the like, and is suitable for decomposing CO generated by various ways 2 The preparation method is simple, and the used raw materials are low in price and environment-friendly.
Description
Technical Field
The application relates to the technical field of electrochemistry and composite materials, in particular to a foam copper catalyst with a trans-scale pore diameter structure and a preparation method thereof.
Background
CO 2 Environmental problems caused by excessive emissions have received considerable attention worldwide, CO 2 Resource utilization is an important approach to solve this problem. Wherein, CO is reduced by electrocatalytic 2 Can be converted into high-added value chemicals, and can not only relieve CO 2 The global warming caused by the method can realize carbon circulation, namely, carbon is converted into a chemical product with high utilization value, so that the method is a technology with important social significance and wide application prospect.
Electrocatalytic CO 2 Performance of reduction and type of catalyst, voltage, electrolyte solution, CO 2 The concentration and the reaction temperature are related, wherein the kind of the catalyst is the most critical to the influence. Copper-based materials are electrodes capable of producing multi-carbon products and are commonly used as CO due to their low cost 2 A reduced catalyst. However, the consumption of active sites and the accumulation of surface carbon during the reaction tend to deactivate the copper-based catalyst and the copper-based catalyst generates C 2+ The stability of the product can be maintained for only tens of hours, rarely hundreds of hours, while silver is used as electrocatalytic CO 2 Reduced catalysts can achieve catalysis for up to thousands of hours, but silver is a noble metal and is costly.
To improve C 2+ Various methods have been explored for efficiency of the product as well as stability during the reduction process. For example, the Chinese patent of application number 202111323665.2 adopts a modification group to modify a copper-based catalyst as an electrochemical catalytic electrode, so that the catalytic efficiency and Faraday efficiency of the existing copper-based catalyst are improved, the loss of input energy is reduced, and the efficient storage and carbon neutralization of electric energy are realized. In the electrochemical reduction preparation process of the copper catalyst, the Chinese patent with the application number of 202210096527.3 utilizes organic anions to coordinate with copper on the surface of the catalyst and induce to form an oriented crystal face, so that the stability and the activity of the nano copper catalyst are improved. The method improves the CO content of the copper-based catalyst 2 Certain advances in product selectivity have been made, but there are still significant challenges in maintaining the performance stability and conversion efficiency of copper-based catalysts.
Disclosure of Invention
The application aims to provide a foam copper catalyst with a cross-scale aperture structure and a preparation method thereof, which solve the problems in the prior art, and the application takes melamine foam as a base template, carries out chemical silver plating (leading the template to be conductive), electrodeposition copper plating, heating oxidation treatment and reduction treatment on the template, and obtains the catalyst which can be used for electrocatalytic CO 2 The preparation process of the foam copper catalyst with the cross-scale aperture structure is simple, the price is lower, and the foam copper catalyst is environment-friendly; the foam copper catalyst with the trans-scale pore diameter structure prepared from foam copper with a porous structure through multiple oxidation and reduction has the advantages of large specific surface area, high conversion efficiency and excellent stability, and is suitable for decomposing CO generated by multiple ways 2 。
In order to achieve the above object, the present application provides the following solutions:
one of the technical schemes of the application is as follows: a foam copper catalyst with a cross-scale pore diameter structure comprises a porous silver framework with a hollow structure and copper metal coated on the porous silver framework.
Further, the trans-scale pore structure comprises a large pore diameter of 160-400 mu m and a small pore diameter of 1-5 mu m; the aperture of the porous silver skeleton is 100-300 mu m, and the thickness of the silver layer is 8-10 mu m; the thickness of the metal copper layer is 20-40 mu m.
The second technical scheme of the application is as follows: the preparation method of the foam copper catalyst with the cross-scale pore diameter structure comprises the following steps:
(1) Placing the porous silver skeleton into electroplating solution containing copper salt for electrodeposition copper plating to obtain a porous copper skeleton;
(2) And (3) oxidizing the porous copper skeleton, and then reducing to obtain the foam copper catalyst (three-dimensional porous structure).
