CN114014350A - Preparation method of copper oxide - Google Patents
Preparation method of copper oxide Download PDFInfo
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- CN114014350A CN114014350A CN202111405858.2A CN202111405858A CN114014350A CN 114014350 A CN114014350 A CN 114014350A CN 202111405858 A CN202111405858 A CN 202111405858A CN 114014350 A CN114014350 A CN 114014350A
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Abstract
The invention relates to a preparation method of copper oxide, which comprises the following steps: preparing a chemical solution with an oxidation function; immersing the copper sheet into a prepared chemical solution for chemical reaction to obtain copper hydroxide with a hierarchical nano structure; and taking out the copper hydroxide with the hierarchical nano structure, drying to obtain the copper hydroxide with the super-hydrophilic characteristic, and dehydrating the copper hydroxide with the super-hydrophilic characteristic to obtain the copper oxide with the super-hydrophobic characteristic. By adopting the method, the wettability of the surface structure of the copper hydroxide can be converted from super-hydrophilicity to super-hydrophobicity by dehydrating the copper hydroxide with the super-hydrophilicity, and the method is simple and convenient to operate.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of copper oxide.
Background
Complex surface structures have been well developed in the last decade for enhanced heat transfer and condensation, with super-hydrophilic surfaces increasing the critical heat flux density of heat-dissipating surfaces and super-hydrophobic surfaces promoting the detachment of liquids during condensation. At present, the wettability of most micro-nano surface structures is not convertible, that is, the super-hydrophobic and super-hydrophilic characteristics cannot be converted, so that a preparation method which can conveniently change the wettability of the surface structure of copper oxide is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of copper oxide, and aims to solve the problem of how to change the wettability of the surface structure of the copper oxide.
The technical scheme for solving the technical problems is as follows: a method of preparing copper oxide, the method comprising:
and 4, dehydrating the copper hydroxide with the super-hydrophilic characteristic to obtain the copper oxide with the super-hydrophobic characteristic.
The invention has the beneficial effects that: according to the method, the copper hydroxide with the hierarchical nano structure can be obtained through the configured chemical reaction between the chemical solution with the oxidation function and the copper sheet, the copper hydroxide with the super-hydrophilic characteristic can be obtained after the copper hydroxide with the hierarchical nano structure is washed and dried, the copper hydroxide with the super-hydrophilic characteristic is the copper sheet with the heat reaction type surface structure, namely the wettability of the nano structure of the copper sheet can be changed under the external condition.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, after the step 4, the method further includes:
and 5, placing the copper oxide with the super-hydrophobic characteristic in deionized water at 120 ℃ for heating to obtain the copper oxide with the super-hydrophilic characteristic.
The copper oxide with the super-hydrophobic characteristic is the copper oxide with the heat reaction type surface structure, namely the wettability of the nano structure of the copper oxide can be changed under external conditions, for example, the surface structure property of the copper oxide with the super-hydrophobic characteristic can be changed by heating the copper oxide with the super-hydrophobic characteristic in deionized water at 120 ℃, so that the copper oxide with the super-hydrophilic characteristic is obtained, the copper oxide with the super-hydrophilic characteristic can be used in the pool boiling enhanced heat transfer field, the conversion process between the super-hydrophobic characteristic and the super-hydrophilic characteristic can be realized only by heating, the preparation method is simple, and no substances polluting the environment are generated in the conversion process.
Further, the step 4 specifically includes:
and heating the copper hydroxide with the super-hydrophilic characteristic, and dehydrating the copper hydroxide for 60 minutes at 200 ℃ to obtain the copper oxide with the super-hydrophobic characteristic.
The method has the advantages that the dehydration treatment can be realized by heating the copper oxide in the environment of 200 ℃ for 60 minutes, the contact angle corresponding to the surface structure of the copper oxide can be changed along with the rise of the temperature, the contact angle with the super-hydrophilic characteristic is smaller than the contact angle corresponding to the super-hydrophobic characteristic, and the contact angle can be increased by heating the copper oxide to 200 ℃ so as to obtain the copper oxide with the super-hydrophobic characteristic.
