CN111019148B - Modified foamed copper material and preparation method and application thereof - Google Patents
Modified foamed copper material and preparation method and application thereof Download PDFInfo
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- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
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Abstract
The invention discloses a modified foamy copper material and a preparation method and application thereof, belonging to the technical field of super-hydrophobic treatment. The preparation method of the modified foam copper material comprises the following steps: carrying out activation pretreatment on the foamy copper, and removing an oxide film on the surface of the foamy copper to obtain the treated foamy copper; mixing the growth liquid and the treated foamy copper, and reacting at the temperature of 100-140 ℃ to obtain a reaction product; and cleaning and drying the reaction product, then soaking the reaction product in a hexadecanethiol solution, and drying the soaked reaction product to obtain the modified foamed copper material. The modified copper foam material has excellent corrosion resistance, higher oil-water separation efficiency, excellent friction resistance and anti-adhesion performance, and can be used for solving the problems of corrosion, oily wastewater treatment, frosting, icing and the like which are easy to occur in production and life.
Description
Technical Field
The invention relates to the technical field of super-hydrophobic treatment, in particular to a modified copper foam material and a preparation method and application thereof.
Background
With the continuous development of science and technology, researchers can realize oil-water separation by constructing a super-hydrophobic surface and enabling the super-hydrophobic surface to have super-oleophilic/super-hydrophobic characteristics. In recent years, Metal Organic Framework (MOFs) materials have been widely used in many fields, such as gas separation, sensing, adsorption, catalysis, proton sensing, etc., and since MOFs can exhibit excellent micro-nano-scale surface chemical properties on many substrates, MOFs-based films and nets with special wettability have been widely used in the oil-water separation field.
The HKUST-1 is a typical MOFs material, has a face-centered cubic structure, a nano channel and adjustable porosity, and has the potential of constructing a super-hydrophobic surface and realizing oil-water separation. However, the existing hydrophobic material constructed by HKUST-1, such as HKUST-1 modified copper Foam material (Cu Foam, CF), still has the problems of poor hydrophobicity, complex preparation process and the like.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method of a modified copper foam material, so as to solve the problems in the background technology.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a preparation method of a modified foam copper material comprises the following steps:
carrying out activation pretreatment on the foamy copper, and removing an oxide film on the surface of the foamy copper to obtain the treated foamy copper;
dissolving copper nitrate trihydrate and trimesic acid in absolute ethyl alcohol to obtain a growth solution;
mixing the growth liquid and the treated foamy copper, and reacting at the temperature of 100-140 ℃ to obtain a reaction product;
and cleaning and drying the reaction product, then soaking the reaction product in a hexadecanethiol solution, and then drying the soaked reaction product to obtain the modified foamed copper material.
As another preferable embodiment of the present invention, the method of pre-activation treatment includes the following steps:
firstly, soaking the foamy copper in hydrochloric acid, then ultrasonically cleaning the foamy copper by using acetone, ethanol and distilled water, and then drying the foamy copper after ultrasonic cleaning to obtain the processed foamy copper.
As another preferable scheme of the embodiment of the invention, the concentration of the hydrochloric acid is 0.1-0.3 mol/L.
In another preferable embodiment of the invention, the molar ratio of the copper nitrate trihydrate to the trimesic acid is (3-7): 1.
As another preferable mode of the embodiment of the present invention, the molar ratio of the copper nitrate trihydrate to the trimesic acid is 4: 1.
As another preferable scheme of the embodiment of the invention, in the step of mixing the growth liquid and the treated copper foam and reacting at the temperature of 100-140 ℃, the reaction time is 10-14 h.
As another preferable scheme of the embodiment of the invention, in the step of soaking the reaction product in a hexadecanethiol solution after cleaning and drying, the soaking time is 2-5 hours.
The embodiment of the invention also aims to provide a modified foam copper material prepared by the preparation method.
Another object of the embodiments of the present invention is to provide a use of the modified copper foam material as a hydrophobic material.
