CN104628411B - Super-macroporous material loaded with copper oxide nanowires - Google Patents
Super-macroporous material loaded with copper oxide nanowires Download PDFInfo
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- CN104628411B CN104628411B CN201510061151.2A CN201510061151A CN104628411B CN 104628411 B CN104628411 B CN 104628411B CN 201510061151 A CN201510061151 A CN 201510061151A CN 104628411 B CN104628411 B CN 104628411B
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Abstract
The invention discloses a copper oxide nanowire-loaded ultra-large pore material, which is characterized in that the ultra-large pore structure of a natural macroporous material is used as a carrier, and the copper oxide nanowire grows on the pore wall of a pore passage through hydrothermal reaction, so that the operation is simple and convenient, the nanowire grows well perpendicular to the pore wall, the size is uniform, and the performance is stable; the copper oxide nanowire-loaded ultra-macroporous material prepared by the invention is a novel nano composite material and has important application in the fields of catalysis and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to a copper oxide nanowire-loaded super-macroporous material.
Background
The porous material is a material with a network structure formed by interconnected or closed pores, the boundaries or surfaces of the pores are formed by pillars or flat plates, and the porous material has a large surface area, so that the catalytic and adsorption performances of the porous material are enhanced, and the porous material is widely applied to the fields of gas adsorption, separation, heterogeneous catalysis, ion exchange and the like.
The nano material is a material which has at least one dimension in a nano scale range (1-100nm) in a three-dimensional space or is formed by taking the nano material as a basic unit, wherein the nano wire, the nano rod, the nano tube, the nano belt and the like are one-dimensional nano materials, have large length-diameter ratio, show unique characteristics of light, electricity, magnetism, thermodynamics and the like, and have potential application prospect in the fields of nano devices, super large scale integrated circuits, bioengineering, medicine and the like. Among metal oxide nanowires, CuO is a p-type narrow bandgap (1.2eV) semiconductor material, which is the narrowest bandgap metal oxide semiconductor material known at present, has high-temperature superconductivity similar to cuprate, but only contains Cu — O bonds, and thus is generally used as a base material for preparing high-temperature superconductors. The CuO nano material has remarkable optical, electric, magnetic and catalytic properties, so that the CuO nano material has great application potential in the aspects of heterogeneous catalysts, battery cathode materials, photo-thermal and light guide materials and the like.
Therefore, the nano CuO and the porous material are integrated, so that the method has important application in the fields of heterogeneous catalysis, device materials and the like, can realize the complete dispersion of the one-dimensional CuO nano material, is free from pollution, is convenient for recycling the material and the like. Currently, scholars adopt a nano-pore template for preparing CuO nanowires in pores, for example, Shanghai et al (proceedings of Jiangsu education college, 2004,21,12) firstly prepare an alumina template with nano-pores by using a secondary anodic oxidation method, and then immerse the prepared alumina template into H
3PO
4Corroding the solution to obtain an alumina template, depositing copper nanowires in nano holes of the alumina template by using an electrochemical method, and oxidizing to obtain CuO nanowires; sudiokun et al (trans. non ferrousmet. soc. china,2007,17,783) use a porous Anodic Aluminum Oxide (AAO) as a template, prepare CuO nanowires by a sol-gel method, enter the gel into the template cavity by using a vacuum system and capillary action, and obtain CuO nanowires by heating to 850K, but no report on the growth of CuO nanowires in large-aperture pore structures is available.
Disclosure of Invention
In view of the above, the present invention aims to provide a copper oxide nanowire-loaded ultra-macroporous material which is simple to prepare and low in cost.
Based on the above purpose, the present invention provides a copper oxide nanowire-loaded super macroporous material, wherein the copper oxide nanowire grows in a natural macroporous material pore channel, the preparation method uses the natural macroporous material as a carrier, and the copper oxide nanowire is loaded on the pore wall of the macroporous material through a hydrothermal reaction, and the preparation method specifically comprises the following steps:
1. taking a commercially available natural macroporous material, slicing, soaking in hydrogen peroxide, ethanol and water at 20-60 ℃ for 2-10 h, and drying;
2. soaking the dried macroporous material in 1-5 mmol/L ethanol solution of copper acetate for 5-24 h, and placing the dried macroporous material in a muffle furnace at the constant temperature of 240-300 ℃ for 0.5-3 h;
3. dripping 0.05-1 mol/L copper salt water solution into 0.5-2 mol/L alkali solution, and quickly stirring for 1-10 h to obtain suspension, wherein the molar ratio of copper ions to alkali is 1: 4-20;
4. transferring the turbid liquid and the pretreated macroporous material into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting at 90-180 ℃ for 6-24 hours, and naturally cooling to room temperature;
5. and (3) soaking the obtained material in ethanol and water at 20-60 ℃ for 1-6 h, naturally cooling to room temperature, and drying to obtain the copper oxide nanowire-loaded super-macroporous material.