Further, the hierarchical nano-structure includes at least one of a single-layer nano-grass structure or a double-layer nano-grass structure, and the step 2 specifically includes:
immersing the copper sheet into a prepared chemical solution for a first time to obtain copper hydroxide with a single-layer nano grass structure;
or immersing the copper sheet into the prepared chemical solution, and reacting for a second time to obtain the copper hydroxide with the double-layer nanometer grass flower structure;
wherein the first time period is not less than 5 minutes, and the second time period is not less than 10 minutes.
The beneficial effect of adopting the further scheme is that as the growth of the nano structure is changed into a double-layer structure from a single-layer structure along with the increase of the reaction time, in the scheme of the invention, the copper hydroxide with the nano structures of different levels can be obtained by controlling the reaction time between the copper sheet and the chemical solution, so that the preparation process of the copper hydroxide with the nano structures of single and double layers is simpler and more convenient to repeat.
Further, before the step 1, the method further comprises the following steps:
and performing impurity removal treatment on the copper sheet to obtain the copper sheet with impurities removed, wherein the impurity removal treatment comprises at least one of physical treatment or chemical treatment.
The copper sheet can be subjected to impurity removal treatment before the copper sheet is subjected to chemical reaction with the chemical solution, so that the impurities on the copper sheet influence the chemical reaction result during the chemical reaction.
Further, when the thickness of the copper sheet is greater than a set value, the step 2 specifically includes:
immersing the copper sheet into a prepared chemical solution at 40 ℃ for chemical reaction to obtain copper hydroxide with a hierarchical nano structure;
when the thickness of the copper sheet is not greater than a set value, the step 2 specifically includes:
and immersing the copper sheet into a prepared chemical solution at normal temperature to perform chemical reaction to obtain the copper hydroxide with the hierarchical nano structure.
The method has the advantages that when the thickness of the copper sheet is larger than the set value, in order to accelerate the reaction speed between the copper sheet and the chemical solution, the chemical solution can be kept at 40 ℃ for carrying out chemical reaction, so that the reaction speed between the copper sheet and the chemical solution is accelerated, and when the thickness of the copper sheet is not larger than the set value, the copper sheet and the chemical solution can carry out chemical reaction at normal temperature and normal pressure.
Further, the step 3 specifically includes:
and taking out the copper hydroxide with the hierarchical nano structure, cleaning, taking out the cleaned copper hydroxide, and naturally drying for 5 minutes at normal temperature to obtain the copper hydroxide with the super-hydrophilic characteristic.
The method has the advantages that in order to avoid chemical solution remaining on the surface of the generated copper hydroxide with the hierarchical nano structure, the copper hydroxide with the hierarchical nano structure can be taken out for cleaning, then the cleaned copper hydroxide is placed at normal temperature for drying, and the dried copper hydroxide (copper sheet) has super-hydrophilic characteristics and can be used for experimental research of heat transfer enhancement.
Further, the step 1 specifically includes: mixing the NaOH solution and (NH)4)2S2O8The solution is configured as a chemical solution having an oxidizing function.
The beneficial effect of adopting the further scheme is that the chemical solution with the oxidation function is more, and in the scheme of the invention, NaOH solution and (NH) are adopted4)2S2O8Compared with other oxidizing solutions, the oxidizing function of the chemical solution obtained by preparing the solution is better, and substances polluting air or harming body health are not generated in the reaction process.
Further, the above NaOH solution and (NH)4)2S2O8The preparation ratio of the solution is 250: 13.
the beneficial effect of adopting the further scheme is that the NaOH solution and (NH) with different concentrations are used4)2S2O8The chemical solution with the configured concentration has different chemical reaction effects with the copper sheet, and NaOH solution and (NH) in the chemical solution are obtained through experiments4)2S2O8The preparation ratio of the solution is 250: 13, the chemical solution prepared in the way has good chemical reaction effect with the copper sheet。
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments of the present invention will be briefly described below.