The embodiment of the invention also aims to provide an application of the modified copper foam material in oil-water separation.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
the preparation method of the modified copper foam material provided by the embodiment of the invention has the characteristics of rapidness, simplicity and convenience and low cost, and utilizes Cu in copper nitrate2+The modified foam copper material is coordinated with carboxyl in trimesic acid, an HKUST-1 framework material with a microporous structure is synthesized in situ on the surface of the foam copper, and then a hydrophobic long chain in Hexadecanethiol (HDT) is grafted to the surface of copper, so that the surface free energy of the material is reduced, and the modified foam copper material with the HKUST-1/HDT/CF superhydrophobic surface can be prepared. The modified foamed copper material prepared by the embodiment of the invention has excellent corrosion resistance, higher oil-water separation efficiency, excellent friction resistance and excellent adhesion resistance, and can be used for solving the problems of corrosion, oily wastewater treatment, frosting, icing and the like which are easy to occur in production and life.
Drawings
FIG. 1 is an infrared spectrum of HKUST-1, HDT, HKUST-1/CF and the modified copper foam material obtained in example 4.
FIG. 2 is the contact angle change curve chart of the modified foam copper material obtained when the molar ratio of the copper nitrate trihydrate to the benzenetricarboxylic acid is different.
FIG. 3 is a diagram showing the contact-to-separation process of the surface of the modified copper foam material obtained in example 4 and water droplets.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a modified foamed copper material and a preparation method thereof, wherein the preparation method of the modified foamed copper material comprises the following steps:
(1) carrying out activation pretreatment on the foamy copper, and removing an oxide film on the surface of the foamy copper to obtain the treated foamy copper; specifically, firstly, selecting foamed copper with the thickness of 3mm, cutting the foamed copper into 2cm multiplied by 2cm, soaking the foamed copper in 0.1mol/L hydrochloric acid for 10min, then carrying out ultrasonic cleaning on the soaked foamed copper for 10min by using acetone, ethanol and distilled water, and then drying the foamed copper subjected to ultrasonic cleaning to obtain the treated foamed copper for later use.
(2) 3mmol of copper nitrate trihydrate and 1mmol of trimesic acid are dissolved in 20mL of absolute ethyl alcohol to obtain a growth solution.
(3) Mixing the growth liquid and the treated foamy copper, and placing the mixture in a stainless steel reactor kettle with a polytetrafluoroethylene lining at 100 ℃ for reaction for 14 hours to obtain a reaction product, namely the HKUST-1/CF material.
(4) And cleaning and drying the reaction product by using absolute ethyl alcohol, then soaking the reaction product in a hexadecanethiol solution for 2 hours, and then drying the soaked reaction product to obtain the modified foamed copper material, namely the HKUST-1/HDT/CF material.
Example 2
The embodiment provides a modified foamed copper material and a preparation method thereof, wherein the preparation method of the modified foamed copper material comprises the following steps:
(1) carrying out activation pretreatment on the foamy copper, and removing an oxide film on the surface of the foamy copper to obtain the treated foamy copper; specifically, firstly, selecting foamed copper with the thickness of 3mm, cutting the foamed copper into 2cm multiplied by 2cm, soaking the foamed copper in 0.3mol/L hydrochloric acid for 10min, then carrying out ultrasonic cleaning on the soaked foamed copper for 10min by using acetone, ethanol and distilled water, and then drying the foamed copper subjected to ultrasonic cleaning to obtain the treated foamed copper for later use.
(2) 7mmol of copper nitrate trihydrate and 1mmol of trimesic acid are dissolved in 20mL of absolute ethyl alcohol to obtain a growth solution.
(3) Mixing the growth liquid and the treated foamy copper, and placing the mixture in a stainless steel reactor kettle with a polytetrafluoroethylene lining at 140 ℃ for reaction for 10 hours to obtain a reaction product, namely the HKUST-1/CF material.
(4) And cleaning and drying the reaction product by using absolute ethyl alcohol, then soaking the reaction product in a hexadecanethiol solution for 5 hours, and then drying the soaked reaction product to obtain the modified foamed copper material, namely the HKUST-1/HDT/CF material.
