CN111659898A - Preparation method of micro-nano copper sheet - Google Patents
Preparation method of micro-nano copper sheet Download PDFInfo
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- CN111659898A CN111659898A CN201910174175.7A CN201910174175A CN111659898A CN 111659898 A CN111659898 A CN 111659898A CN 201910174175 A CN201910174175 A CN 201910174175A CN 111659898 A CN111659898 A CN 111659898A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 83
- 239000010949 copper Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000002028 Biomass Substances 0.000 claims abstract description 126
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 50
- 150000001879 copper Chemical class 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 47
- 238000002386 leaching Methods 0.000 claims abstract description 38
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 239000012266 salt solution Substances 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 239000006227 byproduct Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000007789 sealing Methods 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 12
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229940116318 copper carbonate Drugs 0.000 claims description 8
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 5
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 7
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- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 240000005020 Acaciella glauca Species 0.000 description 1
- 240000007185 Albizia julibrissin Species 0.000 description 1
- 235000011468 Albizia julibrissin Nutrition 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0551—Flake form nanoparticles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a preparation method of a micro-nano copper sheet, which comprises the following steps: collecting and obtaining a plant biomass raw material, and processing the plant biomass raw material to obtain a plant biomass dry material or a plant biomass leaching solution; providing a water-soluble copper salt and dissolving the water-soluble copper salt in water to obtain a copper salt solution; transferring the copper salt solution into a reaction kettle, and adding the plant biomass dry material or the plant biomass leaching solution into the reaction kettle; and sealing the reaction kettle, then carrying out hydrothermal reaction, carrying out solid-liquid separation, collecting a solid reaction product, and separating to remove a byproduct in the solid reaction product to prepare the micro-nano copper sheet. The preparation method of the micro-nano copper sheet provided by the invention has the advantages of simple process, low cost, environmental friendliness and the like.
Description
Technical Field
The invention belongs to the technical field of micro-nano scale materials, and particularly relates to a preparation method of a micro-nano copper sheet.
Background
In recent years, low-dimensional nanomaterials, such as nanowires, nanofibers, nanorods, nanobelts, and nanosheets/disks, are widely used in nanoelectronic devices, biosensors, nanoprobes, nanochemistry, and nanocomposites, etc., due to their unique electrical, thermal, optical, and magnetic properties. The two-dimensional micro-nano copper sheet attracts great attention due to excellent electric conduction, heat conduction and antibacterial performance, and the two-dimensional micro-nano copper sheet is wide in application fields, such as lubricating materials, dielectric materials, catalysts, sensors, biological medicines, flexible electronics and the like.
At present, a plurality of methods for preparing the micro-nano copper sheet are available, and representative methods include a physical mechanical ball milling method and a wet chemical reduction method. The mechanical ball milling method is to extrude ball powder into sheets by a mechanical milling method, although the method can simply realize the large-scale production of the copper sheet, the appearance and the size cannot be strictly controlled, the uniformity of the obtained micro-nano copper sheet is poor, and meanwhile, various milling aids such as lubricants and the like are inevitably added in the method, so that the process is complex. The wet chemical reduction method is characterized in that the controllable preparation of the micro-nano copper sheet can be well realized by adding auxiliary agents such as a dispersing agent, a structure directing agent and the like, but due to the introduction of various auxiliary agents, the separation and purification process of the finally obtained copper sheet is complex, and meanwhile, the method is difficult to realize the large-scale production of the copper sheet.
The existing method for preparing the micro-nano copper sheet inevitably needs to add various auxiliary agents such as a lubricant, a dispersing agent, a stabilizing agent, a structure directing agent and the like to regulate and control the preparation of the copper sheet, and has the disadvantages of complex process, high cost and serious environmental pollution.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a preparation method of a micro-nano copper sheet, which is simple in process, low in cost and green and macroscopic.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a micro-nano copper sheet comprises the following steps:
collecting and obtaining a plant biomass raw material, and processing the plant biomass raw material to obtain a plant biomass dry material or a plant biomass leaching solution;
providing a water-soluble copper salt and dissolving the water-soluble copper salt in water to obtain a copper salt solution;
transferring the copper salt solution into a reaction kettle, and adding the plant biomass dry material or the plant biomass leaching solution into the reaction kettle;
and sealing the reaction kettle, then carrying out hydrothermal reaction, carrying out solid-liquid separation, collecting a solid reaction product, and separating to remove a byproduct in the solid reaction product to prepare the micro-nano copper sheet.