FIG. 1 is a flow chart of a method for preparing copper oxide according to an embodiment of the present invention;
FIG. 2 is a schematic diagram illustrating a relationship between a heating temperature and a contact angle according to another embodiment of the present invention;
FIG. 3 is a schematic flow chart of a method for preparing copper oxide according to another embodiment of the present invention;
FIG. 4 is a schematic diagram illustrating a transition between superhydrophilic and superhydrophobic according to an embodiment of the present invention;
FIG. 5 is a microscope photograph of a corresponding hierarchical nanostructured copper sheet reacted for 5 minutes according to one embodiment of the present invention;
FIG. 6 is a microscope image of a corresponding hierarchical nanostructured copper sheet reflecting for 10 minutes according to one embodiment of the present invention;
FIG. 7 is a microscope photograph of a corresponding hierarchical nanostructured copper sheet reacted for 20 minutes according to one embodiment of the present invention;
FIG. 8 is a microscope image of a copper sheet reflecting a corresponding hierarchical nanostructure for 40 minutes according to one embodiment of the present invention;
FIG. 9 is a schematic illustration of a contact angle of a superhydrophilic surface provided in accordance with an embodiment of the present invention;
fig. 10 is a schematic contact angle diagram of a superhydrophobic surface according to an embodiment of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The technical solution of the present invention and how to solve the above technical problems will be described in detail with specific embodiments below. The following several specific embodiments may be combined with each other, and details of the same or similar concepts or processes may not be repeated in some embodiments. Embodiments of the present invention will be described below with reference to the accompanying drawings.
The scheme provided by the embodiment of the invention can be suitable for any application scene needing to change the wettability of the surface structure of the copper oxide. An embodiment of the present invention provides a possible implementation manner, and as shown in fig. 1, provides a flowchart of a method for preparing copper oxide, and as shown in the flowchart of fig. 1, the method may include the following steps:
step S1, preparing a chemical solution with an oxidation function;
step S2, immersing the copper sheet into the prepared chemical solution for chemical reaction to obtain copper hydroxide with a hierarchical nano structure;
and step S3, taking out the copper hydroxide with the hierarchical nano structure, and drying the copper hydroxide to obtain the copper hydroxide with super-hydrophilic characteristics.
And step S4, dehydrating the copper hydroxide with the super-hydrophilic characteristic to obtain the copper oxide with the super-hydrophobic characteristic.
According to the method, the copper hydroxide with the hierarchical nano structure can be obtained through the configured chemical reaction between the chemical solution with the oxidation function and the copper sheet, the copper hydroxide with the super-hydrophilic characteristic can be obtained after the copper hydroxide with the hierarchical nano structure is washed and dried, the copper hydroxide with the super-hydrophilic characteristic is the copper sheet with the heat reaction type surface structure, namely the wettability of the nano structure of the copper sheet can be changed under the external condition.
The scheme of the present invention is further illustrated below with reference to the following specific examples, in which the preparation method of copper oxide of this embodiment may include the following steps:
step S1, a chemical solution having an oxidizing function is prepared.
The chemical solution with the oxidizing function refers to a chemical solution with oxidizing property, and can perform an oxidizing reaction with the copper sheet. The specific proportion of the chemical solution can be configured based on actual requirements. In practical application, NaOH solution and (NH) can be mixed4)2S2O8The solution is configured as a chemical solution having an oxidizing function. There are many chemical solutions having an oxidizing function, and in the embodiment of the present invention, specific components of the chemical solutions are not limited, and alternatively, NaOH solution and (NH) solution are used4)2S2O8Compared with other oxidizing solutions, the oxidizing function of the chemical solution obtained by preparing the solution is better, and substances polluting air or harming body health are not generated in the reaction process.
Due to different concentrations of NaOH solution and (NH)4)2S2O8The chemical solution with configured concentration has different chemical reaction effect with the copper sheet, and can be obtained through a great deal of experimental data, and in one alternative of the invention, the NaOH solution and the (NH)4)2S2O8The preparation ratio of the solution is 250: 13. experimental verification, in chemical solution, NaOH solution and (NH)4)2S2O8The preparation ratio of the solution is 250: 13, 2.5mol (NH) per liter of chemical solution containing NaOH solution4)2S2O8When the solution is 0.13mol, the chemical reaction effect of the chemical solution and the copper sheet is better.
