CN113304721A - Material capable of directly adsorbing and separating underwater oil and preparation method thereof - Google Patents
Material capable of directly adsorbing and separating underwater oil and preparation method thereof Download PDFInfo
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- CN113304721A CN113304721A CN202110672945.8A CN202110672945A CN113304721A CN 113304721 A CN113304721 A CN 113304721A CN 202110672945 A CN202110672945 A CN 202110672945A CN 113304721 A CN113304721 A CN 113304721A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 240
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000006260 foam Substances 0.000 claims abstract description 84
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 60
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002114 nanocomposite Substances 0.000 claims abstract description 39
- 229960003638 dopamine Drugs 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 10
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 239000007853 buffer solution Substances 0.000 claims description 18
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 9
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 9
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 9
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 238000007385 chemical modification Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000001000 micrograph Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000007664 blowing Methods 0.000 description 7
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002352 surface water Substances 0.000 description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 244000020998 Acacia farnesiana Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention belongs to the field of water treatment, and particularly relates to a material capable of directly adsorbing and separating underwater oil and a preparation method thereof. The material capable of directly adsorbing underwater oil is prepared by chemically modifying foamed nickel. Firstly, preparing a cobalt oxide micro-structure on foam nickel by a hydrothermal method, then modifying by dopamine-octadecylamine to obtain the super-hydrophobic foam nickel with the micro-nano composite structure, and finally carrying out hydrophilic modification treatment on the top end of the microstructure by dopamine. The super-hydrophobic foamed nickel improves the underwater stability of an air layer in the microstructure groove of the super-hydrophobic foamed nickel, and further realizes direct adsorption and separation of underwater oil. Compared with the traditional water treatment product, the invention has the advantages of high efficiency, no noise, no complex equipment, low energy consumption, no secondary pollution and the like, and is particularly suitable for direct adsorption and separation treatment of underwater oil.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a material capable of directly adsorbing and separating underwater oil and a preparation method thereof.
Background
With the development of the petrochemical industry, the discharge amount of industrial oily wastewater in the world rapidly rises, and serious environmental and ecological problems are caused. Oil-like substances are generally present in wastewater in three states: the oil has larger dispersed particles in the wastewater, the particle size is larger than 100 micrometers, and the oil accounts for 60-80% of the total oil in the petroleum sewage; the oil has smaller dispersed particles in the wastewater and is in an emulsified state; the oil is in a dissolved state, and the solubility is about 5-15 mg/L. Currently, oil-containing wastewater is usually recovered from floating oil or heavy oil by using an oil separation tank, such as: oil-water separation is realized by gravity method, flotation method, adsorption method, membrane separation and other methods, so that various problems of complex separation method, low separation efficiency, high energy consumption and the like generally exist.
The special wetting material has become a hot spot of wide attention due to its characteristics of high selectivity, high efficiency and the like. The super-hydrophobic sponge has the excellent characteristics of high porosity, high elasticity, high selectivity and the like, shows extremely high-efficiency and reusable oil absorption capacity, and is widely researched and applied as an ideal adsorbent material. However, the oil absorption capacity of the super-hydrophobic sponge is effective for the adsorption of floating oil on the water surface, and cannot guarantee the adsorption of underwater oil. The principle is studied, the high selective adsorption of the super-hydrophobic sponge is the premise of super-hydrophobicity, the stability of the Cassie infiltration state (the air layer in the super-hydrophobic surface microstructure) plays an extremely important role in oil absorption of oil in water, and once the stability of the air layer is reduced, the underwater oil absorption capacity is rapidly reduced or even completely lost. Therefore, the stability of the air layer in the underwater microstructure is a very key parameter influencing the oil absorption capacity of the super-hydrophobic sponge, and the key of the underwater application of the super-hydrophobic sponge is how to keep high adsorption efficiency under water.
Therefore, there is a need to develop a new material that can have a stable air layer in the underwater microstructure and can maintain high adsorption efficiency under water.