Optionally, the natural macroporous material is a rattan-cage shell.
Optionally, the copper salt is one of copper chloride, copper acetate, copper nitrate and copper sulfate.
Optionally, the alkali solution is one of a sodium carbonate solution, a sodium bicarbonate solution, a potassium carbonate solution, and a potassium bicarbonate solution.
From the above, the super-macroporous material loaded with copper oxide nanowires provided by the invention has the following advantages:
1. the selected natural macroporous material has wide source and low price, and has a natural ordered three-dimensional pore structure, and the porosity reaches more than 80 percent;
2. the material is taken as a carrier, so that the problems of reagent pollution and waste, difficult control of pore size and porosity and the like of a chemically synthesized porous material are avoided;
3. the preparation method of the loaded copper oxide nanowire is simple and easy to operate, and the adopted reaction raw materials are common and cheap chemical reagents.
Drawings
FIG. 1 is a scanning electron microscope image according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
Example 1
Slicing commercially available natural macroporous material, soaking in hydrogen peroxide, ethanol and water at 20 deg.C for 10 hr, and oven drying; soaking the treated macroporous material in 1mmol/L ethanol solution of copper acetate for 5-24 h, and drying; then placing the macroporous material in a muffle furnace, and keeping the temperature at 240 ℃ for 0.5 h;
20mL of 1mol/L Cu (NO)
3)
2The solution was added dropwise to 40mL of 2mol/L Na
2CO
3Quickly stirring the solution for 10 hours to obtain suspension;
transferring the suspension and the pretreated macroporous material into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting at 90 ℃ for 24 hours, and naturally cooling to room temperature; and (3) respectively soaking the obtained material in ethanol and water at 60 ℃ for 1h, naturally cooling to room temperature, and drying to obtain the copper oxide nanowire-loaded super-macroporous material.
Example 2
Slicing commercially available natural macroporous material, soaking in hydrogen peroxide, ethanol and water at 40 deg.C for 5 hr, and oven drying; soaking the treated macroporous material in 3mmol/L ethanol solution of copper acetate for 12 hr, and oven drying; then placing the macroporous material in a muffle furnace, and keeping the temperature at 300 ℃ for 1 h;
20mL of 0.1mol/L Cu (NO)
3)
2The solution was added dropwise to 40mL of 1mol/L Na
2CO
3Quickly stirring the solution for 5 hours to obtain suspension;
transferring the suspension and the pretreated macroporous material into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting at 180 ℃ for 6 hours, and naturally cooling to room temperature; and (3) soaking the obtained material with ethanol and water at 45 ℃ for 3h, naturally cooling to room temperature, and drying to obtain the copper oxide nanowire-loaded super-macroporous material.
Example 3
Slicing commercially available natural macroporous material, soaking in hydrogen peroxide, ethanol and water at 60 deg.C for 2 hr, and oven drying; soaking the treated macroporous material in 5mmol/L ethanol solution of copper acetate for 24 hr, and oven drying; then placing the macroporous material in a muffle furnace, and keeping the temperature at 260 ℃ for 3 hours;
30mL of 0.05mol/L Cu (NO)
3)
2The solution was added dropwise to 30mL of 0.5mol/L Na
2CO
3Quickly stirring the solution for 1 hour to obtain suspension;
transferring the suspension and the pretreated macroporous material into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting at 160 ℃ for 12 hours, and naturally cooling to room temperature; and (3) respectively soaking the obtained material in ethanol and water at 20 ℃ for 6h, naturally cooling to room temperature, and drying to obtain the copper oxide nanowire-loaded super-macroporous material.
Example 4
Slicing commercially available natural macroporous materials, soaking in hydrogen peroxide, ethanol and water at 35 deg.C for 8 hr, and oven drying; soaking the treated macroporous material in 2mmol/L ethanol solution of copper acetate for 10 hr, and oven drying; then placing the macroporous material in a muffle furnace, and keeping the temperature at 270 ℃ for 1 h;
20mL of 0.5mol/L Cu (NO)
3)
2The solution was added dropwise to 50mL of 2mol/L Na
2CO
3Quickly stirring the solution for 1 hour to obtain suspension;
transferring the suspension and the pretreated macroporous material into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting at 140 ℃ for 20 hours, and naturally cooling to room temperature; and (3) soaking the obtained material for 5h at 55 ℃ by using ethanol and water respectively, naturally cooling to room temperature, and drying to obtain the copper oxide nanowire-loaded super-macroporous material.