Optionally, when the chemical solution is prepared, the volume of the chemical solution can be determined according to the volume of the copper sheet, for example, a copper sheet with the size of 10mm (length) × 10mm (width) × 2mm (thickness) can be used, and 30ml of deionized water (for example, DI water) can be taken corresponding to a 50ml beaker, and a NaOH solution with the concentration of 2.5mol/L and (NH) with the concentration of 0.13mol/L can be added4)2S2O8And uniformly stirring the solution to obtain a chemical solution. The prepared chemical solution needs to be kept still to normal temperature for use.
And step S2, immersing the copper sheet into the prepared chemical solution for chemical reaction to obtain the copper hydroxide with the hierarchical nano structure.
The normal temperature and pressure generally refers to a temperature of 25 degrees celsius and a pressure of one atmosphere.
Optionally, the copper sheet may be red copper with a thickness of 2mm and a purity of 99.9%. If the thickness of the copper sheet is over, the reaction speed between the copper sheet and the chemical solution may be affected, and therefore, in an alternative of the present invention, when the thickness of the copper sheet is greater than a set value (alternatively, the set value may be 2mm), the step 2 specifically includes:
immersing the copper sheet into a prepared chemical solution at 40 ℃ for chemical reaction to obtain copper hydroxide with a hierarchical nano structure;
when the thickness of the copper sheet is not more than a set value, the step 2 specifically comprises:
and immersing the copper sheet into a prepared chemical solution at normal temperature to perform chemical reaction to obtain the copper hydroxide with the hierarchical nano structure.
When the thickness of the copper sheet is larger than the set value, the thickness of the copper sheet is too large, which may affect the chemical reaction speed, so that in order to increase the reaction speed between the copper sheet and the chemical solution, the chemical solution may be maintained at 40 ℃ to increase the reaction speed between the copper sheet and the chemical solution. The above setting value can be configured based on actual requirements, for example, based on the reaction time between copper sheets with different thicknesses and the chemical solution. The above 40 degrees celsius may also be modified based on actual requirements, for example, based on the reaction time between the copper sheet and the chemical solution with the same thickness at different temperatures.
In practical applications, considering that the surface of the copper sheet may contain impurities which may affect the result of the chemical reaction between the copper sheet and the chemical solution, the above step 1 further includes:
and performing impurity removal treatment on the copper sheet to obtain the copper sheet with impurities removed, wherein the impurity removal treatment comprises at least one of physical treatment or chemical treatment.
Wherein, the physical treatment refers to removing impurities on the surface of the copper sheet by physical means, for example, polishing treatment is carried out by sand paper; the chemical treatment refers to removing impurities on the surface of the copper sheet by chemical means, for example, ultrasonic cleaning and drying treatment are carried out on the copper sheet by using a hydrochloric acid solution.
Optionally, if the impurity removal treatment includes physical treatment, and the physical treatment is polishing with sand paper, the impurity removal treatment is performed on the copper sheet, and an implementation manner of obtaining the copper sheet with the impurities removed is as follows: and (4) polishing the surface of the copper sheet by using sand paper to obtain the copper sheet with impurities removed. Alternatively, the sandpaper may be 2500grid sandpaper.
Optionally, if the impurity removal treatment includes a chemical treatment, where the chemical treatment is to perform ultrasonic cleaning on the copper sheet with a hydrochloric acid solution and perform drying treatment, the impurity removal treatment on the copper sheet to obtain the copper sheet with impurities removed may be performed in the following manner: and putting the copper sheet into a beaker filled with hydrochloric acid solution for ultrasonic cleaning, and drying the surface of the cleaned copper sheet by using compressed air, wherein the dried copper sheet is the copper sheet with impurities removed. Alternatively, the hydrochloric acid solution may be a dilute hydrochloric acid solution, that is, a hydrochloric acid solution with a mass fraction of less than 20%. The time period for ultrasonic cleaning of the copper sheet in the beaker with the hydrochloric acid solution can be 10 minutes.
Alternatively, if the impurity removing treatment includes a chemical treatment and a physical treatment, the treatment sequence of the chemical treatment and the physical treatment is not limited in the embodiment of the present invention, and the present invention is within the scope of the present invention.