Disclosure of Invention
According to the technical problems that most separation methods have the problems of complex method, low efficiency, high energy consumption and the like when underwater oil is separated at present, and the special wetting material is influenced by the stability of an air layer in an underwater microstructure, the material capable of directly adsorbing and separating the underwater oil and the preparation method thereof are provided. According to the invention, the micro-nano composite structure is mainly prepared on the foamed nickel substrate, so that the surface with super-hydrophobic property is obtained, the stability of an air layer in the underwater microstructure is enhanced by modifying the top end of the super-hydrophobic foamed nickel microstructure of the bionic locust leaf apple with a hydrophilic substance, so that the direct adsorption and separation treatment of the underwater oil is realized, and the method has the advantages of low energy consumption, repeatability, high efficiency, no secondary pollution and the like.
The technical means adopted by the invention are as follows:
a material capable of directly adsorbing and separating underwater oil is characterized in that: the material is super-hydrophobic foam nickel with a micro-nano composite structure, and the top end of the micro-nano composite structure of the super-hydrophobic foam nickel is subjected to hydrophilic modification treatment.
The invention also discloses a preparation method of the material capable of directly adsorbing and separating underwater oil, which is characterized by comprising the following steps: the method comprises the steps of preparing a micro-nano composite structure on a foamed nickel substrate, so as to obtain super-hydrophobic foamed nickel with the micro-nano composite structure, and carrying out hydrophilic modification treatment on the top end of the micro-nano composite structure of the super-hydrophobic foamed nickel, so as to enhance the stability of an air layer in an underwater microstructure of the micro-nano composite structure, and further realize direct adsorption and separation treatment of underwater oil.
Furthermore, the super-hydrophobic nickel foam is obtained by preparing a cobalt oxide micron structure on the nickel foam through the combination of a hydrothermal method and a solution method and then carrying out chemical modification on the cobalt oxide micron structure by using dopamine-octadecylamine.
Furthermore, the combination of the hydrothermal method and the solution method means that the foamed nickel is ultrasonically cleaned in a 2M hydrochloric acid solution for 20 minutes, and then is repeatedly cleaned with deionized water for three times and dried; and (3) putting the prepared solution I and the cleaned foam nickel into a reaction kettle with polytetrafluoroethylene as a substrate for hydrothermal reaction, cleaning the reacted foam nickel by using deionized water, and drying to obtain the foam nickel with a cobalt oxide micron structure, wherein the prepared solution I is ethylene glycol/water solution mixed by cobalt nitrate hexahydrate, urea and ammonium fluoride.
Furthermore, the concentration of cobalt nitrate hexahydrate in the preparation liquid I is 12.0-25.0 mM, the concentration of urea is 20.0-40.0 mM, the concentration of ammonium fluoride is 71.0-105.9 mM, and the volume ratio of ethylene glycol to water is 1: 3.
Further, the hydrothermal reaction temperature is 140-180 ℃, and the hydrothermal reaction time is 12-24 hours.
Further, the dopamine-octadecylamine chemical modification method comprises the steps of putting foam nickel with a cobalt oxide micron structure into the preparation liquid II for reaction for 24 hours, washing with deionized water after the reaction, and drying to obtain super-hydrophobic foam nickel with a micro-nano composite structure, wherein the water contact angle of the super-hydrophobic foam nickel is 150.0-179.0 degrees, and the oil contact angle is 0 degree; wherein the preparation liquid II is ethanol/water solution of dopamine and octadecylamine, and the pH value is adjusted to 8.5 by Tris-HCL.
Further, the concentration of dopamine in the preparation liquid II is 1.2-2.8 g/L, the concentration of octadecylamine is 5.0-10.0 mM, and the volume ratio of ethanol to water is 1: 1.
