CN113800899A - Preparation method of bulk nano-porous CuO - Google Patents
Preparation method of bulk nano-porous CuO Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 73
- 239000000956 alloy Substances 0.000 claims abstract description 73
- 229910017566 Cu-Mn Inorganic materials 0.000 claims abstract description 52
- 229910017871 Cu—Mn Inorganic materials 0.000 claims abstract description 52
- 239000000243 solution Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 238000005260 corrosion Methods 0.000 claims abstract description 23
- 230000007797 corrosion Effects 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 239000011261 inert gas Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 239000006104 solid solution Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000005520 cutting process Methods 0.000 claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims 2
- 239000010949 copper Substances 0.000 description 54
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 51
- 238000003723 Smelting Methods 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 239000005751 Copper oxide Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910000431 copper oxide Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 244000137852 Petrea volubilis Species 0.000 description 7
- 238000007664 blowing Methods 0.000 description 7
- 238000005282 brightening Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 238000005554 pickling Methods 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 229940045803 cuprous chloride Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 210000003041 ligament Anatomy 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
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Abstract
The invention discloses a preparation method of bulk nano-porous CuO, which comprises the following steps: melting a Cu block and a Mn sheet into an alloy through a vacuum melting furnace, carrying out solid solution treatment to obtain a uniform master alloy ingot, then carrying out wire cutting to obtain a Cu-Mn alloy block, then putting the Cu-Mn alloy block into an inert gas atmosphere furnace for heating to carry out stress relief annealing, and cooling to room temperature along with the furnace to obtain a section; cleaning the section bar, putting the section bar into a container filled with chemical corrosion solution, and dealloying; and (3) carrying out oxidation treatment on the de-alloyed section, and cooling the obtained product to room temperature along with the furnace after the oxidation treatment is finished to obtain the nano porous CuO material. The preparation method of the bulk nano-porous CuO can prepare the bulk nano-porous CuO and has simple preparation process.
Description
Technical Field
The invention belongs to the technical field of preparation methods of nano inorganic nonmetallic semiconductor materials, and relates to a preparation method of bulk nano porous CuO.
Background
The copper oxide is used as a p-type semiconductor material, and the forbidden band width is 1.2-1.9eV, so that the copper oxide has wide application prospects in the fields of catalysis, battery electrodes, sensors, adsorption and degradation of organic matters, biological medicines and the like. And the nano-porous CuO is used as a transition metal oxide, which draws great attention to energy storage applications such as super capacitors and the like due to higher electrochemical response, low manufacturing cost and easy processability. Therefore, the exploration and preparation of the large-size CuO with a stable nano porous structure and good mechanical properties has great significance for the application of the nano porous CuO.
Chinese patent | (application No. 201810028579.0, publication No. CN108069455A) discloses a method for preparing nano-copper oxide, which is characterized in that cuprous chloride is used as a raw material, ammonia water is added to dissolve the cuprous chloride, and then beta-hydroxyethyl acetate is added. Then placing the mixture into a closed reaction kettle, stirring for reaction, then filtering, and washing the obtained filter residue with hot pure water to obtain cuprous chloride particles; and (3) preparing a copper nitrate solution, adding cuprous chloride particles for slurrying, adding urea, and stirring for dissolving. Putting the mixture into the high-pressure reaction kettle again, stirring the mixture at high temperature and high pressure for reaction, filtering the mixture, and washing the third filter residue with hot pure water to obtain copper oxide filter residue; and (3) drying the copper oxide filter residue washed by hot water in vacuum, crushing the copper oxide filter residue by airflow, and screening the crushed copper oxide filter residue by a 150-mesh and 250-mesh sieve to obtain the nano copper oxide. The product prepared by the method is powder, and the process is relatively complex, so the application is relatively limited.
Disclosure of Invention
The invention aims to provide a preparation method of bulk nano-porous CuO, which can be used for preparing the bulk nano-porous CuO and has a simple preparation process.