Example 5
Slicing commercially available natural macroporous material, soaking in hydrogen peroxide, ethanol and water at 50 deg.C for 8 hr, and oven drying; soaking the treated macroporous material in 4mmol/L ethanol solution of copper acetate for 15 hr, and oven drying; then placing the macroporous material in a muffle furnace, and keeping the temperature at 250 ℃ for 1.5 h;
20mL of 0.5mol/L Cu (NO)
3)
2The solution was added dropwise to 40mL of 1.5mol/L Na
2CO
3Quickly stirring the solution for 1 hour to obtain suspension;
transferring the suspension and the pretreated macroporous material into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting at 120 ℃ for 15 hours, and naturally cooling to room temperature; and (3) soaking the obtained material for 4 hours at 50 ℃ by using ethanol and water respectively, naturally cooling to room temperature, and drying to obtain the copper oxide nanowire-loaded super-macroporous material.
Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (1)
1. The super-macroporous material loaded with the copper oxide nanowires is characterized in that the preparation method of the material comprises the following steps:
taking a commercially available natural macroporous material, slicing, soaking in hydrogen peroxide, ethanol and water at 20-60 ℃ for 2-10 h, and drying;
soaking the dried macroporous material in 1-5 mmol/L ethanol solution of copper acetate for 5-24 h, and placing the dried macroporous material in a muffle furnace at the constant temperature of 240-300 ℃ for 0.5-3 h;
dripping 0.05-1 mol/L copper salt water solution into 0.5-2 mol/L alkali solution, and quickly stirring for 1-10 h to obtain suspension, wherein the molar ratio of copper ions to alkali is 1: 4-20;
transferring the turbid liquid and the pretreated macroporous material into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting at 90-180 ℃ for 6-24 hours, and naturally cooling to room temperature;
soaking the obtained material in ethanol and water at 20-60 ℃ for 1-6 h, naturally cooling to room temperature, and drying to obtain the copper oxide nanowire-loaded super-macroporous material;
the copper salt is one of copper chloride, copper acetate, copper nitrate and copper sulfate;
the alkali solution is one of a sodium carbonate solution, a sodium bicarbonate solution, a potassium carbonate solution and a potassium bicarbonate solution;
the natural macroporous material is a rattan-pot shell.
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Citations (6)
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|---|---|---|---|---|
| CN102949981A (en) * | 2011-08-17 | 2013-03-06 | 香港城市大学 | Porous substrate and one-dimensional nano-material composite material and its preparation method, and surface-modified composite material and its preparation method |
| CN103332755A (en) * | 2013-06-09 | 2013-10-02 | 燕山大学 | Preparation method of nickel oxide with multistage pore structure |
| CN103408054A (en) * | 2013-06-09 | 2013-11-27 | 燕山大学 | Preparation method of hierarchical zeolite structural copper oxide |
| CN103920521A (en) * | 2014-04-24 | 2014-07-16 | 天津城建大学 | Method for preparing natural zeolite loaded CuO nanotube composite material for removing formaldehyde |
| CN104107689A (en) * | 2013-04-18 | 2014-10-22 | 宁波大学 | Macroporous nanocomposite and preparation method thereof |
| CN104150437A (en) * | 2014-08-01 | 2014-11-19 | 宁波大学 | Macroporous material carried with cerium oxide nano-rods |
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| KR101332422B1 (en) * | 2011-01-07 | 2013-12-02 | 건국대학교 산학협력단 | Templated electrochemical growth of single-crystal Cu2O nanowire arrays |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102949981A (en) * | 2011-08-17 | 2013-03-06 | 香港城市大学 | Porous substrate and one-dimensional nano-material composite material and its preparation method, and surface-modified composite material and its preparation method |
| CN104107689A (en) * | 2013-04-18 | 2014-10-22 | 宁波大学 | Macroporous nanocomposite and preparation method thereof |
| CN103332755A (en) * | 2013-06-09 | 2013-10-02 | 燕山大学 | Preparation method of nickel oxide with multistage pore structure |
| CN103408054A (en) * | 2013-06-09 | 2013-11-27 | 燕山大学 | Preparation method of hierarchical zeolite structural copper oxide |
| CN103920521A (en) * | 2014-04-24 | 2014-07-16 | 天津城建大学 | Method for preparing natural zeolite loaded CuO nanotube composite material for removing formaldehyde |
| CN104150437A (en) * | 2014-08-01 | 2014-11-19 | 宁波大学 | Macroporous material carried with cerium oxide nano-rods |
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Application publication date: 20150520 Assignee: Shunkang Fengyu Food (Zhejiang) Co.,Ltd. Assignor: Ningbo University Contract record no.: X2022980025298 Denomination of invention: A super porous material loaded with copper oxide nanowires Granted publication date: 20200211 License type: Common License Record date: 20221209 |
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Application publication date: 20150520 Assignee: Ningbo Science and Technology Innovation Association Assignor: Ningbo University Contract record no.: X2023980033633 Denomination of invention: A Super Porous Material Loaded with Copper Oxide Nanowires Granted publication date: 20200211 License type: Common License Record date: 20230317 |
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