Further, the hydrophilic modification treatment of the top end of the micro-nano composite structure of the super-hydrophobic foam nickel refers to the step of soaking the super-hydrophobic foam nickel in a dopamine buffer solution, washing the reacted super-hydrophobic foam nickel with deionized water and drying, wherein the water contact angle of the top end of the micro-structure of the super-hydrophobic foam nickel after the hydrophilic modification treatment is 150.0-179.0 degrees, and the oil contact angle is 0 degree
Further, the dopamine buffer solution is prepared from dopamine hydrochloride and a Tris buffer solution, wherein the concentration of the dopamine is 0.05-0.15 mol/L, the Tris buffer solution is prepared from Tris hydroxymethyl aminomethane and water, the pH value of the solution is adjusted to 8.5 by hydrochloric acid titration, and the soaking time is 8-15 minutes.
Compared with the prior art, the invention has the following advantages:
the material capable of directly adsorbing underwater oil is prepared by chemically modifying common foamed nickel. Firstly, preparing a cobalt oxide micro-structure on foam nickel by a hydrothermal method, then modifying by dopamine-octadecylamine to obtain the super-hydrophobic foam nickel with the micro-nano composite structure, and finally carrying out hydrophilic modification treatment on the top end of the microstructure by dopamine. The super-hydrophobic foamed nickel improves the underwater stability of an air layer in the microstructure groove of the super-hydrophobic foamed nickel, and further realizes direct adsorption and separation of underwater oil.
The underwater oil separation material prepared by the preparation method has the advantages of simple method, good hydrophobic effect and strong underwater stability, can efficiently carry out direct adsorption and separation treatment on floating oil on water, particularly submerged oil on water, has the advantages of high efficiency, no noise, no complex equipment, low energy consumption, no secondary pollution and the like compared with the traditional water treatment product, and is particularly suitable for direct adsorption and separation treatment of underwater oil.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing a material capable of directly adsorbing, separating and treating underwater oil according to the invention.
FIG. 2 is a scanning electron microscope image of the superhydrophobic nickel foam prepared in example 1 of the present invention.
FIG. 3 is a water contact angle diagram of super-hydrophobic foam nickel prepared in example 1 of the present invention.
FIG. 4 is a graph of contact angle of super-hydrophobic foam nickel oil prepared in example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The technical solution of the present invention will be further described with reference to the accompanying drawings and examples.
The invention provides a material capable of directly adsorbing and separating underwater oil and a preparation method thereof, wherein the preparation process is shown in figure 1, and the preparation method comprises the following specific steps:
example 1:
(1) carrying out ultrasonic treatment on the foamed nickel for 20 minutes by using a hydrochloric acid aqueous solution with the mass fraction of 2mol/L, repeatedly carrying out ultrasonic cleaning for 2 times by using deionized water, and drying for later use; preparing an ethylene glycol/water solution of 18.0mM cobalt nitrate hexahydrate, 30.0mM urea and 90.0mM ammonium fluoride, wherein the volume ratio of ethylene glycol to water is 1: 3; putting the pretreated nickel foam and the preparation solution into a reaction kettle with a tetrafluoroethylene lining, reacting for 16 hours at 160 ℃, and taking out after reaction; and washing with deionized water, and drying to obtain the foamed nickel treated by the hydrothermal method.
(2) Preparing an ethanol/water solution of 2.0g/L of dopamine and 5.0mM of octadecylamine, wherein the volume ratio of ethanol to water is 1: 1; adjusting the pH to 8.5 with Tris-HCl; transferring the foamed nickel treated by the hydrothermal method into a preparation solution for reaction for 24 hours; and washing the reacted foam nickel with deionized water, and drying to obtain the micro-nano composite structure super-hydrophobic foam nickel.
(3) Preparing a Tirs buffer solution by preparing trihydroxymethyl aminomethane, deionized water and dopamine hydrochloride, and then titrating by using hydrochloric acid to ensure that the pH value is 8.5, wherein the concentration of the dopamine is 0.1M. And (3) transferring the micro-nano composite structure super-hydrophobic foam nickel obtained in the step (2) into the prepared solution for treatment for 10 minutes, then repeatedly washing for 3 times by using a buffer solution and deionized water, and drying by blowing under the nitrogen condition to obtain the micro-structure top hydrophilic super-hydrophobic foam nickel. FIG. 2 is a scanning electron microscope image of the nickel foam, which shows that the nickel foam has a micro-nano composite structure; FIG. 3 shows that the surface water contact angle reaches 165.2 °; fig. 4 shows that the surface oil contact angle reaches 0 °.
