CN110755888B - Preparation method of super-hydrophobic oleophylic material - Google Patents
Preparation method of super-hydrophobic oleophylic material Download PDFInfo
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- CN110755888B CN110755888B CN201911196790.4A CN201911196790A CN110755888B CN 110755888 B CN110755888 B CN 110755888B CN 201911196790 A CN201911196790 A CN 201911196790A CN 110755888 B CN110755888 B CN 110755888B
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Abstract
The invention discloses a super-hydrophobic oleophylic material, which consists of a substrate, a reinforcement body, a coupling agent and a nano coating attached to the surface of the substrate, wherein the substrate is made of one of a stainless steel mesh, foamed nickel, foamed copper or foamed titanium, the coupling agent is dopamine, and the nano coating on the surface is one or two of hexadecylamine and octadecylamine; the reinforcement is graphene. Also discloses a preparation method thereof; the design idea of the invention is that a layer of reduced graphene oxide is coated on a metal wire mesh framework such as nickel foam and the like, the strength of the graphene serving as a reinforcement is improved by taking the graphene as a base material, the graphene oxide with smaller particle size is coated on the graphene, and after reduction, the graphene has thinner sheet layers and can exert the excellent performance of the graphene. In addition, the graphene has hydrophobicity, and a nano-scale low-surface-energy substance is modified on the surface of the graphene, so that the comprehensive performance of the graphene and the graphene is realized, and the hydrophobicity and lipophilicity and the durability in use are improved.
Description
Technical Field
The invention belongs to the field of preparation of materials, and particularly relates to a preparation method of a super-hydrophobic oleophylic material.
Background
The super-hydrophobic oleophilic material is always a hot spot of theoretical research of scientific researchers, and simultaneously, the potential huge market prospect is also an important reason causing great attention of social workers. With the proposition and attention of scientific development theories of new century, new energy, low carbon, environmental protection and the like, the deep improvement and optimization of the high-quality and high-efficiency super-hydrophobic oleophylic material becomes an important part of the environmental protection industry. In the process of global industrialization, human beings have a strong dependence on oil and derived products, however, oil leakage inevitably occurs during oil exploitation and transportation, thereby polluting the environment. Scientific researchers obtain inspiration from the nature, and a series of novel materials with super-hydrophobic oleophylic properties are prepared by utilizing the natural phenomenon of super-hydrophobicity, and hopefully, the novel materials can be used in actual oil pollution treatment. However, these materials have problems of high production cost, complicated technique, and low service life.
At present, most of hydrophobic and oleophilic materials are porous structures of modification materials, and in various porous structures, a wire mesh is the most ideal choice, and the advantages of low cost, high mechanical strength and the porous structure are benefited. The traditional method for preparing the super-hydrophobic oleophylic metal wire mesh is not beneficial to industrial production due to complicated experimental steps and long preparation time.
The invention discloses a CN201610333634.8 novel oil-water separation material and a using method thereof, the oil-water separation material comprises a substrate and a coating attached to the surface of the substrate, the substrate is one of foamed nickel, foamed copper or foamed titanium, and the coating on the surface of the substrate is emulsion of modified resin, organic solvent and low surface energy substances. The material disclosed by the invention has lasting hydrophobic and oleophylic properties, and an established oil-water separation system has large treatment capacity and high separation efficiency, but the overall service life and the mechanical strength of the material are relatively poor, the raw materials and the proportion are complex, and the uniformity of infiltration is not controllable. CN201610937856.0 discloses a method for green preparation of a silver-zinc oxide nanosheet-graphene-foamed nickel composite material, which solves the problem that metal particles of a graphene-based active metal particle composite material are likely to be exposed in an application environment in the application process without falling off, realizes the integration of the performances of graphene, zinc oxide and silver particles, and exerts the respective excellent synergistic effects of electricity, catalysis, sensing and other performances, although the graphene is coated on a foamed nickel framework, the growth and the lamella of the graphene have uncontrollable performance, and the reaction environment has potential safety hazards at high temperature; the invention is mainly applied to the fields of catalysis and sensors.
Therefore, the invention researches a super-hydrophobic oleophylic material with high strength, difficult damage and high efficiency, and has important significance for submarine oil exploration and transportation and sea surface floating oil cleaning.
Disclosure of Invention
In order to solve the problems, the invention provides a high-strength super-hydrophobic oleophylic material which has higher mechanical strength, can be used in a certain pressure environment, has superior hydrophobic oleophylic performance, is not easy to damage in structure and is convenient to operate.