Example 3
The embodiment provides a modified foamed copper material and a preparation method thereof, wherein the preparation method of the modified foamed copper material comprises the following steps:
(1) carrying out activation pretreatment on the foamy copper, and removing an oxide film on the surface of the foamy copper to obtain the treated foamy copper; specifically, firstly, selecting foamed copper with the thickness of 3mm, cutting the foamed copper into 2cm multiplied by 2cm, soaking the foamed copper in 0.1mol/L hydrochloric acid for 10min, then carrying out ultrasonic cleaning on the soaked foamed copper for 10min by using acetone, ethanol and distilled water, and then drying the foamed copper subjected to ultrasonic cleaning to obtain the treated foamed copper for later use.
(2) 3mmol of copper nitrate trihydrate and 1mmol of trimesic acid are dissolved in 20mL of absolute ethyl alcohol to obtain a growth solution.
(3) Mixing the growth liquid and the treated foamy copper, and placing the mixture in a stainless steel reactor kettle with a polytetrafluoroethylene lining at 120 ℃ for reaction for 13 hours to obtain a reaction product, namely the HKUST-1/CF material.
(4) And cleaning and drying the reaction product by using absolute ethyl alcohol, then soaking the reaction product in a hexadecanethiol solution for 2 hours, and then drying the soaked reaction product to obtain the modified foamed copper material, namely the HKUST-1/HDT/CF material.
Example 4
The embodiment provides a modified foamed copper material and a preparation method thereof, wherein the preparation method of the modified foamed copper material comprises the following steps:
(1) carrying out activation pretreatment on the foamy copper, and removing an oxide film on the surface of the foamy copper to obtain the treated foamy copper; specifically, firstly, selecting foamed copper with the thickness of 3mm, cutting the foamed copper into 2cm multiplied by 2cm, soaking the foamed copper in 0.1mol/L hydrochloric acid for 10min, then carrying out ultrasonic cleaning on the soaked foamed copper for 10min by using acetone, ethanol and distilled water, and then drying the foamed copper subjected to ultrasonic cleaning to obtain the treated foamed copper for later use.
(2) 4mmol of copper nitrate trihydrate and 1mmol of trimesic acid are dissolved in 20mL of absolute ethyl alcohol to obtain a growth solution.
(3) Mixing the growth liquid and the treated foamy copper, and placing the mixture in a stainless steel reactor kettle with a polytetrafluoroethylene lining at 120 ℃ for reaction for 13 hours to obtain a reaction product, namely the HKUST-1/CF material.
(4) And cleaning and drying the reaction product by using absolute ethyl alcohol, then soaking the reaction product in a hexadecanethiol solution for 2 hours, and then drying the soaked reaction product to obtain the modified foamed copper material, namely the HKUST-1/HDT/CF material.
Example 5
This example provides a modified copper foamy material and a method for producing the same, wherein the method for producing the modified copper foamy material is the same as in example 4 except that "4 mmol of copper nitrate trihydrate" in step (2) is replaced with "5 mmol of copper nitrate trihydrate".
Example 6
This example provides a modified copper foamy material and a method for producing the same, wherein the method for producing the modified copper foamy material is the same as in example 4 except that "4 mmol of copper nitrate trihydrate" in step (2) is replaced with "6 mmol of copper nitrate trihydrate".
Example 7
This example provides a modified copper foamy material and a method for producing the same, wherein the method for producing the modified copper foamy material is the same as in example 4 except that "4 mmol of copper nitrate trihydrate" in step (2) is replaced with "7 mmol of copper nitrate trihydrate".
Example 8
This example provides a modified copper foam material and a method for producing the same, wherein the method for producing the modified copper foam material is the same as in example 4 except that the reaction time in step (3) is changed from "13 h" to "10 h".
Example 9
This example provides a modified copper foam material and a method for producing the same, wherein the method for producing the modified copper foam material is the same as in example 4 except that the reaction time in step (3) is changed from "13 h" to "11 h".