Example 2:
(1) carrying out ultrasonic treatment on the foamed nickel for 20 minutes by using a hydrochloric acid aqueous solution with the mass fraction of 2mol/L, repeatedly carrying out ultrasonic cleaning for 2 times by using deionized water, and drying for later use; preparing an ethylene glycol/water solution of 12.0mM cobalt nitrate hexahydrate, 20.0mM urea and 71.0mM ammonium fluoride, wherein the volume ratio of ethylene glycol to water is 1: 3; putting the pretreated nickel foam and the preparation solution into a reaction kettle with a tetrafluoroethylene lining, reacting for 24 hours at 140 ℃, and taking out after reaction; and washing with deionized water, and drying to obtain the foamed nickel treated by the hydrothermal method.
(2) Preparing an ethanol/water solution of 1.2g/L of dopamine and 5.0mM of octadecylamine, wherein the volume ratio of ethanol to water is 1: 1; adjusting the pH to 8.5 with Tris-HCl; transferring the foamed nickel treated by the hydrothermal method into a preparation solution for reaction for 24 hours; and washing the reacted foam nickel with deionized water, and drying to obtain the micro-nano composite structure super-hydrophobic foam nickel.
(3) Preparing a Tirs buffer solution by preparing trihydroxymethyl aminomethane, deionized water and dopamine hydrochloride, and then titrating by using hydrochloric acid to ensure that the pH value is 8.5, wherein the concentration of the dopamine is 0.05M. And (3) transferring the micro-nano composite structure super-hydrophobic foam nickel obtained in the step (2) into the prepared solution for treatment for 15 minutes, then repeatedly washing for 3 times by using a buffer solution and deionized water, and drying by blowing under the nitrogen condition to obtain the micro-structure top hydrophilic super-hydrophobic foam nickel. FIG. 2 is a scanning electron microscope image of the nickel foam, which shows that the nickel foam has a micro-nano composite structure; FIG. 3 shows that the surface water contact angle reaches 151.2 °; fig. 4 shows that the surface oil contact angle reaches 0 °.
Example 3:
(1) carrying out ultrasonic treatment on the foamed nickel for 20 minutes by using a hydrochloric acid aqueous solution with the mass fraction of 2mol/L, repeatedly carrying out ultrasonic cleaning for 2 times by using deionized water, and drying for later use; preparing a glycol/water solution of 20.0mM cobalt nitrate hexahydrate, 35.0mM urea and 98.0mM ammonium fluoride, wherein the volume ratio of glycol to water is 1: 3; putting the pretreated nickel foam and the preparation solution into a reaction kettle with a tetrafluoroethylene lining, reacting for 18 hours at 180 ℃, and taking out after reaction; and washing with deionized water, and drying to obtain the foamed nickel treated by the hydrothermal method.
(2) Preparing an ethanol/water solution of 2.8g/L of dopamine and 10.0mM of octadecylamine, wherein the volume ratio of ethanol to water is 1: 1; adjusting the pH to 8.5 with Tris-HCl; transferring the foamed nickel treated by the hydrothermal method into a preparation solution for reaction for 24 hours; and washing the reacted foam nickel with deionized water, and drying to obtain the micro-nano composite structure super-hydrophobic foam nickel.
(3) Preparing a Tirs buffer solution by preparing trihydroxymethyl aminomethane, deionized water and dopamine hydrochloride, and then titrating by using hydrochloric acid to ensure that the pH value is 8.5, wherein the concentration of the dopamine is 0.15M. And (3) transferring the micro-nano composite structure super-hydrophobic foam nickel obtained in the step (2) into the prepared solution for treatment for 8 minutes, then repeatedly washing for 3 times by using a buffer solution and deionized water, and drying by blowing under the nitrogen condition to obtain the micro-structure top hydrophilic super-hydrophobic foam nickel. FIG. 2 is a scanning electron microscope image of the nickel foam, which shows that the nickel foam has a micro-nano composite structure; FIG. 3 shows that the surface water contact angle reaches 175.7 °; fig. 4 shows that the surface oil contact angle reaches 0 °.