The invention is realized by the following technical scheme:
a super-hydrophobic oleophylic material consists of a substrate, a reinforcement, a coupling agent and a nano coating attached to the surface of the substrate, wherein the substrate is one of a stainless steel mesh, foamed nickel, foamed copper or foamed titanium, the coupling agent is dopamine, and the nano coating on the surface is one or two of hexadecylamine and octadecylamine; the reinforcement is graphene.
A preparation method of a super-hydrophobic oleophylic material comprises the following steps;
(1) selecting a foam net material substrate, cleaning, and drying for later use;
(2) preparing a dopamine aqueous solution, adding a graphene oxide aqueous solution under the condition that the pH value is 8-9, ultrasonically vibrating for 8-15 min, stirring for 11-15 h at the temperature of 25-35 ℃, and drying at the temperature of 65-80 ℃ to obtain poly-dopamine-graphene oxide;
(3) adding the graphene oxide obtained in the step (2) into a prepared dopamine solution, carrying out ultrasonic treatment for 15-25 min, immersing the prepared matrix material into the mixed solution, carrying out magnetic stirring at room temperature for 11-15 h, washing with deionized water for 3 times, and drying at 65-75 ℃ to obtain a graphene oxide-polydopamine-foam net matrix;
(4) adding the graphene oxide-polydopamine-foam net matrix obtained in the step (3) into a sodium hydroxide solution, reacting, cleaning and drying to obtain a graphene-polydopamine-foam net matrix;
(5) weighing dopamine and octadecylamine, dissolving the dopamine and octadecylamine with absolute ethyl alcohol, adding a hydrochloric acid solution, carrying out ultrasonic stirring for 10-15 min, adjusting the pH of the solution to 8-9 with a Tris solution, placing the graphene-polydopamine-foam net matrix obtained in the step (4) into the solution, and stirring for 18-26 h at the temperature of 45-55 ℃;
(6) taking out the graphene-polydopamine-foam net matrix in the step (5), ultrasonically cleaning the matrix for 1-2 times by using absolute ethyl alcohol, cleaning the matrix for 2-3 times by using deionized water, and drying the matrix for 2-4 hours at the temperature of 50-65 ℃ to obtain the hydrophobic oleophylic material. Thus, the excessive residual liquid is washed away, and the damage of the groups cannot be caused.
Preferably, the base material in the step (1) is one of a stainless steel mesh, foamed nickel, foamed copper or foamed titanium, the void density is 90 PPI-150 PPI, the cleaning process is absolute ethyl alcohol cleaning for 2-4 times, deionized water cleaning for 2-4 times, ultrasonic vibration cleaning is carried out for 6-10 minutes each time, and the drying temperature is 50 ℃.
Preferably, the concentration of the dopamine in the step (2) is 1.8-2.8 g/L, and the concentration of the graphene oxide aqueous solution is 0.1-3 mg/ml.
Preferably, the concentration of the dopamine in the step (3) is 1.5-2.5 g/L, the graphene is uniformly dispersed by ultrasonic for 15-25 min, and the magnetic stirring is carried out for 11-15 h so as to enable the dopamine to generate poly-dopamine through polymerization reaction, and the poly-dopamine is uniformly attached to the metal mesh framework.
Preferably, the mass fraction of the NaOH solution in the step (4) is 3-9%, the reaction process is ultrasonic vibration for 15-25 min, stirring for 30-50 min at 10-20 ℃, washing for 2-4 times with deionized water, and drying at 65-75 ℃ to obtain the graphene-polydopamine-foam net matrix.
Preferably, the ratio of dopamine in step (5): the mass ratio of the octadecylamine is 10: 5-8, and the concentration of the hydrochloric acid is 0.1M/L.
Advantageous effects
The design idea of the invention is that a layer of reduced graphene oxide is coated on a metal wire mesh framework such as nickel foam and the like, the strength of the graphene serving as a reinforcement is improved by taking the graphene as a base material, the graphene oxide with smaller particle size is coated on the graphene, and after reduction, the graphene has thinner sheet layers and can exert the excellent performance of the graphene. In addition, the graphene has hydrophobicity, and a nano-scale low-surface-energy substance is modified on the surface of the graphene, so that the comprehensive performance of the graphene and the graphene is realized, and the hydrophobicity and lipophilicity and the durability in use are improved.