Specifically, the plant biomass raw material is one or more than two of roots, stems, branches, leaves, flowers, fruits and seeds of plants.
In particular, the plant biomass feedstock is selected from biomass feedstocks of evergreen arbor plants.
Specifically, the processing of the plant biomass raw material to obtain the plant biomass dry material comprises the following steps: placing the plant biomass raw material into baking equipment for baking to obtain the plant biomass dry material; the processing of the plant biomass feedstock to obtain a plant biomass leachate comprises: placing the plant biomass raw material into baking equipment for baking to obtain a plant biomass dry material; and soaking the plant biomass dry material in an aqueous solution for leaching treatment, and then separating out supernatant to obtain plant biomass leaching solution.
Specifically, when the plant biomass raw material is placed in baking equipment for baking, the baking temperature is 50-70 ℃, and the baking time is more than 12 hours; when the plant biomass dry material is soaked in the aqueous solution for leaching treatment, the aqueous solution is boiled for more than 1h by heating.
Specifically, before processing the plant biomass raw material to obtain the plant biomass dry material or the plant biomass leaching solution, the method further comprises the following steps: washing the plant biomass raw material by using water, ethanol and acetone in sequence.
Specifically, the water-soluble copper salt is selected from one or more of copper nitrate, copper acetate, copper chloride, copper sulfate and basic copper carbonate.
Specifically, the concentration of the copper salt solution is 0.1-100 mg/mL.
Specifically, when the plant biomass dry material is selectively added into the reaction kettle, the plant biomass dry material is added according to the mass ratio of the plant biomass dry material to the water-soluble copper salt of 1: 0.01-10; and when the plant biomass leaching solution is selectively added into the reaction kettle, adding the plant biomass leaching solution according to the mass ratio of the plant biomass leaching solution to the water-soluble copper salt of 1: 0.1-100.
Specifically, the temperature of the hydrothermal reaction is 120-300 ℃, and the time is 1-96 h.
According to the preparation method of the micro-nano copper sheet, provided by the embodiment of the invention, the plant biomass is used as a reducing agent component and a structure guiding agent, and the water-soluble copper salt is reduced to obtain the copper sheet with a micro-nano size structure, so that the preparation process is simple and the cost is low. In the preparation process, no other chemical reagent (such as an organic reagent, a reducing agent, a dispersing agent, a structure directing agent and the like) is added except the precursor copper salt, and the preparation method has the advantages of green and macro preparation.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a micro-nano copper sheet according to an embodiment of the invention;
FIGS. 2 and 3 are scanning electron micrographs of a micro-nano copper sheet prepared in example 1 of the invention;
FIG. 4 is an X-ray diffraction diagram of a micro-nano copper sheet prepared in example 1 of the invention;
FIGS. 5 and 6 are scanning electron micrographs of a micro-nano copper sheet prepared in example 2 of the invention;
FIGS. 7 and 8 are scanning electron micrographs of a micro-nano copper sheet prepared in example 3 of the invention;
FIGS. 9 and 10 are scanning electron micrographs of a micro-nano copper sheet prepared in example 4 of the invention;
FIGS. 11 and 12 are scanning electron micrographs of a micro-nano copper sheet prepared in example 5 of the invention;
FIGS. 13 and 14 are scanning electron micrographs of a micro-nano copper sheet prepared in example 6 of the invention;
FIGS. 15 and 16 are scanning electron micrographs of a micro-nano copper sheet prepared in example 7 of the present invention;
FIGS. 17 and 18 are scanning electron micrographs of a micro-nano copper sheet prepared in example 8 of the present invention;
FIGS. 19 and 20 are scanning electron micrographs of a micro-nano copper sheet prepared in example 9 of the present invention;
FIGS. 21 and 22 are SEM images of micro-nano copper sheets prepared in example 10 of the invention;
fig. 23 and 24 are scanning electron micrographs of the micro-nano copper sheet prepared in example 11 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
The embodiment of the invention provides a preparation method of a micro-nano copper sheet, which comprises the following steps of:
s10, collecting and obtaining a plant biomass raw material, and drying the plant biomass raw material to obtain a plant biomass dry material or a plant biomass leaching solution. Wherein the plant biomass raw material is one or more than two of roots, stems, branches, leaves, flowers, fruits and seeds of plants.