Further, the preparation of the porous silver skeleton specifically comprises:
soaking the melamine foam base template in silver-ammonia solution, and then dropwise adding C 6 H 12 O 6 The solution (reducing agent solution) is stirred in a water bath, washed and dried to obtain the porous materialA silver skeleton.
The pore diameter of the melamine foam basic template is 100-300 mu m.
Further, the preparation of the silver ammonia solution specifically comprises the following steps: agNO at a concentration of 20-40 g/L 3 Adding 25% NH by mass into the solution 3 ·H 2 O up to AgNO 3 The solution is clear and transparent, and the silver ammonia solution is prepared; the C is 6 H 12 O 6 The concentration of the solution is 40-80 g/L;
the soaking temperature is 25-40 ℃; the soaking time is 5min; the temperature of the water bath is 25-40 ℃; the stirring time is 10-25 min.
Further, the plating solution containing copper salt uses water as a solvent, cuSO 4 The concentration of (C) is 200-300 g/L, H 2 SO 4 The concentration of (C) is 60-80 g/L, C 2 H 6 O 2 The concentration of (C) is 0.2-0.4 g/L.
Further, the apparent current density of the electrodeposition is 2 to 4A/cm 2 The time is 7-9 h.
Further, the heating mode of the oxidation treatment is as follows: firstly heating to 150-250 ℃, and preserving heat for 15-30 min; heating to 300-500 ℃, and preserving heat for 30-60 min; the atmosphere of the reduction treatment is H 2 :N 2 =1:9, heating mode: firstly heating to 450-550 ℃, and preserving heat for 150-300 min; then heating to 750-850 deg.C, and preserving heat for 60-120 min.
Further, the preparation method of the foam copper catalyst with the cross-scale pore diameter structure further comprises the step of repeating the step (2) for 1-5 times.
Repeating the treatment of step (2) can increase the effective specific surface area of the copper foam catalyst.
The third technical scheme of the application: the foam copper catalyst with the trans-scale pore diameter structure is used for catalytically decomposing CO 2 Is used in the field of applications.
The application discloses the following technical effects:
(1) The foam copper with the cross-scale aperture structure has the advantages of large specific surface area and high conversion efficiencyGood cycle stability, and the like, and is suitable for decomposing CO generated by various ways 2 。
(2) The preparation method is simple, and the used raw materials are low in price and environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a copper foam catalyst having a cross-scale pore structure prepared in example 1 of the present application, wherein (a) is a skeleton image of a porous copper foam that has not been subjected to a redox treatment, and (b) is a further enlarged image of the porous copper foam skeleton that has not been subjected to a redox treatment;
fig. 2 is an SEM image of a copper foam catalyst having a trans-scale pore structure prepared in example 2 of the present application, in which (a) is a skeleton image of porous copper foam subjected to 3 redox treatments and (b) is a further enlarged image of the porous copper foam skeleton subjected to 3 redox treatments.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
A preparation method of a foam copper catalyst with a trans-scale pore diameter structure, which comprises the following steps:
(1) Preparation of porous silver skeleton
A. Preparing silver ammonia solution: deionized water is used as solvent, and AgNO is used as the solvent 3 Preparation of AgNO at a concentration of 20g/L 3 Solution, then in AgNO 3 Adding 25% NH by mass into the solution 3 ·H 2 O up to AgNO 3 The solution is clear and transparent, and the silver ammonia solution is prepared.
B. Preparing a reducing agent solution: deionized water is taken as solvent according to C 6 H 12 O 6 Preparation of C at a concentration of 40g/L (purity 99.9%) 6 H 12 O 6 And (3) preparing a solution of the reducing agent.
C. Preparation of a porous silver skeleton: soaking a melamine foam basic template (with the pore size of 100-300 mu m) in silver-ammonia solution with the temperature of 25 ℃ for 5min, then dripping reducing agent solution, stirring in water bath (25 ℃) for 10min, washing with deionized water, and drying at room temperature for 1h to obtain a porous silver skeleton (with the pore size of 100-300 mu m and the silver layer thickness of 8-10 mu m).
(2) Preparation of copper foam catalyst
A. Preparing electroplating solution: deionized water is taken as solvent, and CuSO is adopted 4 Is 200g/L, and is concentrated H 2 SO 4 Is 60g/L, C 2 H 6 O 2 The concentration is 0.2g/L, and the plating solution is obtained by stirring and preparing.