Optionally, when the copper sheet is immersed in the prepared chemical solution for chemical reaction, the chemical solution can be stirred at the same time, so as to shorten the reaction time of the copper sheet and the chemical solution.
In the embodiment of the present invention, since the growth of the nanostructure may change from a single-layer structure to a double-layer structure with the increase of the reaction time, in the embodiment of the present invention, the copper hydroxide having different levels of nanostructures may be obtained by controlling the reaction time between the copper sheet and the chemical solution, and the step 2 specifically includes:
immersing the copper sheet into a prepared chemical solution for a first time to obtain copper hydroxide with a single-layer nano grass structure;
or immersing the copper sheet into the prepared chemical solution, and reacting for a second time to obtain the copper hydroxide with the double-layer nanometer grass flower structure;
wherein the first time period is not less than 5 minutes, and the second time period is not less than 10 minutes.
The first time period and the second time period may be set based on actual conditions, and optionally, the first time period is 5 minutes, and the second time period is 10 minutes. One layer of the double-layer nanometer grass flower structure is a nanometer grass structure, and the other layer of the double-layer nanometer grass flower structure is a nanometer flower structure. By the mode, if copper hydroxide with a single-layer nanometer grass structure is obtained, the copper sheet can be controlled to be immersed into the prepared chemical solution for the first time, and at the moment, the reacted copper sheet can be taken out for subsequent treatment. And if the copper hydroxide with the double-layer nanometer grass flower structure is obtained, the copper sheet can be controlled to be immersed into the prepared chemical solution for reaction for a second time, and at the moment, the reacted copper sheet is taken out for subsequent treatment.
Step S3, the copper hydroxide with the hierarchical nano-structure is taken out and dried (e.g., naturally dried at room temperature), so as to obtain the copper hydroxide with super-hydrophilic characteristics.
In order to avoid the chemical solution remaining on the surface of the generated hierarchical nano-structured copper hydroxide, in an alternative embodiment of the present invention, the step 3 specifically includes:
and taking out the copper hydroxide with the hierarchical nano structure, cleaning, taking out the cleaned copper hydroxide, and naturally drying for 5 minutes at normal temperature to obtain the copper hydroxide with the super-hydrophilic characteristic.
In an alternative scheme of the invention, the taken-out copper hydroxide with the hierarchical nano structure can be cleaned by deionized water (DI water), optionally for 1 minute, to obtain the cleaned copper hydroxide, and then the cleaned copper hydroxide is placed at normal temperature for natural drying, so that the surface of the copper sheet has no moisture, and the dried copper hydroxide (copper sheet) has super-hydrophilic characteristics and can be used for experimental research of heat transfer enhancement.
And step S4, dehydrating the copper hydroxide with the super-hydrophilic characteristic to obtain the copper oxide with the super-hydrophobic characteristic.
Optionally, one implementation manner of the step 4 of performing dehydration on the copper hydroxide with super-hydrophilic property is as follows: and (3) placing the copper hydroxide with the super-hydrophilic characteristic in an environment of 200 ℃ for dehydration treatment for 60 minutes. There are many ways of heating, for example, placing the heating plate on a heating table for heating, or placing the heating plate in a thermostat higher than normal temperature for heating, or welding for heating.
After the dehydration treatment, the dehydrated copper oxide needs to be cooled to room temperature.
Alternatively, the temperature of the oven may be 200 degrees celsius, and the time of the dehydration treatment may be 60 minutes.
After obtaining the copper oxide with the super-hydrophobic characteristic, further processing the copper oxide with the super-hydrophobic characteristic to obtain the copper oxide with the super-hydrophilic characteristic, namely, realizing the conversion between the super-hydrophilic characteristic and the super-hydrophobic characteristic, wherein the specific implementation mode is as follows: and (3) placing the copper oxide with the super-hydrophobic characteristic in deionized water at 120 ℃ for heating in the deionized water liquid to obtain the copper oxide with the super-hydrophilic characteristic.