The technical scheme adopted by the invention is that a preparation method of bulk nano-porous CuO is implemented according to the following steps:
step one, preparing raw materials
Weighing the following components in percentage by mass: 25-45% of industrial pure Cu blocks and 55-75% of industrial pure Mn sheets, wherein the sum of the mass percentages of the components is 100%;
step two, preparing alloy section bar
Melting the Cu block and the Mn sheet weighed in the step one into alloy through a vacuum melting furnace, carrying out solid solution treatment to obtain uniform master alloy cast ingot, then carrying out wire cutting to obtain a Cu-Mn alloy block, then placing the Cu-Mn alloy block into an inert gas atmosphere furnace for heating for stress relief annealing, and cooling to room temperature along with the furnace to obtain a section;
step three, cleaning the section obtained in the step two, and putting the section into a container filled with a chemical corrosion solution for dealloying;
and step four, carrying out oxidation treatment on the section obtained in the step three, and cooling the section to room temperature along with a furnace after the oxidation treatment is finished to obtain the nano porous CuO material.
The present invention is also characterized in that,
in the second step, the temperature of the solution treatment is 800-900 ℃, and the heat preservation time is 24 h.
And in the second step, the Cu-Mn alloy block is placed into an inert gas atmosphere furnace for stress relief annealing at the heating temperature of 300-500 ℃ for 2 h.
The thickness of the alloy cut in the second step is 0.5mm-2 mm.
The chemical corrosion solution in the third step is HCL or H with the concentration of 0.5-1.5M2SO4And (3) solution.
In the case of the HCL solution in the third step, the ratio of the amount of Mn to the amount of HCL is 1: 3 if H2SO4Solution of Mn and H2SO4The ratio of the amounts of substances (1): 1.5.
in the third step, the dealloying corrosion time is 8-24h, and the corrosion temperature is 0-40 ℃.
In the fourth step, the oxidation temperature is 230-.
The invention has the beneficial effects that:
the Cu and Mn metals selected by the invention are not noble metal materials, so the cost is low, and the Cu-Mn master alloy prepared by a smelting method can make an alloy base material into a bulk material so as to obtain bulk nano porous CuO by dealloying. The strength of the nano-porous CuO is effectively improved by performing stress relief annealing on the Cu-Mn alloy block in inert atmosphere gas. HCL is selected as a corrosive solution in the process of dealloying corrosion, so that the prepared nano porous CuO material has uniformly distributed pores, and the material has a bicontinuous ligament structure through SEM scanning electron microscope observation. The material has certain mechanical property integrally and completely, is stable in air and is not easy to denature. The preparation process is simple, and has certain production and application prospects.
Drawings
Fig. 1 is a macroscopic picture of bulk nanoporous CuO prepared in a method for preparing a bulk nanoporous CuO material according to the present invention.
FIG. 2 is an XRD pattern of nanoporous CuO prepared in a method of preparing a bulk nanoporous CuO material according to the present invention;
fig. 3 is an SEM image of nanoporous CuO prepared in a method for preparing a bulk nanoporous CuO material according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of bulk nano-porous CuO, which is implemented by the following steps:
step one, preparing raw materials
Weighing the following components in percentage by mass: 25-45% of industrial pure Cu blocks and 55-75% of industrial pure Mn sheets, wherein the sum of the mass percentages of the components is 100%;
step two, preparing alloy section bar
Smelting the Cu block and the Mn sheet weighed in the step one into an alloy through a vacuum smelting furnace, carrying out solid solution treatment at the temperature of 800-900 ℃ for 24h to obtain a uniform master alloy ingot, then carrying out wire cutting to obtain a Cu-Mn alloy block, wherein the thickness of the cut Cu-Mn alloy block is 0.5-2 mm, then placing the Cu-Mn alloy block into an inert gas atmosphere furnace for heating for stress relief annealing at the heating temperature of 300-500 ℃ for 2h, and cooling to room temperature along with the furnace to obtain a section;
step three, cleaning the section obtained in the step two, putting the section into a container filled with a chemical corrosion solution for dealloying, wherein the chemical corrosion solution is HCL or H with the concentration of 0.5-1.5M2SO4In the case of a HCL solution, the ratio of the amount of Mn to HCL is 1: 3 if H2SO4Solution of Mn and H2SO4The ratio of the amounts of substances (1): 1.5, dealloying and corroding for 8-24h at 0-40 ℃;
and step four, carrying out oxidation treatment on the section obtained in the step three in a muffle furnace, wherein the oxidation temperature is 230-300 ℃, the heat preservation time is 3-5h, and cooling the section to room temperature along with the furnace after the oxidation treatment is finished to obtain the nano porous CuO material.