In a preferred embodiment, the plant biomass feedstock is selected from biomass feedstocks of evergreen arbor plants. The evergreen arbor plant is, for example: chinese pine, cedar, Korean pine, Chinese pine, Pinus sylvestris, Chinese red pine, slash pine, Chinese fir, spruce, arborvitae, juniper, Japanese cypress, ligustrum lucidum, pistacia chinensis, magnolia grandiflora, gardenia, dulcamara, albizia julibrissin, banyan, cinnamomum camphora, bay, sweet osmanthus, longan, lychee, lutea and the like, and can be one or more than two evergreen wood plants.
Specifically, the processing of the plant biomass raw material to obtain the plant biomass dry material comprises the following steps: and placing the plant biomass raw material into a baking device for baking to obtain the plant biomass dry material. Preferably, the baking temperature is 50-70 ℃, and the baking time is more than 12 h; in a more preferable technical scheme, the baking time is 12-24 h.
Specifically, the processing of the plant biomass raw material to obtain the plant biomass leaching solution comprises: firstly, preparing and obtaining the plant biomass dry material according to the method for obtaining the plant biomass dry material; and then soaking the plant biomass dry material in an aqueous solution for leaching treatment, and then separating out supernatant to obtain plant biomass leaching solution. Preferably, the heating causes the aqueous solution to boil for more than 1 h. In a more preferred embodiment, the aqueous solution is boiled for 2 to 10 hours by heating.
Specifically, before processing the plant biomass raw material to obtain the plant biomass dry material or the plant biomass leaching solution, the method further comprises the following steps: washing the plant biomass raw material by using water, ethanol and acetone in sequence.
S20, providing water-soluble copper salt and dissolving the copper salt in water to obtain copper salt solution.
Specifically, the water-soluble copper salt is selected from one or more of copper nitrate, copper acetate, copper chloride, copper sulfate and basic copper carbonate. In a preferable scheme, the concentration of the copper salt solution is prepared within the range of 0.1-100 mg/mL.
S30, transferring the copper salt solution to a reaction kettle, and adding the plant biomass dry material or the plant biomass leaching solution into the reaction kettle. When the plant biomass leaching solution is selectively added into the reaction kettle, the plant biomass leaching solution and the copper salt solution are uniformly mixed and then are transferred into the reaction kettle.
Specifically, when the plant biomass dry material is selectively added into the reaction kettle, the plant biomass dry material is added according to the mass ratio of the plant biomass dry material to the water-soluble copper salt of 1: 0.01-10; and when the plant biomass leaching solution is selectively added into the reaction kettle, adding the plant biomass leaching solution according to the mass ratio of the plant biomass leaching solution to the water-soluble copper salt of 1: 0.1-100.
S40, sealing the reaction kettle, carrying out hydrothermal reaction, carrying out solid-liquid separation, collecting a solid reaction product, and separating to remove a byproduct in the solid reaction product to obtain the micro-nano copper sheet.
Specifically, the temperature of the hydrothermal reaction is 120-300 ℃, and the time is 1-96 h. After the hydrothermal reaction is finished, performing solid-liquid separation to collect a solid reaction product, removing other by-products (such as two-dimensional nano carbon and the like) in the solid reaction product by adopting a centrifugal separation process, and finally obtaining the micro-nano copper sheet.
In the above hydrothermal reaction: on one hand, macromolecular components (cellulose, starch and the like) contained in the plant biomass are hydrolyzed into glucose to serve as a reducing agent, and small molecular components (ketone, phenol and the like) contained in the plant biomass serve as a structure directing agent, so that the water-soluble copper salt is reduced into the simple substance metal copper sheet with a specific structure under the combined action of the macromolecular components and the structure directing agent; on the other hand, the copper salt catalyzes and carbonizes organic matters in the plant biomass to obtain the two-dimensional nano carbon. The invention aims to prepare the micro-nano copper sheet, so that two-dimensional nano carbon is separated and removed from a final product, and the micro-nano copper sheet is reserved. The yield of the micro-nano copper sheets can be increased by increasing the proportion of the copper salt to the plant biomass dry material or the plant biomass leaching solution, so that in an optimal technical scheme, the mass ratio of the water-soluble copper salt in the reaction kettle to the plant biomass dry material or the plant biomass leaching solution is more than 1.