The high-strength material graphene with hydrophobic property is coated on the framework of the metal matrix, so that the strength of the original metal matrix is improved, the oxidation of the material in the use period is reduced, and the service life is prolonged; the nano-modified layer on the surface provides a nano rough three-dimensional structure, so that the hydrophobic oleophylic function is more superior. The material is mainly applied to the environments of sea oil cleaning, inland river oil stain removal and the like, has the advantages of high durability, long service life and high strength, and can play a certain role in submarine oil exploitation and transportation.
Drawings
FIG. 1 is an SEM image of a high-strength superhydrophobic oleophilic material prepared in example 1;
FIG. 2 is a graph of the experimental hydrophobic property test of the high-strength superhydrophobic oleophilic material prepared in example 2;
FIG. 3 is a macroscopic graph of the oil absorption performance of the high strength superhydrophobic oleophilic material prepared in example 2;
fig. 4 is an SEM image of comparative example 1.
Fig. 5 is an experimental chart of comparative example 1.
Fig. 6 is a schematic view.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
(1) Selecting a sample with the void density of 110PPI, cutting the foamed nickel material into 5cm by 0.3cm, firstly cleaning with absolute ethyl alcohol for 3 times, then cleaning with deionized water for 3 times, ultrasonically vibrating and cleaning, drying for later use at 50 ℃ for 10 minutes each time;
(2) weighing 0.25g of dopamine in 95mL of water, adjusting the pH value of the solution to 8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding 5mL of graphene oxide aqueous solution with the concentration of 0.5mg/mL, ultrasonically shaking for 10min, magnetically stirring for 12h at 25 ℃, carrying out vacuum filtration, and drying at 75 ℃ to obtain the poly-dopamine-graphene oxide.
(3) Weighing 0.20g of dopamine in 100ml of water, adjusting the pH value of the solution to 8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding the polydopamine-graphene oxide obtained in the step (2) into the prepared dopamine solution, carrying out ultrasonic treatment for 20min, soaking the prepared foam nickel into the mixed solution, carrying out magnetic stirring at room temperature for 15h, washing with deionized water for 3 times, and drying at 70 ℃ to obtain graphene oxide-polydopamine-foam nickel.
(4) And (3) adding the graphene oxide-polydopamine-foamed nickel obtained in the step (3) into a NaOH solution with the mass fraction of 5%, ultrasonically vibrating for 20min, stirring for 40min at 20 ℃, ultrasonically cleaning for 4 times by using deionized water, and drying at 75 ℃ to obtain the graphene-polydopamine-foamed nickel.
(5) Weighing dopamine and octadecylamine with the mass of 0.10g and 0.067g respectively, dissolving with absolute ethyl alcohol, ultrasonically stirring for 15min, adjusting the solution to pH =8.6 with 0.1M/L hydrochloric acid solution and Tris solution, placing the graphene-polydopamine-foamed nickel obtained in the step (4) into the solution, and stirring for 26h at 50 ℃.
(6) And (3) taking out the graphene-polydopamine-nickel foam obtained in the step (5), ultrasonically cleaning the graphene-polydopamine-nickel foam for 2 times by using absolute ethyl alcohol, cleaning the graphene-polydopamine-nickel foam for 2 times by using deionized water, and drying the graphene-polydopamine-nickel foam for 3 hours at the temperature of 65 ℃ to obtain the hydrophobic oleophylic material.
The microscopic electronic scanning photograph of the hydrophobic oleophilic material prepared according to the embodiment 1 is shown in the attached figure 1, wherein, the figure 1a is the photograph of the skeleton of the low-power foam nickel, the surface-modified metal surface loses the characteristics of smoothness and cleanness, and a layer of convex particles is added, so that the metal surface becomes rough; fig. 1b is a microscopic photograph of graphene-poly-dopamine-nickel foam, and it can be seen from the figure that the dopamine as an intermediate coupling agent causes graphene to be tightly attached to the surface of the nickel foam skeleton through oxidative self-polymerization reaction in water and self-adsorption, and the graphene sheet layer is thinner, which is more beneficial to exerting the function of the reinforcement; fig. 1c is a photomicrograph of the final hydrophobic oleophilic material treated with octadecylamine in step (5), from which it can be seen that there is a layer of spherical particles on the surface of graphene, which are the result of the combined action of dopamine and octadecylamine, while also providing a rough nanocoating to the nickel foam backbone, which is beneficial to exert its hydrophobic oleophilic effect.