The pore wall of the bulk nano-porous CuO prepared by the method is in a nano level, the whole porous CuO has a macroscopic large size, and the size of a sample shown in an experiment can reach 35mm in length and 5mm in width, but the sample is not limited to the size, can be adjusted according to the cutting size, and can be adjusted in thickness of 0.5-2 mm according to different process parameters. The nano porous CuO block prepared by the method has the thickness of 4.3-14.5 m2The specific surface area per gram and the bending strength are adjustable within 2.5MPa to 15.1 MPa.
Example 1
Step one, pretreatment and preparation of raw materials:
polishing and brightening the pure Cu blocks by using sand paper, and cleaning and drying by using alcohol; and (3) pickling the industrial electrolytic Mn sheet by using 3% nitric acid and alcohol, washing by using alcohol, and then blowing to dry to remove oxide skins and impurities on the surfaces of the copper blocks and the Mn sheet. And (3) mixing the cleaned Cu block with the Mn piece according to the mass ratio of 3: and 7, weighing.
Step two, preparing the alloy section:
repeatedly smelting the Cu block and the Mn sheet for 3 times by a vacuum smelting furnace to obtain a master alloy ingot, wherein the smelting temperature is 3000 ℃ each time. And putting the smelted Cu-Mn alloy into an inert gas atmosphere furnace, heating to 900 ℃, preserving heat for 24 hours, and cooling by adopting a water quenching mode. The cooled Cu-Mn single-phase solid solution is processed into a block with the thickness of 2mm by wire cutting. And then putting the Cu-Mn alloy block into an inert gas atmosphere furnace, heating to 500 ℃, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain the section.
Step three, chemical dealloying treatment
And cleaning the cut Cu-Mn alloy block, weighing the mass, then putting the Cu-Mn alloy block into 1mol/L HCL solution for dealloying free corrosion, and removing Mn in the alloy to obtain the block nano porous Cu. Wherein the mass ratio of Mn to HCL solution in the Cu-Mn single-phase solid solution is 1: 3, the temperature of the corrosive liquid is 20 ℃, and the corrosion time is 24 hours.
Step four, oxidation treatment
And (3) placing the bulk nano-porous Cu obtained in the third step into a crucible, and placing the crucible and the bulk nano-porous Cu into a heating furnace together for oxidation treatment at 230 ℃ for 3h to obtain the bulk CuO material with the nano-porous structure.
The nanoporous CuO prepared in this example had a specific surface area of 13.5m2(iv)/g, flexural strength was 9.9 MPa.
Fig. 1 is a macroscopic topography of bulk nanoporous CuO prepared in example 1. It can be seen from fig. 1 that the bulk nanoporous CuO prepared has an integral macroscopic size and the size thereof is 35mm × 5mm × 2 mm.
Fig. 2 is an XRD pattern of bulk nanoporous CuO prepared in the present example 1. As can be seen from fig. 2, the peak positions of the (110), (111), (202) and other crystal planes of the substance coincide with the standard spectrum of CuO, indicating that the sample prepared after the oxidation treatment in step 4 is indeed CuO.
Fig. 3 is an SEM image of bulk nanoporous CuO prepared in example 1. It can be seen from the figure that the CuO prepared by the embodiment of the present invention is nano-scale and has a porous structure with bicontinuous ligaments.
Example 2
Step one, pretreatment and preparation of raw materials:
polishing and brightening the pure Cu blocks by using sand paper, and cleaning and drying by using alcohol; and (3) pickling the industrial electrolytic Mn sheet by using 3% nitric acid and alcohol, washing by using alcohol, and then blowing to dry to remove oxide skins and impurities on the surfaces of the copper blocks and the Mn sheet. And (3) mixing the cleaned Cu block with the Mn piece according to the mass ratio of 3: and 7, weighing.