Example 4:
(1) carrying out ultrasonic treatment on the foamed nickel for 20 minutes by using a hydrochloric acid aqueous solution with the mass fraction of 2mol/L, repeatedly carrying out ultrasonic cleaning for 2 times by using deionized water, and drying for later use; preparing 25.0mM cobalt nitrate hexahydrate, 40.0mM urea and 105.9mM ammonium fluoride glycol/water solution, wherein the volume ratio of glycol to water is 1: 3; putting the pretreated nickel foam and the preparation solution into a reaction kettle with a tetrafluoroethylene lining, reacting for 17 hours at 170 ℃, and taking out after reaction; and washing with deionized water, and drying to obtain the foamed nickel treated by the hydrothermal method.
(2) Preparing an ethanol/water solution of 2.2g/L of dopamine and 8.0mM of octadecylamine, wherein the volume ratio of ethanol to water is 1: 1; adjusting the pH to 8.5 with Tris-HCl; transferring the foamed nickel treated by the hydrothermal method into a preparation solution for reaction for 24 hours; and washing the reacted foam nickel with deionized water, and drying to obtain the micro-nano composite structure super-hydrophobic foam nickel.
(3) Preparing a Tirs buffer solution by preparing trihydroxymethyl aminomethane, deionized water and dopamine hydrochloride, and then titrating by using hydrochloric acid to ensure that the pH value is 8.5, wherein the concentration of the dopamine is 0.12M. And (3) transferring the micro-nano composite structure super-hydrophobic foam nickel obtained in the step (2) into the prepared solution for treatment for 10 minutes, then repeatedly washing for 3 times by using a buffer solution and deionized water, and drying by blowing under the nitrogen condition to obtain the micro-structure top hydrophilic super-hydrophobic foam nickel. FIG. 2 is a scanning electron microscope image of the nickel foam, which shows that the nickel foam has a micro-nano composite structure; FIG. 3 shows that the surface water contact angle reaches 168.2 °; fig. 4 shows that the surface oil contact angle reaches 0 °.
Example 5:
(1) carrying out ultrasonic treatment on the foamed nickel for 20 minutes by using a hydrochloric acid aqueous solution with the mass fraction of 2mol/L, repeatedly carrying out ultrasonic cleaning for 2 times by using deionized water, and drying for later use; preparing an ethylene glycol/water solution of 15.0mM cobalt nitrate hexahydrate, 28.0mM urea and 85.0mM ammonium fluoride, wherein the volume ratio of ethylene glycol to water is 1: 3; putting the pretreated nickel foam and the preparation solution into a reaction kettle with a tetrafluoroethylene lining, reacting for 20 hours at 158 ℃, and taking out after reaction; and washing with deionized water, and drying to obtain the foamed nickel treated by the hydrothermal method.
(2) Preparing an ethanol/water solution of 1.8g/L of dopamine and 7.8mM of octadecylamine, wherein the volume ratio of ethanol to water is 1: 1; adjusting the pH to 8.5 with Tris-HCl; transferring the foamed nickel treated by the hydrothermal method into a preparation solution for reaction for 24 hours; and washing the reacted foam nickel with deionized water, and drying to obtain the micro-nano composite structure super-hydrophobic foam nickel.
(3) Preparing a Tirs buffer solution by preparing trihydroxymethyl aminomethane, deionized water and dopamine hydrochloride, and then titrating by using hydrochloric acid to ensure that the pH value is 8.5, wherein the concentration of the dopamine is 0.08M. And (3) transferring the micro-nano composite structure super-hydrophobic foam nickel obtained in the step (2) into the prepared solution for treatment for 12 minutes, then repeatedly washing for 3 times by using a buffer solution and deionized water, and drying by blowing under the nitrogen condition to obtain the micro-structure top hydrophilic super-hydrophobic foam nickel. FIG. 2 is a scanning electron microscope image of the nickel foam, which shows that the nickel foam has a micro-nano composite structure; FIG. 3 shows that the surface water contact angle reaches 161.6 °; fig. 4 shows that the surface oil contact angle reaches 0 °.