B. Electrodepositing copper plating: the porous silver skeleton was put into a plating solution to be subjected to electrodeposition copper plating (apparent current density of 2A/cm) 2 And 7 h) taking out, cleaning and drying the porous copper skeleton.
C. And (3) heating and oxidizing: and (3) placing the porous copper skeleton in a muffle furnace, heating to 150 ℃, preserving heat for 15min, heating to 300 ℃, preserving heat for 30min, naturally cooling to room temperature, and taking out to obtain the porous copper oxide skeleton.
D. Reduction treatment: placing a porous copper oxide skeleton in a tube furnace, at H 2 :N 2 In a sintering atmosphere of 1:9, firstly heating to 450 ℃, keeping the temperature for 150min, then heating to 750 ℃, keeping the temperature for 60min, naturally cooling to room temperature, and taking out to obtain the foam copper catalyst (porous structure, thickness of the metal copper layer is 23 μm) with a cross-scale pore diameter (small pore diameter of 1-5 μm and large pore diameter of 160-300 μm) structure.
Example 2
The difference from example 1 is that the procedure of the heat oxidation treatment and the reduction treatment was repeated 3 times to obtain a foam copper catalyst having a trans-scale pore diameter structure (porous structure, thickness of the metal copper layer of 23 μm) with a larger number of small pores and a number ratio of small pores to large pores of about 3000:1.
Example 3
A preparation method of a foam copper catalyst with a trans-scale pore diameter structure, which comprises the following steps:
(1) Preparation of porous silver skeleton
A. Preparing silver ammonia solution: deionized water is used as solvent, and AgNO is used as the solvent 3 Preparation of AgNO at a concentration of 40g/L 3 Solution, then in AgNO 3 Adding 25% NH by mass into the solution 3 ·H 2 O up to AgNO 3 The solution is clear and transparent, and the silver ammonia solution is prepared.
B. Preparing a reducing agent solution: deionized water is taken as solvent according to C 6 H 12 O 6 Preparation of C at a concentration of 60g/L (purity 99.9%) 6 H 12 O 6 And (3) preparing a solution of the reducing agent.
C. Preparation of a porous silver skeleton: the melamine foam basic template is soaked in silver ammonia solution with the temperature of 30 ℃ for 5min, then reducing agent solution is dripped, water bath (30 ℃) is stirred for 15min, deionized water is used for washing, and then the porous silver skeleton (with the pore size of 100-300 mu m and the silver layer thickness of 8-10 mu m) is obtained after drying for 1h at room temperature.
(2) Preparation of copper foam catalyst
A. Preparing electroplating solution: deionized water is taken as solvent, and CuSO is adopted 4 Is 250g/L, and H 2 SO 4 Is 75g/L, C 2 H 6 O 2 The concentration is 0.3g/L, and the plating solution is obtained by stirring and preparing.
B. Electrodepositing copper plating: the porous silver skeleton was put into a plating solution to be subjected to electrodeposition copper plating (apparent current density of 4A/cm) 2 The electrodeposition time is 9 h), and the porous copper skeleton is obtained after taking out, cleaning and drying.
C. And (3) heating and oxidizing: and (3) placing the porous copper skeleton in a muffle furnace, heating to 200 ℃, preserving heat for 20min, heating to 400 ℃, preserving heat for 50min, naturally cooling to room temperature, and taking out to obtain the porous copper oxide skeleton.
D. Reduction treatment: placing a porous copper oxide skeleton in a tube furnace, at H 2 :N 2 In the sintering atmosphere of 1:9, firstly heating to 550 ℃, keeping the temperature for 200min, then heating to 800 ℃, keeping the temperature for 120min, finally naturally cooling to room temperature, and taking out to obtain the product with the cross-scale aperture (small aperture of 1-5 μm and 185-3.)A large pore size of 00 μm and a number ratio of about 1300:1) of the structure of the copper foam catalyst (porous structure, thickness of the metal copper layer of 32 μm).