Step two, preparing the alloy section:
repeatedly smelting the Cu block and the Mn sheet for 3 times by a vacuum smelting furnace to obtain a master alloy ingot, wherein the smelting temperature is 3000 ℃ each time. And putting the smelted Cu-Mn alloy into an inert gas atmosphere furnace, heating to 850 ℃, preserving heat for 24h, and cooling by adopting a water quenching mode. The cooled Cu-Mn single-phase solid solution is processed into a block with the thickness of 1.5mm by wire cutting. And then putting the Cu-Mn alloy block into an inert gas atmosphere furnace, heating to 400 ℃, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain the section.
Step three, chemical dealloying treatment
And cleaning the cut Cu-Mn alloy block, weighing the mass, then putting the Cu-Mn alloy block into 0.5mol/L HCL solution for dealloying free corrosion, and removing Mn in the alloy to obtain the block nano porous Cu. Wherein the mass ratio of Mn to HCL solution in the Cu-Mn single-phase solid solution is 1: 3, the temperature of the corrosive liquid is 40 ℃, and the corrosion time is 12 hours.
Step four, oxidation treatment
And (3) placing the bulk nano-porous Cu obtained in the third step into a crucible, and placing the crucible and the bulk nano-porous Cu into a heating furnace together for oxidation treatment at 250 ℃ for 3h to obtain the bulk CuO material with the nano-porous structure.
The nanoporous CuO prepared in this example had a specific surface area of 14.1m2(iv)/g, flexural strength was 4.9 MPa.
Example 3
Step one, pretreatment and preparation of raw materials:
polishing and brightening the pure Cu blocks by using sand paper, and cleaning and drying by using alcohol; and (3) pickling the industrial electrolytic Mn sheet by using 3% nitric acid and alcohol, washing by using alcohol, and then blowing to dry to remove oxide skins and impurities on the surfaces of the copper blocks and the Mn sheet. And (3) mixing the cleaned Cu block with the Mn piece according to the mass ratio of 3.5: and 6.5, weighing.
Step two, preparing the alloy section:
repeatedly smelting the Cu block and the Mn sheet for 3 times by a vacuum smelting furnace to obtain a master alloy ingot, wherein the smelting temperature is 3000 ℃ each time. And putting the smelted Cu-Mn alloy into an inert gas atmosphere furnace, heating to 850 ℃, preserving heat for 24h, and cooling by adopting a water quenching mode. The cooled Cu-Mn single-phase solid solution is processed into a block with the thickness of 1.5mm by wire cutting. And then putting the Cu-Mn alloy block into an inert gas atmosphere furnace, heating to 400 ℃, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain the section.
Step three, chemical dealloying treatment
And cleaning the cut Cu-Mn alloy block, weighing the mass, then putting the Cu-Mn alloy block into 0.5mol/L HCL solution for dealloying free corrosion, and removing Mn in the alloy to obtain the block nano porous Cu. Wherein the mass ratio of Mn to HCL solution in the Cu-Mn single-phase solid solution is 1: 3, the temperature of the corrosive liquid is 0 ℃, and the corrosion time is 18 h.
Step four, oxidation treatment
And (3) placing the bulk nano-porous Cu obtained in the third step into a crucible, and placing the crucible and the bulk nano-porous Cu into a heating furnace together for oxidation treatment at 250 ℃ for 4h to obtain the bulk CuO material with the nano-porous structure.
The nanoporous CuO prepared in this example had a specific surface area of 11.9m2(ii)/g, flexural strength was 11.2 MPa.
Example 4
Step one, pretreatment and preparation of raw materials:
polishing and brightening the pure Cu blocks by using sand paper, and cleaning and drying by using alcohol; and (3) pickling the industrial electrolytic Mn sheet by using 3% nitric acid and alcohol, washing by using alcohol, and then blowing to dry to remove oxide skins and impurities on the surfaces of the copper blocks and the Mn sheet. And (3) mixing the cleaned Cu block with the Mn sheet according to the mass ratio of 2.5: 7.5 weight.