Example 6:
(1) carrying out ultrasonic treatment on the foamed nickel for 20 minutes by using a hydrochloric acid aqueous solution with the mass fraction of 2mol/L, repeatedly carrying out ultrasonic cleaning for 2 times by using deionized water, and drying for later use; preparing an ethylene glycol/water solution of 22.0mM cobalt nitrate hexahydrate, 38.0mM urea and 102.0mM ammonium fluoride, wherein the volume ratio of ethylene glycol to water is 1: 3; putting the pretreated nickel foam and the preparation solution into a reaction kettle with a tetrafluoroethylene lining, reacting for 16 hours at 150 ℃, and taking out after reaction; and washing with deionized water, and drying to obtain the foamed nickel treated by the hydrothermal method.
(2) Preparing an ethanol/water solution of 1.5g/L of dopamine and 6.5mM of octadecylamine, wherein the volume ratio of ethanol to water is 1: 1; adjusting the pH to 8.5 with Tris-HCl; transferring the foamed nickel treated by the hydrothermal method into a preparation solution for reaction for 24 hours; and washing the reacted foam nickel with deionized water, and drying to obtain the micro-nano composite structure super-hydrophobic foam nickel.
(3) Preparing a Tirs buffer solution by preparing trihydroxymethyl aminomethane, deionized water and dopamine hydrochloride, and then titrating by using hydrochloric acid to ensure that the pH value is 8.5, wherein the concentration of the dopamine is 0.06M. And (3) transferring the micro-nano composite structure super-hydrophobic foam nickel obtained in the step (2) into the prepared solution for treatment for 14 minutes, then repeatedly washing for 3 times by using a buffer solution and deionized water, and drying by blowing under the nitrogen condition to obtain the micro-structure top hydrophilic super-hydrophobic foam nickel. FIG. 2 is a scanning electron microscope image of the nickel foam, which shows that the nickel foam has a micro-nano composite structure; FIG. 3 shows that the surface water contact angle reaches 160.2 °; fig. 4 shows that the surface oil contact angle reaches 0 °.
Example 7:
(1) carrying out ultrasonic treatment on the foamed nickel for 20 minutes by using a hydrochloric acid aqueous solution with the mass fraction of 2mol/L, repeatedly carrying out ultrasonic cleaning for 2 times by using deionized water, and drying for later use; preparing an ethylene glycol/water solution of 18.8mM cobalt nitrate hexahydrate, 30.6mM urea and 93.2mM ammonium fluoride, wherein the volume ratio of ethylene glycol to water is 1: 3; putting the pretreated nickel foam and the preparation solution into a reaction kettle with a tetrafluoroethylene lining, reacting for 24 hours at 158 ℃, and taking out after reaction; and washing with deionized water, and drying to obtain the foamed nickel treated by the hydrothermal method.
(2) Preparing an ethanol/water solution of 2.4g/L of dopamine and 9.6mM of octadecylamine, wherein the volume ratio of ethanol to water is 1: 1; adjusting the pH to 8.5 with Tris-HCl; transferring the foamed nickel treated by the hydrothermal method into a preparation solution for reaction for 24 hours; and washing the reacted foam nickel with deionized water, and drying to obtain the micro-nano composite structure super-hydrophobic foam nickel.