In the scheme of the invention, the copper oxide with the super-hydrophobic characteristic is placed in deionized water to be heated (external conditions), the contact angle of the surface of the copper sheet is gradually reduced along with the increase of the temperature, the wettability of the surface of the nano structure can be changed from super-hydrophobic to super-hydrophilic, and the copper oxide with the super-hydrophilic characteristic can be obtained after heating.
According to the scheme of the invention, the contact angle of the copper oxide with the super-hydrophobic characteristic is gradually reduced along with the increase of the heating temperature, the contact angle of the copper oxide with the super-hydrophobic characteristic is smaller, the super-hydrophobic characteristic is less obvious, and the super-hydrophobic characteristic can be converted into super-hydrophilicity along with the reduction of the contact angle. Specifically, referring to fig. 2, which is a schematic diagram illustrating a change of the Contact angle corresponding to different heating temperatures, where the abscissa (Temperature) in fig. 2 is the heating Temperature, and the ordinate is the Contact angle (Contact angle), as can be seen from fig. 2, the Contact angle gradually decreases with an increase of the heating Temperature, for example, at 100 degrees celsius, the corresponding Contact angle is 150 degrees, at 110 degrees celsius, the corresponding Contact angle is 90 degrees celsius, and at 120 degrees celsius, the corresponding Contact angle is 10 degrees. When the contact angle is 10 degrees, the copper oxide at this time is super-hydrophilic.
For a better illustration and understanding of the principles of the method provided by the present invention, the solution of the invention is described below with reference to an alternative embodiment. It should be noted that the specific implementation manner of each step in this specific embodiment should not be construed as a limitation to the scheme of the present invention, and other implementation manners that can be conceived by those skilled in the art based on the principle of the scheme provided by the present invention should also be considered as within the protection scope of the present invention.
In this embodiment, referring to the flow chart of a method for preparing copper hydroxide or copper oxide shown in fig. 3, the method may include the following steps:
And 3, immersing the treated copper sheet into the chemical solution prepared in the step 2 under normal pressure, stirring the solution, reacting for 5 minutes to obtain copper hydroxide with a single-layer nanometer grass structure (shown as (3) in fig. 3), gradually changing the single-layer nanometer grass structure into a double-layer nanometer grass structure with the increase of the reaction time to obtain copper hydroxide with the double-layer nanometer grass structure (shown as (4) in fig. 3), wherein the upper layer of the double-layer nanometer grass structure is of the nanometer grass structure, the lower layer of the double-layer nanometer grass structure is of the nanometer grass structure, and the density of the single-layer nanometer grass structure changes with the increase of the reaction time.
As an example, see the microscope images of the corresponding hierarchical nanostructured copper sheets at different reaction times shown in fig. 5-8; after the treated copper sheet is immersed in the chemical solution prepared in the step 2 and the solution is stirred to react for 5 minutes, copper hydroxide with a single-layer nanometer grass structure as shown in fig. 5 can be obtained. And reacting for 5 minutes (after the copper sheet is immersed in the chemical solution, the reaction lasts for 10 minutes totally), and stirring is not carried out, so that the copper sheet with the double-layer nanometer grass flower structure shown in the figure 6 can be obtained, wherein the upper layer is the sparse nanometer flower structure, and the lower layer is the nanometer grass structure. The reaction is continued for 10 minutes (after the copper sheet is immersed in the chemical solution, the reaction lasts for 20 minutes totally), the solution is not stirred, and the copper sheet with the double-layer nanometer grass flower structure shown in figure 7 can be obtained, wherein the upper layer is the medium-density nanometer flower structure, and the lower layer is the nanometer grass structure. The reaction is continued for 20 minutes (after the copper sheet is immersed in the chemical solution, the reaction lasts for 40 minutes totally), the solution is not stirred, and the copper sheet with the double-layer nanometer grass flower structure shown in fig. 8 can be obtained, wherein the upper layer is the dense nanometer flower structure, and the lower layer is the nanometer grass structure.
And 4, taking out the copper sheet with the grown hierarchical nano structure (at least one of copper hydroxide with a single-layer nano grass structure or copper hydroxide with a double-layer nano grass structure), washing the copper sheet with DI water for 1 minute to ensure that no chemical solution is remained on the surface of the copper sheet, and standing and drying the washed copper sheet at room temperature for 5 minutes to obtain the copper sheet with the super-hydrophilic characteristic.