Example 2
(1) Selecting a sample with the void density of 125PPI, cutting the foam nickel material into 5cm by 0.3cm, cleaning the sample with absolute ethyl alcohol for 3 times, cleaning the sample with deionized water for 3 times, ultrasonically vibrating and cleaning the sample for 10 minutes each time, and drying the sample at 50 ℃ for later use;
(2) weighing 0.25g of dopamine in 93mL of water, adjusting the solution to pH =8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding 7mL of graphene oxide aqueous solution with the concentration of 0.5mg/mL, ultrasonically vibrating for 15min, magnetically stirring for 11h at 25 ℃, carrying out vacuum filtration, and drying at 65 ℃ to obtain the poly-dopamine-graphene oxide.
(3) Weighing 0.20g of dopamine in 100ml of water, adjusting the pH of the solution to =8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding the polydopamine-graphene oxide obtained in the step (2) into the prepared dopamine solution, carrying out ultrasonic treatment for 20min, immersing the prepared substrate material into the mixed solution, carrying out magnetic stirring at room temperature for 15h, washing with deionized water for 3 times, and drying at 65 ℃ to obtain graphene oxide-polydopamine-nickel foam.
(4) And (3) adding the graphene oxide-polydopamine-foamed nickel obtained in the step (3) into a NaOH solution with the concentration of 6%, ultrasonically vibrating for 18min, stirring for 40min at 20 ℃, washing for 3 times by using deionized water, and drying at 75 ℃ to obtain the graphene-polydopamine-foamed nickel.
(5) Weighing 0.10g of dopamine and 0.080g of octadecylamine respectively, dissolving with absolute ethyl alcohol, ultrasonically stirring for 15min, adjusting the pH value of the solution to 8.6 by using 0.1M/L hydrochloric acid solution and Tris solution, placing the graphene-polydopamine-foamed nickel obtained in the step (4) into the solution, and stirring for 24h at the temperature of 50 ℃.
(6) And (4) taking out the metal wire mesh in the step (5), ultrasonically cleaning the metal wire mesh for 2 times by using absolute ethyl alcohol, cleaning the metal wire mesh for 3 times by using deionized water, and drying the metal wire mesh for 3 hours at the temperature of 65 ℃ to obtain the hydrophobic oleophylic material.
Experimental Performance of the hydrophobic oleophilic material prepared according to example 2 As shown in the accompanying figures 2 and 3, figure 2a shows the water permeability of the material, the hydrophobic oleophilic nickel foam prepared according to example 2 rises to float at the surface of the water when naturally immersed in water, while the untreated raw nickel foam sinks to the bottom of the water, and after both are taken out of the water and placed on a white paper, as shown in figure 2b, the raw nickel foam carries a certain amount of water, whereas the material of example 2 is cleaner; FIG. 2c is a water drop test chart, and the wetting angle of the material prepared in example 2 and water is 135-153 degrees, which proves that the hydrophobicity is better. FIG. 3 shows the oleophilic property of the hydrophobic oleophilic material prepared in example 2, after the prepared oleophilic and hydrophobic nickel foam is placed in the aqueous solution containing crude oil and stirred and dragged lightly, the crude oil will be immersed into the modified nickel foam, which shows the excellent oleophilic effect of the material.
Example 3
(1) Selecting a sample of which the void density is 130PPI foamed titanium material is cut into 5cm by 0.3cm, cleaning with absolute ethyl alcohol for 2 times, cleaning with deionized water for 2 times, ultrasonically vibrating and cleaning for 6 minutes each time, and drying at 50 ℃ for later use;
(2) weighing 0.18g of dopamine in 90mL of water, adjusting the solution to pH =8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding 10mL of graphene oxide aqueous solution with the concentration of 0.1mg/mL, ultrasonically vibrating for 15min, magnetically stirring for 14h at 25 ℃, carrying out vacuum filtration, and drying at 65 ℃ to obtain the poly-dopamine-graphene oxide.
(3) Weighing 0.15g of dopamine in 100ml of water, adjusting the pH of the solution to =8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding the polydopamine-graphene oxide obtained in the step (2) into the prepared dopamine solution, carrying out ultrasonic treatment for 15min, immersing the prepared substrate material into the mixed solution, carrying out magnetic stirring at room temperature for 11h, washing with deionized water for 2 times, and drying at 65 ℃ to obtain graphene oxide-polydopamine-foam titanium.