According to the preparation method of the micro-nano copper sheet, macromolecular components (cellulose, starch and the like) contained in plant biomass are hydrolyzed into glucose to serve as a reducing agent, small molecular components (ketone, phenol and the like) contained in the plant biomass serve as a structure directing agent, the large molecular components and the small molecular components act together to reduce water-soluble copper salt into the elemental metal copper sheet with a specific structure, and no other chemical reagent (such as an organic reagent, a reducing agent, a dispersing agent, a structure directing agent and the like) is added except for precursor copper salt in the preparation process, so that the preparation method has the advantages of simple process, low cost, greenness, macroscopicity and the like. According to the preparation method of the micro-nano copper sheet, the thickness of the prepared micro-nano copper sheet is within the range of 5 nm-5 microns, and the radial dimension of the micro-nano copper sheet is within the range of 30 nm-50 mm.
The micro-nano copper sheet in the embodiment of the invention is a micro-nano copper sheet with a thickness of a nano size order or a micron size order.
Example 1
And (3) collecting Chinese pine leaves, washing the Chinese pine leaves by using water, ethanol and acetone in sequence, and drying the Chinese pine leaves in an oven at the temperature of 60 ℃ for 12 hours to obtain dried Chinese pine leaves serving as plant biomass dry materials.
Weighing 4mg of copper nitrate, dissolving in 40mL of water, and fully stirring to completely dissolve the copper nitrate to obtain a copper salt solution.
The copper nitrate solution was transferred to a reaction kettle and 4mg of dried Chinese pine leaves were added.
And (3) sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature to be 120 ℃, and reacting for 1 hour.
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 2 and 3 are SEM images of the micro-nano copper sheet prepared in this example, and fig. 4 is an XRD image of the micro-nano copper sheet prepared in this example.
Example 2
Collecting the branches of the dragon juniper, washing the branches of the dragon juniper sequentially by using water, ethanol and acetone, and drying the branches of the dragon juniper in an oven at 65 ℃ for 14 hours to obtain dried branches of the dragon juniper as plant biomass dry materials.
Weighing 150mg of copper nitrate, dissolving in 150mL of water, and fully stirring to completely dissolve the copper nitrate to obtain a copper salt solution.
The above copper nitrate solution was transferred to a reaction kettle and 15mg of dried dragon juniper branches were added.
And (3) sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature to be 160 ℃, and reacting for 3 hours.
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 5 and 6 are SEM images of the micro-nano copper sheet prepared in this example.
Example 3
Collecting southern magnolia leaves, washing with water, ethanol and acetone in sequence, and drying in an oven at 50 ℃ for 16 hours to obtain dried southern magnolia leaves as plant biomass dry material.
Weighing 400mg of copper acetate, dissolving the copper acetate in 300mL of water, and fully stirring to completely dissolve the copper acetate to obtain a copper salt solution.
The copper acetate solution was transferred to a reaction kettle and 200mg of dried magnolia grandiflora leaves was added.
And (3) sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature to be 180 ℃, and reacting for 8 hours.
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 7 and 8 are SEM images of the micro-nano copper sheet prepared in this example.
Example 4
Collecting banyan root, washing with water, ethanol and acetone in sequence, and drying in an oven at 60 ℃ for 18 hours to obtain dried banyan root as plant biomass dry material.
Weighing 500mg of basic copper carbonate, dissolving the basic copper carbonate in 400mL of water, and fully stirring to completely dissolve the basic copper carbonate to obtain a copper salt solution which is the basic copper carbonate solution.
Transferring the basic copper carbonate solution into a reaction kettle, and adding 300mg of dry ficus microcarpa roots.
And (3) sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature to be 200 ℃, and reacting for 10 hours.
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 9 and 10 are SEM images of the micro-nano copper sheet prepared in this example.
Example 5
Collecting camphor tree leaves, washing the camphor tree leaves by using water, ethanol and acetone in sequence, and drying the camphor tree leaves in an oven at 70 ℃ for 18 hours to obtain dried camphor tree leaves as plant biomass dry materials.
Weighing 600mg of copper acetate, dissolving the copper acetate in 600mL of water, and fully stirring to completely dissolve the copper acetate to obtain a copper salt solution.
The copper acetate solution was transferred to a reaction kettle and 500mg of dried camphor leaves were added.