And 5, placing the copper sheet with the super-hydrophilic characteristic obtained in the step 4 in a constant temperature box (shown as (5) in fig. 3) with the temperature of 200 ℃ for heating for 60 minutes to perform dehydration treatment, so that the copper hydroxide is changed into copper oxide, placing the copper sheet after the dehydration treatment in a normal temperature to cool to the normal temperature, and enabling the cooled copper sheet to have the super-hydrophobic characteristic.
And 6, placing the copper sheet with the super-hydrophobic characteristic obtained in the step 5 on a heating table ((7) shown in fig. 3), heating the copper sheet in an environment of DI water ((6) shown in fig. 3), wherein the heating temperature is 120 ℃, and the contact angle of the surface of the copper sheet is gradually reduced along with the increase of the temperature, so that the copper sheet becomes the copper sheet with the super-hydrophilic characteristic.
In the scheme of the invention, by the method, conversion from super-hydrophilic to super-hydrophobic and from super-hydrophobic to super-hydrophilic can be realized, specifically, refer to a schematic diagram of conversion between super-hydrophilic and super-hydrophobic shown in fig. 4, a first step shows a nano structure with super-hydrophilic characteristics (the copper sheet with super-hydrophilic characteristics obtained in step 4), in step 5, the copper sheet with super-hydrophilic characteristics is placed in a constant temperature cabinet with a temperature of 200 ℃ for 60 minutes to be dehydrated (corresponding to heating 200 ℃ shown in fig. 4), and then the dehydrated copper sheet is placed in a constant temperature cabinet to be cooled to the normal temperature (corresponding to natural cooling shown in fig. 4), so that the copper sheet with super-hydrophobic characteristics (corresponding to cooling device shown in fig. 4) is obtained. And 6, placing the copper sheet with the super-hydrophobic characteristic on a heating table, heating the copper sheet in the DI water environment at the heating temperature of 100-120 ℃, and gradually reducing the contact angle of the surface of the copper sheet along with the temperature rise to finally form the copper sheet with the super-hydrophilic characteristic (shown in the third figure 4).
The contact angle of the superhydrophilic surface can be seen in fig. 9, and the contact angle of the superhydrophobic surface can be seen in fig. 10, wherein the contact angle corresponding to the superhydrophilic characteristic is not greater than 15 degrees, and the contact angle corresponding to the superhydrophobic characteristic is greater than 150 degrees.
Through the scheme of the invention, the following beneficial effects are achieved:
in the first aspect, the solution of the present invention can realize the generation of copper hydroxide with a hierarchical nano structure under normal pressure and temperature, the method is simple, the manufacturing process does not generate substances (such as fluoropolymer) polluting air or harmful to human health, and the method has a short reaction time (based on the foregoing description, the reaction time is approximately between 81 minutes and 116 minutes, and the reaction time is typically 7 to 14 hours in the prior art), and the cost is low.
In a second aspect, the density of the upper layer nanostructures in the hierarchical nanostructure can be controlled by controlling the reaction time.
In a third aspect, the wettability (superhydrophobicity and ultraphobicity) of the nanostructured surface can be reversibly switched under external heating conditions.
The foregoing description is only exemplary of the preferred embodiments of the invention and is illustrative of the principles of the technology employed. It will be appreciated by those skilled in the art that the scope of the disclosure herein is not limited to the particular combination of features described above, but also encompasses other embodiments in which any combination of the features described above or their equivalents is encompassed without departing from the spirit of the disclosure. For example, the above features and (but not limited to) features having similar functions disclosed in the present invention are mutually replaced to form the technical solution.
Claims (9)
1. The preparation method of the copper oxide is characterized by comprising the following steps:
step 1, preparing a chemical solution with an oxidation function;
step 2, immersing a copper sheet into the prepared chemical solution for chemical reaction to obtain copper hydroxide with a hierarchical nano structure;
step 3, taking out the copper hydroxide with the hierarchical nano structure, and drying to obtain the copper hydroxide with super-hydrophilic property;
and 4, dehydrating the copper hydroxide with the super-hydrophilic characteristic to obtain copper oxide with the super-hydrophobic characteristic.