(3) Preparing a Tirs buffer solution by preparing trihydroxymethyl aminomethane, deionized water and dopamine hydrochloride, and then titrating by using hydrochloric acid to ensure that the pH value is 8.5, wherein the concentration of the dopamine is 0.13M. And (3) transferring the micro-nano composite structure super-hydrophobic foam nickel obtained in the step (2) into the prepared solution for treatment for 9 minutes, then repeatedly washing for 3 times by using a buffer solution and deionized water, and drying by blowing under the nitrogen condition to obtain the micro-structure top hydrophilic super-hydrophobic foam nickel. FIG. 2 is a scanning electron microscope image of the nickel foam, which shows that the nickel foam has a micro-nano composite structure; FIG. 3 shows that the surface water contact angle reaches 155.5 °; fig. 4 shows that the surface oil contact angle reaches 0 °.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A material capable of directly adsorbing and separating underwater oil is characterized in that: the material is super-hydrophobic foam nickel with a micro-nano composite structure, and the top end of the micro-nano composite structure of the super-hydrophobic foam nickel is subjected to hydrophilic modification treatment.
2. A method for preparing the material capable of directly adsorbing and separating underwater oil according to claim 1, which comprises the following steps: the method comprises the steps of preparing a micro-nano composite structure on a foamed nickel substrate, so as to obtain super-hydrophobic foamed nickel with the micro-nano composite structure, and carrying out hydrophilic modification treatment on the top end of the micro-nano composite structure of the super-hydrophobic foamed nickel, so as to enhance the stability of an air layer in an underwater microstructure of the micro-nano composite structure, and further realize direct adsorption and separation treatment of underwater oil.
3. The method of claim 2, wherein: the super-hydrophobic nickel foam is obtained by preparing a cobalt oxide micron structure on nickel foam through a hydrothermal method and a solution method, and then carrying out chemical modification on the cobalt oxide micron structure by using dopamine-octadecylamine.
4. The production method according to claim 3, characterized in that: the hydrothermal method and the solution method are combined, namely, the preparation liquid I and the cleaned foam nickel are put into a reaction kettle with polytetrafluoroethylene as a substrate for hydrothermal reaction, the foam nickel after the reaction is cleaned by deionized water and dried to obtain the foam nickel with a cobalt oxide micron structure, wherein the preparation liquid I is ethylene glycol/water solution mixed by cobalt nitrate hexahydrate, urea and ammonium fluoride.
5. The method of claim 4, wherein: the concentration of cobalt nitrate hexahydrate in the preparation liquid I is 12.0-25.0 mM, the concentration of urea is 20.0-40.0 mM, the concentration of ammonium fluoride is 71.0-105.9 mM, and the volume ratio of ethylene glycol to water is 1: 3.
6. The method of claim 5, wherein: the hydrothermal reaction temperature is 140-180 ℃, and the hydrothermal reaction time is 12-24 hours.
7. The method of claim 6, wherein: the dopamine-octadecylamine chemical modification method comprises the steps of putting foam nickel with a cobalt oxide micron structure into a preparation liquid II for reaction, washing with deionized water after the reaction, and drying to obtain super-hydrophobic foam nickel, wherein the water contact angle of the super-hydrophobic foam nickel is 150.0-179.0 degrees, and the oil contact angle is 0 degree; wherein the preparation liquid II is ethanol/water solution of dopamine and octadecylamine, and the pH value is adjusted to 8.5 by Tris-HCL.
8. The method of claim 7, wherein: the concentration of dopamine in the preparation liquid II is 1.2-2.8 g/L, the concentration of octadecylamine is 5.0-10.0 mM, and the volume ratio of ethanol to water is 1: 1.
9. The method of claim 8, wherein: the hydrophilic modification treatment of the top end of the micro-nano composite structure of the super-hydrophobic foam nickel refers to the step of soaking the super-hydrophobic foam nickel in a dopamine buffer solution, washing the reacted super-hydrophobic foam nickel with deionized water and drying, wherein the water contact angle of the super-hydrophobic foam nickel subjected to hydrophilic modification treatment of the top end of the micro-structure is 150.0-179.0 degrees, and the oil contact angle is 0 degree.
10. The method of claim 9, wherein: the dopamine buffer solution is prepared from dopamine hydrochloride and a Tris buffer solution, wherein the concentration of the dopamine is 0.05-0.15 mol/L, the Tris buffer solution is prepared from Tris (hydroxymethyl) aminomethane and water, the pH value is 8.5 by using a hydrochloric acid titration solution, and the soaking time is 8-15 minutes.
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