Example 10
This example provides a modified copper foam material and a method for producing the same, wherein the method for producing the modified copper foam material is the same as in example 4 except that the reaction time in step (3) is changed from "13 h" to "12 h".
Example 11
This example provides a modified copper foam material and a method for producing the same, wherein the method for producing the modified copper foam material is the same as in example 4 except that the reaction time in step (3) is changed from "13 h" to "14 h".
Example 12
This example provides a modified copper foam material and a method for producing the same, wherein the method for producing the modified copper foam material is the same as in example 4 except that the soaking time in step (4) is changed from "2 h" to "3 h".
Example 13
This example provides a modified copper foam material and a method for producing the same, wherein the method for producing the modified copper foam material is the same as in example 4 except that the soaking time in step (4) is changed from "2 h" to "4 h".
Example 14
This example provides a modified copper foam material and a method for producing the same, wherein the method for producing the modified copper foam material is the same as in example 4 except that the soaking time in step (4) is changed from "2 h" to "5 h".
Comparative example 1
This comparative example provides a treated Copper Foam (CF) which was treated in the same manner as in step (1) of example 4.
Comparative example 2
This comparative example provides an HKUST-1/CF material prepared as follows:
(1) carrying out activation pretreatment on the foamy copper, and removing an oxide film on the surface of the foamy copper to obtain the treated foamy copper; specifically, firstly, selecting foamed copper with the thickness of 3mm, cutting the foamed copper into 2cm multiplied by 2cm, soaking the foamed copper in 0.1mol/L hydrochloric acid for 10min, then carrying out ultrasonic cleaning on the soaked foamed copper for 10min by using acetone, ethanol and distilled water, and then drying the foamed copper subjected to ultrasonic cleaning to obtain the treated foamed copper for later use.
(2) 4mmol of copper nitrate trihydrate and 1mmol of trimesic acid are dissolved in 20mL of absolute ethyl alcohol to obtain a growth solution.
(3) Mixing the growth liquid and the treated foamy copper, and placing the mixture in a stainless steel reactor kettle with a polytetrafluoroethylene lining at 120 ℃ for reaction for 13 hours to obtain a reaction product, namely the HKUST-1/CF material.
Comparative example 3
This comparative example provides an HDT/CF material prepared as follows:
(1) carrying out activation pretreatment on the foamy copper, and removing an oxide film on the surface of the foamy copper to obtain the treated foamy copper; specifically, firstly, selecting foamed copper with the thickness of 3mm, cutting the foamed copper into 2cm multiplied by 2cm, soaking the foamed copper in 0.1mol/L hydrochloric acid for 10min, then carrying out ultrasonic cleaning on the soaked foamed copper for 10min by using acetone, ethanol and distilled water, and then drying the foamed copper subjected to ultrasonic cleaning to obtain the treated foamed copper for later use.
(2) And (3) soaking the treated foamy copper in a hexadecanethiol solution for 2h, and then drying the soaked reaction product to obtain the HDT/CF material.
Comparative example 4
This comparative example provides a modified copper foam material, wherein the production method of the modified copper foam material was the same as in example 4 except that "4 mmol of copper nitrate trihydrate" in step (2) was replaced with "1 mmol of copper nitrate trihydrate".
Comparative example 5
This comparative example provides a modified copper foam material, wherein the production process of the modified copper foam material was the same as in example 4 except that "4 mmol of copper nitrate trihydrate" in step (2) was replaced with "2 mmol of copper nitrate trihydrate".
Comparative example 6
This comparative example provides a modified copper foam material, wherein the production method of the modified copper foam material was the same as in example 4 except that "4 mmol of copper nitrate trihydrate" in step (2) was replaced with "8 mmol of copper nitrate trihydrate".
Comparative example 7
This comparative example provides a modified copper foam material, which was prepared in the same manner as in example 4 except that the reaction time in step (3) was changed from "13 h" to "9 h".
Comparative example 8
This example provides a modified copper foam material, wherein the method for preparing the modified copper foam material is the same as in example 4 except that the soaking time in step (4) is changed from "2 h" to "1 h".