And (3) sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature to be 200 ℃, and reacting for 24 hours.
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 11 and 12 are SEM images of the micro-nano copper sheet prepared in this example.
Example 6
Collecting the branches of the osmanthus fragrans, washing the branches of the osmanthus fragrans by using water, ethanol and acetone in sequence, and drying the branches of the osmanthus fragrans in a 70 ℃ drying oven for 20 hours to obtain dried branches of the osmanthus fragrans as plant biomass dry materials.
Weighing 2g of copper chloride, dissolving in 3L of water, and fully stirring to completely dissolve the copper chloride to obtain a copper salt solution.
And transferring the copper chloride solution to a reaction kettle, and adding 8g of dried osmanthus branches.
And (3) sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature to be 250 ℃, and reacting for 48 hours.
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 13 and 14 are SEM images of the micro-nano copper sheet prepared in this example.
Example 7
Collecting longan tree roots, washing the longan tree roots by using water, ethanol and acetone in sequence, and drying the longan tree roots in an oven at the temperature of 60 ℃ for 22 hours to obtain dried longan tree roots serving as plant biomass dry materials.
Weighing 4g of copper chloride, dissolving in 4L of water, and fully stirring to completely dissolve the copper chloride to obtain a copper salt solution.
Transferring the copper chloride solution to a reaction kettle, and adding 3g of dried longan tree roots.
And (3) sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature to be 250 ℃, and reacting for 96 hours.
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 15 and 16 are SEM images of the micro-nano copper sheet prepared in this example.
Example 8
Collecting the litchi stems, washing the litchi stems by using water, ethanol and acetone in sequence, and drying the litchi stems in an oven at 50 ℃ for 24 hours to obtain dried litchi stems as plant biomass dry materials.
Weighing 4g of copper sulfate, dissolving in 6L of water, and fully stirring to completely dissolve the copper sulfate, wherein the obtained copper salt solution is a copper sulfate solution.
Transferring the copper sulfate solution to a reaction kettle, and adding 20g of dried litchi stems.
Sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature at 300 ℃ and the reaction time at 48 hours
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 17 and 18 are SEM images of the micro-nano copper sheet prepared in this example.
Example 9
Collecting southern magnolia stems, washing the southern magnolia stems by using water, ethanol and acetone in sequence, and then placing the southern magnolia stems in an oven at 65 ℃ for drying for 14 hours to obtain dried southern magnolia stems as plant biomass dry materials.
Weighing 20mg of dried magnolia grandiflora stems, putting the dried magnolia grandiflora stems into 200mL of water, heating and boiling for 2h, centrifugally separating supernate, and collecting plant biomass extract.
Weighing 200mg of copper nitrate, dissolving in 200mL of water, and fully stirring to completely dissolve the copper nitrate to obtain a copper salt solution.
And uniformly mixing the copper nitrate solution and the plant biomass leaching solution, transferring the mixture into a reaction kettle with a proper size, sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature to be 160 ℃, and reacting for 3 hours.
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 19 and 20 are SEM images of the micro-nano copper sheet prepared in this example.
Example 10
Collecting the leaves of the pistacia chinensis bunge, washing the leaves by using water, ethanol and acetone in sequence, and then drying the leaves in a drying oven at the temperature of 65 ℃ for 18 hours to obtain dried leaves of the pistacia chinensis bunge as plant biomass dry materials.
Weighing 200mg of dried pistacia chinensis bunge leaves, putting the leaves into 300mL of water, heating and boiling for 5h, and centrifugally separating supernatant fluid to obtain plant biomass leaching solution.
Weighing 2g of copper sulfate, dissolving in 300mL of water, and fully stirring to completely dissolve the copper sulfate to obtain a copper salt solution.
And (3) uniformly mixing the copper sulfate solution and the plant biomass leaching solution, transferring the mixture into a reaction kettle with a proper size, sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature to be 180 ℃, and reacting for 5 hours.
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 21 and 22 are SEM images of the micro-nano copper sheet prepared in this example.
Example 11
Collecting the roots of the osmanthus trees, washing the roots by using water, ethanol and acetone in sequence, and then drying the roots in a 70 ℃ drying oven for 20 hours to obtain dried roots of the osmanthus trees as plant biomass dry materials.