Step two, preparing the alloy section:
repeatedly smelting the Cu block and the Mn sheet for 3 times by a vacuum smelting furnace to obtain a master alloy ingot, wherein the smelting temperature is 3000 ℃ each time. And putting the smelted Cu-Mn alloy into an inert gas atmosphere furnace, heating to 900 ℃, preserving heat for 24 hours, and cooling by adopting a water quenching mode. The cooled Cu-Mn single-phase solid solution is processed into a block with the thickness of 1mm by wire cutting. And then putting the Cu-Mn alloy block into an inert gas atmosphere furnace, heating to 500 ℃, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain the section.
Step three, chemical dealloying treatment
And cleaning the cut Cu-Mn alloy block, weighing the mass, then putting the Cu-Mn alloy block into 0.1mol/L HCL solution for dealloying free corrosion, and removing Mn in the alloy to obtain the block nano porous Cu. Wherein the mass ratio of Mn to HCL solution in the Cu-Mn single-phase solid solution is 1: 3, the temperature of the corrosive liquid is 20 ℃, and the corrosion time is 18 h.
Step four, oxidation treatment
And (3) placing the bulk nano-porous Cu obtained in the third step into a crucible, and placing the crucible and the bulk nano-porous Cu into a heating furnace together for oxidation treatment at 230 ℃ for 3h to obtain the bulk CuO material with the nano-porous structure.
The nanoporous CuO prepared in this example had a specific surface area of 14.5m2(ii)/g, flexural strength was 2.5 MPa.
Example 5
Step one, pretreatment and preparation of raw materials:
polishing and brightening the pure Cu blocks by using sand paper, and cleaning and drying by using alcohol; and (3) pickling the industrial electrolytic Mn sheet by using 3% nitric acid and alcohol, washing by using alcohol, and then blowing to dry to remove oxide skins and impurities on the surfaces of the copper blocks and the Mn sheet. And (3) mixing the cleaned Cu block with the Mn piece according to the mass ratio of 3.5: and 6.5, weighing.
Step two, preparing the alloy section:
repeatedly smelting the Cu block and the Mn sheet for 3 times by a vacuum smelting furnace to obtain a master alloy ingot, wherein the smelting temperature is 3000 ℃ each time. And putting the smelted Cu-Mn alloy into an inert gas atmosphere furnace, heating to 800 ℃, preserving heat for 24h, and cooling by adopting a water quenching mode. The cooled Cu-Mn single-phase solid solution is processed into a block with the thickness of 1mm by wire cutting. And then putting the Cu-Mn alloy block into an inert gas atmosphere furnace, heating to 300 ℃, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain the section.
Step three, chemical dealloying treatment
Cleaning the cut Cu-Mn alloy block, weighing the mass, and then putting the mass into 0.5mol/LH2SO4And carrying out dealloying free corrosion in the solution, and removing Mn in the alloy to obtain the bulk nano porous Cu. Wherein the mass ratio of Mn to HCL solution in the Cu-Mn single-phase solid solution is 1: 1.5, the temperature of the corrosive liquid is 20 ℃, and the corrosion time is 10 hours.
Step four, oxidation treatment
And (3) placing the bulk nano-porous Cu obtained in the third step into a crucible, and placing the crucible and the bulk nano-porous Cu into a heating furnace together for oxidation treatment at 250 ℃ for 4h to obtain the bulk CuO material with the nano-porous structure.
The nanoporous CuO prepared in this example had a specific surface area of 9.2m2(iv)/g, flexural strength 8.7 MPa.
Example 6
Step one, pretreatment and preparation of raw materials:
polishing and brightening the pure Cu blocks by using sand paper, and cleaning and drying by using alcohol; and (3) pickling the industrial electrolytic Mn sheet by using 3% nitric acid and alcohol, washing by using alcohol, and then blowing to dry to remove oxide skins and impurities on the surfaces of the copper blocks and the Mn sheet. And (3) mixing the cleaned Cu block with the Mn piece according to the mass ratio of 4: and 6, weighing.