2. The method of claim 1, wherein step 4 is further followed by:
and 5, heating the copper oxide with the super-hydrophobic characteristic in deionized water at 120 ℃ to obtain the copper oxide with the super-hydrophilic characteristic.
3. The method according to claim 1, wherein the step 4 specifically comprises:
and (3) placing the copper hydroxide with the super-hydrophilic characteristic in an environment of 200 ℃ for dehydration treatment for 60 minutes to obtain the copper oxide with the super-hydrophobic characteristic.
4. The method according to any one of claims 1 to 3, wherein the hierarchical nanostructure comprises at least one of a single-layer nanograss structure or a double-layer nanograss structure, and wherein the step 2 specifically comprises:
immersing the copper sheet into the prepared chemical solution for a first time to react to obtain copper hydroxide with a single-layer nano grass structure;
or immersing the copper sheet into the prepared chemical solution, and reacting for a second time to obtain the copper hydroxide with the double-layer nanometer grass flower structure;
wherein the first time period is not less than 5 minutes, and the second time period is not less than 10 minutes.
5. The method according to any one of claims 1 to 3, characterized by further comprising, before step 1, the steps of:
and carrying out impurity removal treatment on the copper sheet to obtain the copper sheet with impurities removed, wherein the impurity removal treatment comprises at least one of physical treatment or chemical treatment.
6. The method according to any one of claims 1 to 3, wherein when the thickness of the copper sheet is greater than a predetermined value, the step 2 specifically comprises:
immersing the copper sheet into a prepared chemical solution at 40 ℃ for chemical reaction to obtain copper hydroxide with a hierarchical nano structure;
when the thickness of the copper sheet is not greater than the set value, the step 2 specifically includes:
and immersing the copper sheet into a prepared chemical solution at normal temperature to perform chemical reaction to obtain the copper hydroxide with the hierarchical nano structure.
7. The method according to any one of claims 1 to 3, wherein the step 3, in particular, comprises:
and taking out the copper hydroxide with the hierarchical nano structure for cleaning, taking out the cleaned copper hydroxide, and naturally drying for 5 minutes at normal temperature to dry the surface of the cleaned copper hydroxide, thereby obtaining the copper hydroxide with super-hydrophilic characteristics.
8. The method according to any one of claims 1 to 3, wherein the step 1 specifically comprises:
mixing the NaOH solution and (NH)4)2S2O8The solution is configured as the chemical solution having an oxidizing function.
9. The method of claim 8, wherein the NaOH solution and the (NH) are4)2S2O8The preparation ratio of the solution is 250: 13.
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| CN115744961A (en) * | 2022-11-09 | 2023-03-07 | 天津大学 | Preparation method and device of structurally-controllable super-hydrophilic copper-based compound material |
| CN117101186A (en) * | 2023-06-21 | 2023-11-24 | 中南民族大学 | Method for regulating and controlling wettability of oil-water separation material |
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| CN110029349A (en) * | 2019-04-08 | 2019-07-19 | 青岛大学 | A kind of preparation and regulation method of super-hydrophobic/super hydrophilic reversible adjusting metal surface |
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| CN110029349A (en) * | 2019-04-08 | 2019-07-19 | 青岛大学 | A kind of preparation and regulation method of super-hydrophobic/super hydrophilic reversible adjusting metal surface |
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| CN115744961A (en) * | 2022-11-09 | 2023-03-07 | 天津大学 | Preparation method and device of structurally-controllable super-hydrophilic copper-based compound material |
| CN115744961B (en) * | 2022-11-09 | 2024-03-22 | 天津大学 | Preparation method and device of structure-controllable super-hydrophilic copper-based compound material |
| CN117101186A (en) * | 2023-06-21 | 2023-11-24 | 中南民族大学 | Method for regulating and controlling wettability of oil-water separation material |
| CN117101186B (en) * | 2023-06-21 | 2024-04-02 | 中南民族大学 | Method for regulating and controlling wettability of oil-water separation material |
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