(4) And (3) adding the graphene oxide-polydopamine-titanium foam obtained in the step (3) into a NaOH solution with the concentration of 3%, ultrasonically vibrating for 25min, stirring for 30min at 20 ℃, washing for 2 times by using deionized water, and drying at 65 ℃ to obtain the graphene-polydopamine-titanium foam.
(5) Weighing dopamine and octadecylamine with the mass of 0.10g and 0.050g respectively, dissolving with absolute ethyl alcohol, ultrasonically stirring for 16min, adjusting the solution to pH =8.6 with 0.1M/L hydrochloric acid solution and Tris solution, placing the graphene-poly-titanium foam obtained in the step (4) in the solution, and stirring at 50 ℃ for 24 h.
(6) And (4) taking out the metal wire mesh in the step (5), ultrasonically cleaning the metal wire mesh for 2 times by using absolute ethyl alcohol, cleaning the metal wire mesh for 3 times by using deionized water, and drying the metal wire mesh for 3 hours at the temperature of 65 ℃ to obtain the hydrophobic oleophylic material.
Example 4
(1) Selecting a sample of a foamed copper material with the void density of 115PPI, cutting the sample into 5cm by 0.3cm, cleaning the sample with absolute ethyl alcohol for 2 times, cleaning the sample with deionized water for 3 times, ultrasonically vibrating and cleaning the sample for 5 minutes each time, and drying the sample at 55 ℃ for later use;
(2) weighing 0.22g of dopamine in 87mL of water, adjusting the solution to pH =8.7 by using 0.1M/L hydrochloric acid solution and Tris solution, adding 13mL of graphene oxide aqueous solution with the concentration of 0.1mg/mL, ultrasonically vibrating for 15min, magnetically stirring for 15h at 25 ℃, carrying out vacuum filtration, and drying at 64 ℃ to obtain the poly-dopamine-graphene oxide.
(3) Weighing 0.16g of dopamine in 100ml of water, adjusting the pH of the solution to =8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding the polydopamine-graphene oxide obtained in the step (2) into the prepared dopamine solution, carrying out ultrasonic treatment for 15min, immersing the prepared substrate material into the mixed solution, carrying out magnetic stirring at room temperature for 10h, washing with deionized water for 3 times, and drying at 65 ℃ to obtain the graphene oxide-polydopamine-copper foam.
(4) And (3) adding the graphene oxide-polydopamine-foam titanium obtained in the step (3) into a NaOH solution with the concentration of 3%, ultrasonically vibrating for 28min, stirring for 35min at 22 ℃, washing for 2 times by using deionized water, and drying at 60 ℃ to obtain graphene-polydopamine-foam copper.
(5) Weighing 0.08g and 0.042g of dopamine and 0.042g of octadecylamine respectively, dissolving with absolute ethyl alcohol, ultrasonically stirring for 17min, adjusting the pH of the solution to be 8.6 by using 0.1M/L hydrochloric acid solution and Tris solution, placing the graphene-polydopamine-copper foam obtained in the step (4) into the solution, and stirring for 24h at the temperature of 55 ℃.
(6) And (4) taking out the metal wire mesh in the step (5), ultrasonically cleaning the metal wire mesh by using absolute ethyl alcohol for 3 times, then cleaning the metal wire mesh by using deionized water for 3 times, and drying the metal wire mesh for 2.5 hours at the temperature of 68 ℃ to obtain the hydrophobic oleophylic material.
Example 5
(1) Selecting a sample with the void density of 110PPI, cutting the foam sponge material into 5cm by 0.5cm, cleaning with absolute ethyl alcohol for 2 times, cleaning with deionized water for 2 times, ultrasonically vibrating and cleaning for 3 minutes each time, and drying at 40 ℃ for later use;
(2) weighing 0.18g of dopamine in 90mL of water, adjusting the solution to pH =8.7 by using 0.1M/L hydrochloric acid solution and Tris solution, adding 10mL of graphene oxide aqueous solution with the concentration of 0.2mg/mL, ultrasonically vibrating for 13min, magnetically stirring, carrying out vacuum filtration at 25 ℃, and drying at 55 ℃ to obtain the poly-dopamine-graphene oxide.
(3) Weighing 0.18g of dopamine in 100ml of water, adjusting the pH of the solution to be =8.6 by using 0.1M/L hydrochloric acid solution and Tris solution, adding the polydopamine-graphene oxide obtained in the step (2) into the prepared dopamine solution, carrying out ultrasonic treatment for 15min, immersing the prepared matrix material into the mixed solution, carrying out magnetic stirring at room temperature for 12h, washing with deionized water for 2 times, and drying at 60 ℃ to obtain the graphene oxide-polydopamine-foam sponge.