The modified copper foamy material (HKUST-1/HDT/CF) obtained in example 4, the conventional HKU ST-1 material, Hexadecanethiol (HDT) and the HKUST-1/CF material obtained in comparative example 2 were respectively subjected to infrared spectrum tests, and the corresponding obtained infrared spectrum is shown in FIG. 1, wherein curve i is HKUS T-1; curve ii is HDT; curve iii is HKUST-1/CF; curve iv is HKUST-1/HDT/CF. As can be seen from i in FIG. 1, the peak of benzene ring bending is 731cm-1Appears, and the peak of benzene ring vibration appears at 1150cm-1(ii) a Due to the bending of the C-H bond, the bending strength is 1111cm-1A peak appears; characteristic peak of-COOH group in HKUST-1 ranges from 1150 to 1700cm-1. Ii in FIG. 1, at 2750cm-1The characteristic peak appearing there is the peak of-SH in the thiol. As can be seen from iii in FIG. 1, HKUST-1 was still observedThe peak of COOH, indicating that HKUST-1 grown in situ in the HKUST-1/CF material was not destroyed. As can be seen from iv in FIG. 1, both HKUST-1 and mercaptan are present in the modified copper foam material, i.e., a peak of-COOH and a peak of-SH are present, which indicates that the structure of HKUST-1 in the modified copper foam material is not destroyed all the time, and mercaptan is only grafted to the surface of the copper foam material to perform surface modification, thereby reducing the surface energy.
The materials obtained in example 4 and comparative examples 1 to 3 were subjected to a contact angle (angle between the gas-liquid interface and the solid-liquid interface tension) test with water, and the test results are shown in table 1.
TABLE 1
| Test items | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Contact angle (°) | 159.5 | 136.5 | 0 | 151.2 |
The contact angle test of the materials obtained in the above examples 3 to 7 and comparative examples 4 to 6 with water is shown in the attached figure 2, wherein the abscissa in the figure is the corresponding molar ratio of the copper nitrate trihydrate to the trimesic acid. As can be seen from the figure, when the molar ratio of the copper nitrate trihydrate to the trimesic acid is 4:1, the contact angle of the surface of the produced modified copper foam material with water is the largest, because when the ratio of the metal to the stoichiometric amount of the ligand is 4:1, the ligand can be sufficiently coordinated in a multidentate form, and the metal will have unsaturated sites, the structural framework of the produced HKU ST-1 is more stable than that of the ligand in a monodentate form, and the contact angle is also the largest. When the molar ratio is less than or greater than 4:1, when the ligand is subjected to multidentate coordination, the ligand is insufficient or excessive, and the formed HKUST-1 framework and the reached water contact angle are not optimal.
The contact angle test of the materials obtained in example 4, examples 8 to 11, and comparative example 7 with water was performed, and the test results are shown in table 2.
TABLE 2
| Test items | Example 4 | Example 8 | Example 9 | Example 10 | Example 11 | Comparative example 7 |
| Contact angle (°) | 159.5 | 155.3 | 156.4 | 158.4 | 159.3 | 151.1 |
The contact angle test of the materials obtained in example 4, examples 12 to 14, and comparative example 8 with water was performed, and the test results are shown in table 3.
TABLE 3
| Test items | Example 4 | Example 12 | Example 13 | Example 14 | Comparative example 8 |
| Contact angle (°) | 159.5 | 159.9 | 160.2 | 159.4 | 154.1 |
The modified copper foam material obtained in the example 4 is subjected to an oil-water separation performance test, wherein the oil-water mixture used in the test is carbon tetrachloride and distilled water in a volume ratio of 1:1, the water is dyed by methylene blue, and the oil is dyed by a threo-dye reagent. After the experiment is finished, the oil-water separation rate is calculated according to the oil-water content before and after separation, and the oil-water separation rate measured by the test is 95.6%.
The modified copper foam material obtained in the above example 4 was subjected to a water pressure performance test, and the test result was: the maximum water pressure which can be borne by the modified foam copper material with the diameter of 1cm is 10 cm.