Step two, preparing the alloy section:
repeatedly smelting the Cu block and the Mn sheet for 3 times by a vacuum smelting furnace to obtain a master alloy ingot, wherein the smelting temperature is 3000 ℃ each time. And putting the smelted Cu-Mn alloy into an inert gas atmosphere furnace, heating to 800 ℃, preserving heat for 24h, and cooling by adopting a water quenching mode. The cooled Cu-Mn single-phase solid solution is processed into a block with the thickness of 0.5mm by wire cutting. And then putting the Cu-Mn alloy block into an inert gas atmosphere furnace, heating to 400 ℃, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain the section.
Step three, chemical dealloying treatment
Cleaning the cut Cu-Mn alloy block, weighing the mass, and then putting the mass into 0.1mol/LH2SO4And carrying out dealloying free corrosion in the solution, and removing Mn in the alloy to obtain the bulk nano porous Cu. Wherein the mass ratio of Mn to HCL solution in the Cu-Mn single-phase solid solution is 1: 1.5, the temperature of the corrosive liquid is 20 ℃, and the corrosion time is 8 hours.
Step four, oxidation treatment
And (3) placing the bulk nano-porous Cu obtained in the third step into a crucible, and placing the crucible and the bulk nano-porous Cu into a heating furnace together for oxidation treatment at 300 ℃ for 5h to obtain the bulk CuO material with the nano-porous structure.
The nanoporous CuO prepared in this example had a specific surface area of 5.7m2(iv)/g, flexural strength was 12.3 MPa.
Example 7
Step one, pretreatment and preparation of raw materials:
polishing and brightening the pure Cu blocks by using sand paper, and cleaning and drying by using alcohol; and (3) pickling the industrial electrolytic Mn sheet by using 3% nitric acid and alcohol, washing by using alcohol, and then blowing to dry to remove oxide skins and impurities on the surfaces of the copper blocks and the Mn sheet. And (3) mixing the cleaned Cu block with the Mn sheet according to the mass ratio of 4.5: and 5.5, weighing.
Step two, preparing the alloy section:
repeatedly smelting the Cu block and the Mn sheet for 3 times by a vacuum smelting furnace to obtain a master alloy ingot, wherein the smelting temperature is 3000 ℃ each time. And putting the smelted Cu-Mn alloy into an inert gas atmosphere furnace, heating to 800 ℃, preserving heat for 24h, and cooling by adopting a water quenching mode. The cooled Cu-Mn single-phase solid solution is processed into a block with the thickness of 0.5mm by wire cutting. And then putting the Cu-Mn alloy block into an inert gas atmosphere furnace, heating to 300 ℃, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain the section.
Step three, chemical dealloying treatment
Cleaning the cut Cu-Mn alloy block, weighing the mass, and then putting the mass into 0.5mol/LH2SO4And carrying out dealloying free corrosion in the solution, and removing Mn in the alloy to obtain the bulk nano porous Cu. Wherein the mass ratio of Mn to HCL solution in the Cu-Mn single-phase solid solution is 1: 1.5, the temperature of the corrosive liquid is 20 ℃, and the corrosion time is 12 h.
Step four, oxidation treatment
And (3) placing the bulk nano-porous Cu obtained in the third step into a crucible, and placing the crucible and the bulk nano-porous Cu into a heating furnace together for oxidation treatment at 300 ℃ for 5h to obtain the bulk CuO material with the nano-porous structure.
The nanoporous CuO prepared in this example had a specific surface area of 4.3m2(iv)/g, flexural strength 15.1 MPa.
Claims (8)
1. A preparation method of bulk nano-porous CuO is characterized by comprising the following steps:
step one, preparing raw materials
Weighing the following components in percentage by mass: 25-45% of industrial pure Cu blocks and 55-75% of industrial pure Mn sheets, wherein the sum of the mass percentages of the components is 100%;
step two, preparing alloy section bar
Melting the Cu block and the Mn sheet weighed in the step one into alloy through a vacuum melting furnace, carrying out solid solution treatment to obtain uniform master alloy cast ingot, then carrying out wire cutting to obtain a Cu-Mn alloy block, then placing the Cu-Mn alloy block into an inert gas atmosphere furnace for heating for stress relief annealing, and cooling to room temperature along with the furnace to obtain a section;
step three, cleaning the section obtained in the step two, and putting the section into a container filled with a chemical corrosion solution for dealloying;
and step four, carrying out oxidation treatment on the section obtained in the step three, and cooling the section to room temperature along with a furnace after the oxidation treatment is finished to obtain the nano porous CuO material.