(4) And (3) adding the oxidized graphene-polydopamine-foam sponge in the step (3) into a NaOH solution with the concentration of 3%, ultrasonically vibrating for 30min, stirring for 33min at 20 ℃, washing for 2 times by using deionized water, and drying at 55 ℃ to obtain the graphene-polydopamine-foam sponge.
(5) Weighing dopamine and octadecylamine with the mass of 0.12g and 0.053g respectively, dissolving with absolute ethyl alcohol, ultrasonically stirring for 19min, adjusting the solution to pH =8.6 with 0.1M/L hydrochloric acid solution and Tris solution, placing the graphene-polydopamine-foam sponge obtained in the step (4) into the solution, and stirring for 20h at 55 ℃.
(6) And (4) taking out the metal wire mesh in the step (5), ultrasonically cleaning the metal wire mesh for 2 times by using absolute ethyl alcohol, cleaning the metal wire mesh for 2 times by using deionized water, and drying the metal wire mesh for 2 hours at the temperature of 55 ℃ to obtain the hydrophobic oleophylic material.
Comparative example 1
Under the same other conditions, when the mass ratio of dopamine to graphene oxide in the step (2) and the mass ratio of octadecylamine to dopamine in the step (5) in the example 1 are respectively less than 0.12-5.6: 1 and 0.5-0.8: 1, a good hydrophobic oleophilic material cannot be obtained, and the following steps are carried out:
(1) selecting a sample with the void density of 110PPI, cutting the foamed nickel material into 5cm by 0.3cm, firstly cleaning with absolute ethyl alcohol for 3 times, then cleaning with deionized water for 3 times, ultrasonically vibrating and cleaning, drying for later use at 50 ℃ for 10 minutes each time;
(2) weighing 0.15g of dopamine in 95mL of water, adjusting the pH value of the solution to 8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding 5mL of graphene oxide aqueous solution with the concentration of 0.5mg/mL, ultrasonically shaking for 10min, magnetically stirring for 12h at 25 ℃, carrying out vacuum filtration, and drying at 75 ℃ to obtain the poly-dopamine-graphene oxide.
(3) Weighing 0.20g of dopamine in 100ml of water, adjusting the pH value of the solution to 8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding the polydopamine-graphene oxide obtained in the step (2) into the prepared dopamine solution, carrying out ultrasonic treatment for 20min, soaking the prepared foam nickel into the mixed solution, carrying out magnetic stirring at room temperature for 15h, washing with deionized water for 3 times, and drying at 70 ℃ to obtain graphene oxide-polydopamine-foam nickel.
(4) And (3) adding the graphene oxide-polydopamine-foamed nickel obtained in the step (3) into a NaOH solution with the mass fraction of 5%, ultrasonically vibrating for 20min, stirring for 40min at 20 ℃, ultrasonically cleaning for 4 times by using deionized water, and drying at 75 ℃ to obtain the graphene-poly-foamed nickel.
(5) Weighing 0.07g of dopamine and 0.067g of octadecylamine respectively, dissolving with absolute ethyl alcohol, ultrasonically stirring for 15min, adjusting the pH of the solution to be 8.6 by using 0.1M/L hydrochloric acid solution and Tris solution, placing the graphene-poly-nickel foam obtained in the step (4) into the solution, and stirring for 26h at the temperature of 50 ℃.
(6) And (3) taking out the graphene-poly-nickel foam obtained in the step (5), ultrasonically cleaning the graphene-poly-nickel foam for 2 times by using absolute ethyl alcohol, cleaning the graphene-poly-nickel foam for 2 times by using deionized water, and drying the graphene-poly-nickel foam for 3 hours at the temperature of 65 ℃ to obtain the hydrophobic oleophylic material.
The microscopic electronic scanning photograph of the hydrophobic oleophilic material prepared according to the comparative example 1 is shown in the attached figure 4, and as can be seen from figure 4a, the roughness of the foamed nickel metal skeleton is low, and the surface modified particles are few; as can be seen from the high magnification photograph of fig. 4b, the graphene attached to the surface of the nickel foam skeleton is less, and the spherical octadecylamine particles are less, which is in significant contrast to the microscopic photograph of the material in example 1, and thus the strength and hydrophobic-oleophilic property are both significantly lower than those of example 1. The dripping experiment of fig. 5 also confirmed that the material prepared in this comparative example is poor in hydrophobicity and water drops can easily penetrate the prepared material.