Example 4
A preparation method of a foam copper catalyst with a trans-scale pore diameter structure, which comprises the following steps:
(1) Preparation of porous silver skeleton
A. Preparing silver ammonia solution: deionized water is used as solvent, and AgNO is used as the solvent 3 Preparation of AgNO at a concentration of 30g/L 3 Solution, then in AgNO 3 Adding 25% NH by mass into the solution 3 ·H 2 O up to AgNO 3 The solution is clear and transparent, and the silver ammonia solution is prepared.
B. Preparing a reducing agent solution: deionized water is taken as solvent according to C 6 H 12 O 6 Preparation of C at a concentration of 80g/L (purity 99.9%) 6 H 12 O 6 And (3) preparing a solution of the reducing agent.
C. Preparation of a porous silver skeleton: the melamine foam basic template is soaked in silver ammonia solution with the temperature of 40 ℃ for 5min, then reducing agent solution is dripped, water bath (35 ℃) is stirred for 25min, deionized water is used for washing, and then the porous silver skeleton (with the pore size of 100-300 mu m and the silver layer thickness of 8-10 mu m) is obtained after drying for 1h at room temperature.
(2) Preparation of copper foam catalyst
A. Preparing electroplating solution: deionized water is taken as solvent, and CuSO is adopted 4 The concentration of (2) is 300g/L, and the concentration is H 2 SO 4 Is 80g/L, C 2 H 6 O 2 The concentration is 0.4g/L, and the plating solution is obtained by stirring and preparing.
B. Electrodepositing copper plating: the porous silver skeleton was put into a plating solution to be subjected to electrodeposition copper plating (apparent current density of 3A/cm) 2 The electrodeposition time is 8.5 h), and the porous copper skeleton is obtained after taking out, cleaning and drying.
C. And (3) heating and oxidizing: and (3) placing the porous copper skeleton in a muffle furnace, heating to 250 ℃, preserving heat for 30min, heating to 500 ℃, preserving heat for 60min, naturally cooling to room temperature, and taking out to obtain the porous copper oxide skeleton.
D. Reduction treatment: placing a porous copper oxide skeleton in a tube furnace, at H 2 :N 2 In a sintering atmosphere of 1:9, firstly heating to 500 ℃, keeping the temperature for 300min, then heating to 850 ℃, keeping the temperature for 90min, naturally cooling to room temperature, and taking out to obtain the foam copper catalyst (porous structure, thickness of the metal copper layer is 35 μm) with a cross-scale pore diameter (small pore diameter of 1-5 μm and large pore diameter of 190-300 μm) structure with the quantity ratio of about 1500:1.
Comparative example 1
As in example 1, the difference is that the apparent current density at the time of electrodeposition copper plating was 0.5A/cm 2 The obtained foam copper catalyst has a small pore diameter of 1-5 mu m and a large pore diameter of 120-300 mu m, and the number ratio is about 700:1.
Comparative example 2
The difference from example 1 is that the electrodeposition time at the time of electrodeposition copper plating is 4 hours, and the obtained foam copper catalyst has a small pore diameter of 1 to 5 μm and a large pore diameter of 110 to 300 μm, and the number ratio is about 900:1.
Effect example 1
The specific surface area, conversion efficiency and stability of the copper foam catalysts prepared in the examples and comparative examples of the present application were measured, and the results are shown in table 1.
The measurement method is as follows: the same catalyst was used repeatedly until its catalytic activity was reduced to 10% of the first catalytic efficiency, the number of times of the recycling was recorded, and the test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the specific surface area of the foam copper catalyst with the trans-scale pore diameter structure prepared by the application reaches 2.039-2.256 m 2 The cross-scale pore diameter structure of the foam copper catalyst can increase the contact area of the foam copper catalyst, thereby improving the catalytic efficiency (the catalytic efficiency is improved to 92-95%) and the circulationTimes (cycle times up to 9 times).
As can be seen from example 1 and comparative example 1, the specific surface area of the foam copper catalyst having a trans-scale pore structure formed after the current density was reduced was smaller (0.847 m 2 And/g), resulting in a reduction in its catalytic efficiency (65%) and a reduction in the number of cycles to 5.