2. The method for preparing bulk nano-porous CuO according to claim 1, wherein the temperature of the solution treatment in the second step is 800-900 ℃ and the holding time is 24 h.
3. The method for preparing bulk nano-porous CuO according to claim 2, wherein in the second step, the Cu-Mn alloy bulk is placed into an inert gas atmosphere furnace for stress relief annealing at a heating temperature of 300 ℃ and 500 ℃ for a holding time of 2 h.
4. The method as claimed in claim 3, wherein the thickness of the alloy cut in the second step is 0.5mm-2 mm.
5. The method of claim 1, wherein the etching solution in step three is HCL or H with a concentration of 0.5-1.5M2SO4And (3) solution.
6. According to claim 5The preparation method of the bulk nano-porous CuO is characterized in that, in the third step, if the bulk nano-porous CuO is a HCL solution, the ratio of the Mn to the HCL is 1: 3 if H2SO4Solution of Mn and H2SO4The ratio of the amounts of substances (1): 1.5.
7. the method for preparing bulk nano porous CuO according to claim 6, wherein the dealloying time in the third step is 8-24h, and the etching temperature is 0-40 ℃.
8. The method for preparing bulk nano-porous CuO according to claim 1, wherein the oxidation temperature in the fourth step is 230-.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN102602982A (en) * | 2012-03-14 | 2012-07-25 | 西安理工大学 | Method for preparing porous ZnO by means of combining dealloying method with ceramic coating |
| CN104528803A (en) * | 2014-12-24 | 2015-04-22 | 西安理工大学 | Preparation method of ZnO flaky porous nanometer material |
| CN104986793A (en) * | 2015-06-26 | 2015-10-21 | 西安理工大学 | Preparation method for ZnO nanomaterial with hierarchical porous structure |
| CN111254309A (en) * | 2020-03-04 | 2020-06-09 | 山东大学 | Preparation method of nano porous metal or alloy |
| CN111634938A (en) * | 2020-06-16 | 2020-09-08 | 东莞理工学院 | Preparation method of nano porous powder material |
| CN112226727A (en) * | 2020-09-30 | 2021-01-15 | 西安理工大学 | Preparation method of surface gradient nano porous copper film |
-
2021
- 2021-08-12 CN CN202110922794.7A patent/CN113800899A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN102602982A (en) * | 2012-03-14 | 2012-07-25 | 西安理工大学 | Method for preparing porous ZnO by means of combining dealloying method with ceramic coating |
| CN104528803A (en) * | 2014-12-24 | 2015-04-22 | 西安理工大学 | Preparation method of ZnO flaky porous nanometer material |
| CN104986793A (en) * | 2015-06-26 | 2015-10-21 | 西安理工大学 | Preparation method for ZnO nanomaterial with hierarchical porous structure |
| CN111254309A (en) * | 2020-03-04 | 2020-06-09 | 山东大学 | Preparation method of nano porous metal or alloy |
| CN111634938A (en) * | 2020-06-16 | 2020-09-08 | 东莞理工学院 | Preparation method of nano porous powder material |
| CN112226727A (en) * | 2020-09-30 | 2021-01-15 | 西安理工大学 | Preparation method of surface gradient nano porous copper film |
Non-Patent Citations (3)
| Title |
|---|
| 刘海等: "Cu0.3Mn0.7去合金化制备纳米多孔铜块体材料", 《稀有金属材料与工程》 * |
| 姚彦菲等: "纳米晶Cu-Al合金去合金化制备纳米多孔铜及其力学性能研究", 《功能材料》 * |
| 陈丹等主编: "《金属学与热处理》", 30 November 2017, 北京理工大学出版社 * |
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