Comparative example 2
Under the same other conditions, when the mass ratio of dopamine to graphene oxide in the step (2) and the mass ratio of octadecylamine to dopamine in the step (5) in the example 1 are respectively greater than 0.12-5.6: 1 and 0.5-0.8: 1, a good hydrophobic oleophilic material cannot be obtained, and the following steps are carried out:
(1) selecting a sample with the void density of 110PPI, cutting the foamed nickel material into 5cm by 0.3cm, firstly cleaning with absolute ethyl alcohol for 3 times, then cleaning with deionized water for 3 times, ultrasonically vibrating and cleaning, drying for later use at 50 ℃ for 10 minutes each time;
(2) weighing 0.40g of dopamine in 95mL of water, adjusting the pH value of the solution to 8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding 5mL of graphene oxide aqueous solution with the concentration of 0.5mg/mL, ultrasonically shaking for 10min, magnetically stirring for 12h at 25 ℃, carrying out vacuum filtration, and drying at 75 ℃ to obtain the poly-dopamine-graphene oxide.
(3) Weighing 0.20g of dopamine in 100ml of water, adjusting the pH value of the solution to 8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding the polydopamine-graphene oxide obtained in the step (2) into the prepared dopamine solution, carrying out ultrasonic treatment for 20min, soaking the prepared foam nickel into the mixed solution, carrying out magnetic stirring at room temperature for 15h, washing with deionized water for 3 times, and drying at 70 ℃ to obtain graphene oxide-polydopamine-foam nickel.
(4) And (3) adding the graphene oxide-polydopamine-foamed nickel obtained in the step (3) into a NaOH solution with the mass fraction of 5%, ultrasonically vibrating for 20min, stirring for 40min at 20 ℃, ultrasonically cleaning for 4 times by using deionized water, and drying at 75 ℃ to obtain the graphene-polydopamine-foamed nickel.
(5) Weighing 0.07g of dopamine and 0.12g of octadecylamine respectively, dissolving with absolute ethyl alcohol, ultrasonically stirring for 15min, adjusting the pH of the solution to be 8.6 by using 0.1M/L hydrochloric acid solution and Tris solution, placing the graphene-polydopamine-foamed nickel obtained in the step (4) into the solution, and stirring for 26h at the temperature of 50 ℃.
(6) And (3) taking out the graphene-polydopamine-nickel foam obtained in the step (5), ultrasonically cleaning the graphene-polydopamine-nickel foam for 2 times by using absolute ethyl alcohol, cleaning the graphene-polydopamine-nickel foam for 2 times by using deionized water, and drying the graphene-polydopamine-nickel foam for 3 hours at the temperature of 65 ℃ to obtain the hydrophobic oleophylic material.
Comparative example 3
The other conditions are the same, the graphene oxide in the embodiment 1 is directly replaced by graphene, and the deionized water in the step (2) is replaced by an alcohol solution, so that a good hydrophobic oleophilic material cannot be obtained, and the steps are as follows:
(1) selecting a sample with the void density of 110PPI, cutting the foamed nickel material into 5cm by 0.3cm, firstly cleaning with absolute ethyl alcohol for 3 times, then cleaning with deionized water for 3 times, ultrasonically vibrating and cleaning, drying for later use at 50 ℃ for 10 minutes each time;
(2) weighing 0.25g of dopamine in 100ml of alcohol, adjusting the pH of the solution to 8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding 0.25mg of graphene, carrying out ultrasonic vibration for 10min, carrying out magnetic stirring for 12h at 25 ℃, carrying out vacuum filtration, and drying at 75 ℃ to obtain the poly-dopamine-graphene.
(3) Weighing 0.20g of dopamine in 100ml of water, adjusting the pH value of the solution to 8.5 by using 0.1M/L hydrochloric acid solution and Tris solution, adding the polydopamine-graphene obtained in the step (2) into the prepared dopamine solution, carrying out ultrasonic treatment for 20min, soaking the prepared foam nickel into the mixed solution, carrying out magnetic stirring at room temperature for 15h, washing with deionized water for 3 times, and drying at 70 ℃ to obtain the graphene-polydopamine-foam nickel.