As can be seen from example 1 and comparative example 2, the specific surface area of the foam copper catalyst having a cross-scale pore structure formed after the reduction of the electrodeposition time was smaller (0.993 m 2 And/g), resulting in a reduction in its catalytic efficiency (69%) and a reduction in the number of cycles to 5.
As is clear from examples 1 to 4, repeating the redox process, increasing the apparent density of the current, and increasing the electrodeposition time a plurality of times all increased the specific surface area of the copper foam catalyst having a trans-scale pore structure, thereby improving the catalytic efficiency and the number of cycles.
Effect example 2
Influence of Faraday efficiency of electric energy conversion chemical energy converted from carbon dioxide electrocatalytic reduction into methane and catalytic efficiency of carbon dioxide reduction
Faraday efficiency is the percentage of the amount of actual product and theoretical product, i.e., the electrons transferred from the catalytic electrode by the electrons generated by the electric energy, and is calculated as the number of electrons transferred from the catalytic reaction, which is theoretically used for the reduction of CO 2 Total amount of product that can be produced. The content of the product is detected by gas chromatography.
The copper foam catalyst with a trans-scale pore diameter structure prepared in the embodiment is taken as a cathode, an inert metal platinum electrode is taken as an anode, and the concentration is CO 2 Saturated 0.1M sodium bicarbonate solution is used as electrolyte to construct a carbon dioxide reduction energy storage system, and CO is used as a catalyst 2 The gas source is introduced into the electrolyte of the system to be saturated, the solar power supply system is adopted to supply power for electrochemical catalytic reaction, the working voltage applied to the cathode is-0.82V (and a silver/silver chloride electrode is used as a reference electrode), the reaction temperature is room temperature, and the pH value is 6.8.
Table 2 comparison of methane faraday efficiencies for different examples
As can be seen from table 2, the copper foam catalyst with a trans-scale pore structure prepared through multiple redox processes (example 2) catalyzed methanogenesis reached a maximum faradaic efficiency of 93%. The Faraday efficiency of CO in the main byproducts is lower than 2%, and the Faraday efficiency of ethylene is lower than 3%. In the case of changing the apparent density of the current and the electrodeposition time, the catalytic methanogenesis of the example 1, the example 3 and the example 4 achieves the Faraday efficiency of more than or equal to 90%, the Faraday efficiency of CO of less than 4% and the Faraday efficiency of ethylene of less than 3%.
The above embodiments are only illustrative of the preferred embodiments of the present application and are not intended to limit the scope of the present application, and various modifications and improvements made by those skilled in the art to the technical solutions of the present application should fall within the protection scope defined by the claims of the present application without departing from the design spirit of the present application.
Claims (5)
1. Copper foam catalyst with trans-scale pore diameter structure for catalytic decomposition of CO 2 The catalyst is characterized by comprising a porous silver framework with a hollow structure and copper metal coated on the porous silver framework;
the trans-scale aperture structure comprises a large aperture of 160-400 mu m and a small aperture of 1-5 mu m; the aperture of the porous silver skeleton is 100-300 mu m, and the thickness of the silver layer is 8-10 mu m; the thickness of the metal copper layer is 20-40 mu m;
the preparation method of the foam copper catalyst with the trans-scale pore diameter structure comprises the following steps:
(1) Placing the porous silver skeleton into electroplating solution containing copper salt for electrodeposition copper plating to obtain a porous copper skeleton;
the apparent current density of the electrodeposition is 2-4A/cm 2 The time is 7-9 h;
(2) Oxidizing the porous copper skeleton, and then reducing to obtain the foam copper catalyst;
the heating mode of the oxidation treatment is as follows: firstly heating to 150-250 ℃, and preserving heat for 15-30 min; heating to 300-500 ℃, and preserving heat for 30-60 min; the atmosphere of the reduction treatment is H 2 :N 2 =1:9, heating mode: firstly heating to 450-550 ℃, and preserving heat for 150-300 min; then heating to 750-850 deg.C, and preserving heat for 60-120 min.
2. The use according to claim 1, characterized in that the preparation of the porous silver skeleton comprises in particular:
soaking the melamine foam base template in silver-ammonia solution, and then dropwise adding C 6 H 12 O 6 Stirring the solution in a water bath, washing and drying to obtain the porous silver skeleton;
the pore diameter of the melamine foam basic template is 100-300 mu m.