The modified copper foam material obtained in the above example 4 was subjected to a friction resistance test, the test method being: the sample was placed down on sandpaper using sandpaper (2000 mesh) as a rubbing surface, and then pulled in the same direction at a speed of 5mm/s under a pressure of a 50g weight for different distances, and a contact angle test with water was performed every 10cm of pulling, and the test results are shown in table 4.
TABLE 4
| Dragging distance (cm) | 10 | 20 | 30 | 40 | 50 |
| Contact angle (°) | 159.5 | 158.4 | 150.0 | 137.1 | 135.4 |
As can be seen from table 4 above, the contact angle value decreases gradually but still exceeds 90 ° with increasing dragging distance. After the dragging distance is 50cm, the modified copper foam material still has strong hydrophobic property, which indicates that the modified copper foam material obtained in the embodiment of the invention has better friction resistance and more stable hydrophobic property.
The modified copper foam material obtained in the above example 4 was subjected to a durability test by the following method: the modified foamed copper material is placed in a beaker filled with ethanol by an ultrasonic destruction method, ultrasonic destruction is continuously carried out at the frequency of 40KHz, contact angles are measured once at intervals, and the test results are shown in Table 5.
TABLE 5
| Ultrasonic destruction time (min) | 0 | 20 | 40 | 60 | 80 |
| Contact angle (°) | 159.5 | 157.4 | 152.1 | 146.1 | 142.0 |
From the above table 5, it can be known that when the ultrasonic damage time is greater than 40min, the copper foam substrate starts to change from the super-hydrophobic state to the hydrophobic state, i.e. the contact angle starts to be less than 150 °, and as the ultrasonic damage time further increases, the contact angle starts to become smaller but still has stronger hydrophobicity, which indicates that the modified copper foam material obtained in the embodiment of the invention has better durability.
The modified copper foam material obtained in the above example 4 was subjected to a self-cleaning test, which was carried out by the following steps: the water drops are in adhesive contact with the surface of the modified copper foam material, extruded and separated by the microsyringe, the test process is shown in figure 3, and the figure shows that the water drops are obviously deformed but still remain on the needle point of the microsyringe after separation, and no residual liquid drops are left on the surface of the copper foam material, which shows that the copper foam material can obviously reduce the adhesion between the water drops and the surface of the copper foam material, namely the modified copper foam material obtained by the embodiment of the invention has excellent self-cleaning property.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (6)
1. A preparation method of a modified foam copper material is characterized by comprising the following steps:
carrying out activation pretreatment on the foamy copper, and removing an oxide film on the surface of the foamy copper to obtain the treated foamy copper;
dissolving copper nitrate trihydrate and trimesic acid in absolute ethyl alcohol to obtain a growth solution;
mixing the growth liquid and the treated foamy copper, and reacting at the temperature of 100-140 ℃ to obtain a reaction product;
cleaning and drying the reaction product, then soaking the reaction product in a hexadecanethiol solution, and then drying the soaked reaction product to obtain the modified foamed copper material;
wherein the molar ratio of the copper nitrate trihydrate to the trimesic acid is 4: 1;
the method for the pre-activation treatment comprises the following steps:
firstly, soaking foamy copper in hydrochloric acid, then ultrasonically cleaning the foamy copper by using acetone, ethanol and distilled water, and then drying the foamy copper subjected to ultrasonic cleaning to obtain treated foamy copper; the concentration of the hydrochloric acid is 0.1-0.3 mol/L.
2. The preparation method of the modified copper foam material according to claim 1, wherein the step of mixing the growth liquid and the treated copper foam and reacting at 100-140 ℃ to obtain a reaction product is carried out for 10-14 hours.
3. The method for preparing the modified copper foam material according to claim 1, wherein the reaction product is washed, dried and then soaked in a hexadecanethiol solution for 2-5 hours.
4. A modified copper foam material prepared by the preparation method of any one of claims 1 to 3.
5. Use of the modified copper foam material of claim 4 as a hydrophobic material.
6. The use of the modified copper foam material of claim 4 in the separation of oil and water.
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