(4) Weighing dopamine and octadecylamine with the mass of 0.10g and 0.067g respectively, dissolving with absolute ethyl alcohol, ultrasonically stirring for 15min, adjusting the solution to pH =8.6 with 0.1M/L hydrochloric acid solution and Tris solution, placing the graphene-polydopamine-foamed nickel obtained in the step (4) into the solution, and stirring for 26h at 50 ℃.
(6) And (3) taking out the graphene-polydopamine-nickel foam obtained in the step (5), ultrasonically cleaning the graphene-polydopamine-nickel foam for 2 times by using absolute ethyl alcohol, cleaning the graphene-polydopamine-nickel foam for 2 times by using deionized water, and drying the graphene-polydopamine-nickel foam for 3 hours at the temperature of 65 ℃ to obtain the material.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (6)
1. A preparation method of super-hydrophobic oleophylic material comprises a substrate, a reinforcement body, a coupling agent and a nano coating attached to the surface of the substrate, and is characterized in that the substrate is made of one of stainless steel mesh, foamed nickel, foamed copper or foamed titanium, the coupling agent is dopamine, and the nano coating on the surface is one or two of hexadecylamine and octadecylamine; the reinforcement is graphene;
the method is characterized by comprising the following steps;
(1) selecting a foam net material substrate, cleaning, and drying for later use;
(2) preparing a dopamine aqueous solution, adding a graphene oxide aqueous solution under the condition of pH 8-9, ultrasonically vibrating for 8-15 min, stirring for 11-15 h at the temperature of 25-35 ℃, and drying at the temperature of 65-80 ℃ to obtain poly-dopamine-graphene oxide;
(3) adding the graphene oxide obtained in the step (2) into a prepared dopamine solution, carrying out ultrasonic treatment for 15-25 min, immersing the prepared metal foam net into the mixed solution, carrying out magnetic stirring at room temperature for 11-15 h, washing with deionized water for 3 times, and drying at 65-75 ℃ to obtain a graphene oxide-polydopamine-metal foam net;
(4) adding the oxidized graphene-polydopamine-metal foam net obtained in the step (3) into a sodium hydroxide solution, reacting, cleaning and drying to obtain an oxidized graphene-polydopamine-metal foam net;
(5) weighing dopamine and octadecylamine, dissolving the dopamine and octadecylamine with absolute ethyl alcohol, adding a hydrochloric acid solution, carrying out ultrasonic stirring for 10-15 min, adjusting the pH of the solution to 8-9 with a Tris solution, placing the graphene-polydopamine-metal foam net obtained in the step (4) into the solution, and stirring for 18-26 h at the temperature of 45-55 ℃;
(6) taking out the graphene-polydopamine-metal foam net in the step (5), ultrasonically cleaning the graphene-polydopamine-metal foam net for 1-2 times by using absolute ethyl alcohol, cleaning the graphene-polydopamine-metal foam net for 2-3 times by using deionized water, and drying the graphene-polydopamine-metal foam net for 2-4 hours at the temperature of 50-65 ℃ to obtain the hydrophobic oleophylic material.
2. The preparation method according to claim 1, wherein the base material in the step (1) is one of stainless steel mesh, foamed nickel, foamed copper or foamed titanium, the void density is 90PPI to 150PPI, the cleaning process comprises 2 to 4 times of absolute ethyl alcohol cleaning, 2 to 4 times of deionized water cleaning, ultrasonic vibration cleaning for 6 to 10 minutes each time, and the drying temperature is 50 ℃.
3. The preparation method according to claim 1, wherein the concentration of the dopamine in the step (2) is 1.8-2.8 g/L, the concentration of the graphene oxide aqueous solution is 0.1-3g/L, and the mass of the dopamine is as follows: the mass of the graphene oxide is 0.12-5.6: 1.
4. The preparation method according to claim 1, wherein the concentration of the dopamine in the step (3) is 1.5-2.5 g/L, the ultrasonic treatment is carried out for 15-25 min, and the magnetic stirring is carried out for 11-15 h.
5. The preparation method according to claim 1, wherein the mass fraction of the sodium hydroxide solution in the step (4) is 3-9%, the reaction process is ultrasonic vibration for 15-25 min, stirring for 30-50 min at 10-20 ℃, washing for 2-4 times with deionized water, and drying at 65-75 ℃ to obtain the graphene-polydopamine-metal foam net.
6. The method according to claim 1, wherein the ratio of octadecylamine in step (5): the mass ratio of the dopamine is 0.5-0.8: 1, and the concentration of the hydrochloric acid is 0.1M.
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