3. The use according to claim 2, wherein the preparation of the silver-ammonia solution comprises in particular: agNO at a concentration of 20-40 g/L 3 Adding 25% NH by mass into the solution 3 ·H 2 O up to AgNO 3 The solution is clear and transparent, and the silver ammonia solution is prepared;
the C is 6 H 12 O 6 The concentration of the solution is 40-80 g/L;
the soaking temperature is 25-40 ℃; the soaking time is 5min; the temperature of the water bath is 25-40 ℃; the stirring time is 10-25 min.
4. The use according to claim 1, wherein the copper salt-containing electroplating solution comprises water as solvent, cuSO 4 The concentration of (C) is 200-300 g/L, H 2 SO 4 The concentration of (C) is 60-80 g/L, C 2 H 6 O 2 The concentration of (C) is 0.2-0.4 g/L.
5. The use of claim 1, further comprising repeating step (2) 1-5 times.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800898A (en) * | 2012-07-31 | 2012-11-28 | 武汉银泰科技电源股份有限公司 | Manufacturing method for lead-carbon battery used for mild hybrid vehicle |
| CN104175615A (en) * | 2014-08-21 | 2014-12-03 | 四川大学 | Light composite material with high conductivity and high electromagnetic shielding and preparation method of composite material |
| WO2017121203A1 (en) * | 2016-01-11 | 2017-07-20 | 苏州大学张家港工业技术研究院 | Micrometer/nanometer silver-loaded barium titanate foam ceramic and preparation method therefor |
| CN109898107A (en) * | 2019-02-28 | 2019-06-18 | 昆明理工大学 | Foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material and preparation method |
| CN109909504A (en) * | 2019-02-28 | 2019-06-21 | 昆明理工大学 | A kind of porous foam enhancing metallic composite and preparation method thereof |
| CN110331310A (en) * | 2019-06-19 | 2019-10-15 | 中国科学院金属研究所 | Three-dimensional gradient hole foam metal and its preparation method and application |
| CN112194818A (en) * | 2020-09-27 | 2021-01-08 | 东华大学 | Copper/silver-based electrode with conductive bacterial cellulose composite membrane as substrate |
| CN112604689A (en) * | 2020-11-25 | 2021-04-06 | 电子科技大学 | Preparation of porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition |
| WO2021258233A1 (en) * | 2020-06-22 | 2021-12-30 | 苏州楚捷新材料科技有限公司 | Preparation method for mofs photocatalytic material having high visible light response |
-
2022
- 2022-11-21 CN CN202211454570.9A patent/CN115869967B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800898A (en) * | 2012-07-31 | 2012-11-28 | 武汉银泰科技电源股份有限公司 | Manufacturing method for lead-carbon battery used for mild hybrid vehicle |
| CN104175615A (en) * | 2014-08-21 | 2014-12-03 | 四川大学 | Light composite material with high conductivity and high electromagnetic shielding and preparation method of composite material |
| WO2017121203A1 (en) * | 2016-01-11 | 2017-07-20 | 苏州大学张家港工业技术研究院 | Micrometer/nanometer silver-loaded barium titanate foam ceramic and preparation method therefor |
| CN109898107A (en) * | 2019-02-28 | 2019-06-18 | 昆明理工大学 | Foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material and preparation method |
| CN109909504A (en) * | 2019-02-28 | 2019-06-21 | 昆明理工大学 | A kind of porous foam enhancing metallic composite and preparation method thereof |
| CN110331310A (en) * | 2019-06-19 | 2019-10-15 | 中国科学院金属研究所 | Three-dimensional gradient hole foam metal and its preparation method and application |
| WO2021258233A1 (en) * | 2020-06-22 | 2021-12-30 | 苏州楚捷新材料科技有限公司 | Preparation method for mofs photocatalytic material having high visible light response |
| CN112194818A (en) * | 2020-09-27 | 2021-01-08 | 东华大学 | Copper/silver-based electrode with conductive bacterial cellulose composite membrane as substrate |
| CN112604689A (en) * | 2020-11-25 | 2021-04-06 | 电子科技大学 | Preparation of porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition |
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