Weighing 3g of dried osmanthus tree root, placing the dried osmanthus tree root in 500mL of water, heating and boiling for 10h, centrifugally separating supernatant, and collecting plant biomass leaching solution.
Weighing 5g of copper chloride, dissolving in 500mL of water, and fully stirring to completely dissolve the copper chloride to obtain a copper salt solution.
And uniformly mixing the copper chloride solution and the plant biomass leaching solution, transferring the mixture into a reaction kettle with a proper size, sealing the reaction kettle, placing the reaction kettle in a hydrothermal oven for hydrothermal reaction, setting the reaction temperature to be 200 ℃, and reacting for 12 hours.
And after the reaction is finished and the temperature is naturally reduced, carrying out solid-liquid separation to collect a solid reaction product, and removing other byproducts in the solid reaction product by adopting a centrifugal separation process to obtain the micro-nano copper sheet.
Fig. 23 and 24 are SEM images of the micro-nano copper sheet prepared in this example.
In conclusion, the preparation method of the micro-nano copper sheet provided by the invention has the advantages of simple process, low cost, environmental friendliness and the like.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (10)
1. A method for preparing a micro-nano copper sheet is characterized by comprising the following steps:
collecting and obtaining a plant biomass raw material, and processing the plant biomass raw material to obtain a plant biomass dry material or a plant biomass leaching solution;
providing a water-soluble copper salt and dissolving the water-soluble copper salt in water to obtain a copper salt solution;
transferring the copper salt solution to a reaction kettle, and adding the plant biomass dry material or the plant biomass leaching solution into the reaction kettle;
and sealing the reaction kettle, then carrying out hydrothermal reaction, carrying out solid-liquid separation, collecting a solid reaction product, and separating to remove a byproduct in the solid reaction product to prepare the micro-nano copper sheet.
2. The method for preparing the micro-nano copper sheet according to claim 1, wherein the plant biomass raw material is one or more than two of roots, stems, branches, leaves, flowers, fruits and seeds of plants.
3. The method for preparing the micro-nano copper sheet according to claim 2, wherein the plant biomass raw material is selected from biomass raw materials of evergreen arbor plants.
4. The method for preparing the micro-nano copper sheet according to any one of claims 1 to 3, which is characterized in that,
the processing of the plant biomass raw material to obtain the plant biomass dry material comprises the following steps: placing the plant biomass raw material into baking equipment for baking to obtain a plant biomass dry material;
the processing of the plant biomass feedstock to obtain a plant biomass leachate comprises: placing the plant biomass raw material into baking equipment for baking to obtain a plant biomass dry material; and soaking the plant biomass dry material in an aqueous solution for leaching treatment, and then separating out supernatant to obtain plant biomass leaching solution.
5. The method for preparing the micro-nano copper sheet according to claim 4, wherein,
when the plant biomass raw material is placed in baking equipment for baking, the baking temperature is 50-70 ℃, and the baking time is more than 12 hours;
when the plant biomass dry material is soaked in the aqueous solution for leaching treatment, the aqueous solution is boiled for more than 1h by heating.
6. The method for preparing the micro-nano copper sheet according to claim 4, wherein before the plant biomass raw material is processed to obtain the plant biomass dry material or the plant biomass leaching solution, the method further comprises the following steps: washing the plant biomass raw material by using water, ethanol and acetone in sequence.
7. The method for preparing the micro-nano copper sheet according to claim 1, wherein the water-soluble copper salt is one or more than two selected from copper nitrate, copper acetate, copper chloride, copper sulfate and basic copper carbonate.
8. The method for preparing the micro-nano copper sheet according to claim 7, wherein the concentration of the copper salt solution is 0.1-100 mg/mL.
9. The method for preparing the micro-nano copper sheet according to any one of claims 1, 7 or 8, which is characterized in that,
when the plant biomass dry material is selected to be added into the reaction kettle, adding the plant biomass dry material according to the mass ratio of the plant biomass dry material to the water-soluble copper salt of 1: 0.01-10;
and when the plant biomass leaching solution is selectively added into the reaction kettle, adding the plant biomass leaching solution according to the mass ratio of the plant biomass leaching solution to the water-soluble copper salt of 1: 0.1-100.
10. The method for preparing the micro-nano copper sheet according to claim 1, wherein the temperature of the hydrothermal reaction is 120-300 ℃ and the time is 1-96 h.
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