CN114452683A - Silica gel/PDA/COFs three-layer composite material for oil-water separation and preparation method thereof - Google Patents
Silica gel/PDA/COFs three-layer composite material for oil-water separation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a silica gel/PDA/COFs three-layer composite material for oil-water separation, which comprises the following steps: s1: preparing a silicon source containing methyl into CH 3-silica gel by a sol-gel method; s2: adding dopamine into CH 3-silicon gel to polymerize the dopamine on CH 3-silicon gel to form a polydopamine film, standing for curing for a period of time, and then cleaning and drying to obtain a two-layer composite material; s3: dissolving the two layers of composite materials and a precursor substance of COFs in an organic solvent, adding a catalyst, and heating and reacting for a period of time under the environment that the PH is neutral; adding alkyl silane for reaction, and cleaning and drying a reaction product to obtain a three-layer composite material; the three-layer composite material for oil-water separation can greatly improve the oil-water separation effect, well adsorb oil-water pollutants with different sizes, realize cyclic utilization of recovered oil, protect the environment and save resources.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a silica gel/PDA/COFs three-layer composite material for oil-water separation and a preparation method thereof.
Background
Oil pollution in water is one of the common pollution in daily life, which is generally caused by human activities, such as industrial discharged oily wastewater, leakage in ship operation and crude oil extraction, and harmful aromatic hydrocarbon substances contained in leaked crude oil can not only cause death of marine organisms, but also can be enriched to finally affect human health. The traditional treatment method generally comprises four modes, namely a physical method, a chemical method, a physical-chemical method and a biochemical method. Physical methods include centrifugation, filtration, gravity separation, and the like; chemical methods are separation by means of neutralization or flocculation; the physical and chemical method is separation by physical means such as electrolysis, electromagnetism, and ultrasonic wave. However, most of the above methods have problems such as low efficiency, incomplete separation, and difficulty in recovering the separated oil, and therefore, the search for materials that can be used in the field of oil-water separation is urgent.
The silicon dioxide aerogel is a three-dimensional nano porous material formed by mutually connecting nano particles, and has wide application value in the aspects of catalyst carriers, sound insulation materials, gas-liquid adsorption, oil-water separation and the like due to the properties of low density (0.003g/cm3), large specific surface area (800-.
However, in practical application environments, the oil-water separation environment is often complex, besides oil and water, other pollutants are also in the environment, and a relatively ideal oil-water separation effect is difficult to obtain by using silica aerogel alone.
Disclosure of Invention
Aiming at least one defect or improvement requirement in the prior art, the invention provides a silica gel/PDA/COFs three-layer composite material for oil-water separation and a preparation method thereof, which can greatly improve the effect of oil-water separation, can well adsorb pollutants with different sizes, can realize cyclic utilization of recovered oil, protect the environment and save resources.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a silica gel/PDA/COFs three-layer composite material for oil-water separation, comprising the steps of:
s1: preparing a silicon source containing methyl into CH 3-silica gel by a sol-gel method;
s2: adding dopamine into CH 3-silica gel while stirring, polymerizing the dopamine on CH 3-silica gel to form a polydopamine film, standing, curing for a period of time, and then cleaning and drying to obtain a two-layer composite material CH 3-silica gel/PDA;
s3: dissolving CH 3-silica gel/PDA and COFs precursor substances in an organic solvent, adding a catalyst, and heating and reacting for a period of time under the condition that the PH is neutral; then adding alkyl silane for reaction, and cleaning and drying the reaction product to obtain the three-layer composite material CH 3-silica gel/PDA/nCOFs-R.
Preferably, step S1 includes:
adding a silicon source containing methyl into an organic solvent, stirring uniformly to fully dissolve the silicon source, adjusting the solution environment to be alkalescent, standing until the solution is stable, and then carrying out vacuum drying to obtain CH 3-silica gel, wherein the vacuum drying temperature is 20-25 ℃, and the vacuum drying time is 12-24 hours.
Preferably, the standing and curing time in the step S2 is 18-24 hours, and the reaction product after standing and curing is kept standing in absolute ethyl alcohol for 24 hours; after washing and drying, CH 3-silica gel/PDA was obtained.
Preferably, the heating temperature in the step S3 is 100-120 ℃, and the reaction time is 12-24 h.
Preferably, the catalyst in step S3 is one of acetic acid and ammonia water.
Preferably, in step S2, the methyl-containing silicon source includes methyltriethoxysilane mixed with one or more other methyl-containing silicon sources.
Preferably, in step S3, the precursor of the COFs is one or more of 1, 3, 5-tris (4-aminophenyl) benzene, 1, 4-dicarboxyl-2, 5-divinylbenzene, II SERP-COF 2-beta, COF-300-AR, COF-1, 2, 5-dihydroxyterephthalic acid, 2, 3, 5, 6-tetrafluoro-terephthalic acid formaldehyde, 1, 4-o-phthalaldehyde, 2, 6-diisopropylaniline, tetraphenylmethane, perfluorooctyltriethoxysilane, 3-aminopropyltriethoxysilane, terephthalic acid, 4' -biphenylcarbaldehyde, and the like.
Preferably, the organic solvents used in steps S1 and S3 are: anhydrous methanol, anhydrous ethanol, acetone, N-hexane, ethyl acetate, N-dimethylformamide, N-diethylformamide, dichloromethane, trichloromethane, tetrachloromethane, petroleum ether, tetrahydrofuran, pyridine, pyrrole, acetonitrile, toluene, 1, 4-dioxane, N-butanol, N-hexylether, acetic acid, and a mixture of any one or more of 1, 2-dichlorobenzene.
Preferably, the alkylsilane is a mixture of two or more of propyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecylmethyldimethoxysilane, octyltriethoxysilane and hexadecyltrimethoxysilane.
According to another aspect of the invention, the invention also provides the silica gel/PDA/COFs three-layer composite material for oil-water separation synthesized according to the preparation method.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) according to the silica gel/PDA/COFs three-layer composite material for oil-water separation and the preparation method thereof, CH 3-silica gel, PDA and COFs are compounded to form the three-layer composite material for oil-water separation, alkylsilane of the COFs layer on the outermost layer has certain hydrophobic performance, primary separation of oil and water can be achieved, secondary separation of oil and water is further performed through the CH 3-silica gel on the innermost layer, and compared with pure silica aerogel, the effect of oil-water separation effect can be greatly improved.
(2) According to the silica gel/PDA/COFs three-layer composite material for oil-water separation and the preparation method thereof, MTMS (methyl triethoxysilane) and other methyl-containing silicon source substances are compounded to serve as a mixed silicon source to prepare the silica aerogel, so that the hydrophobicity and lipophilicity of the material are enhanced, the oil-water separation effect can be further enhanced, oil storage and extrusion oil discharge like a sponge can be achieved, the oil is recycled, the environment is protected, and resources are saved.
(3) According to the silicone gel/PDA/COFs three-layer composite material for oil-water separation and the preparation method thereof, provided by the invention, the mechanical strength and stability of the three-layer composite material are improved by utilizing the crosslinking effect of the COFs material, and the silicone gel/PDA/COFs three-layer composite material is coated on the outermost periphery of the composite material and can further play a role in protecting gel. In addition, the CH 3-silica gel and the COFs layer are bonded through PDA, so that the mechanical stability of the structure of the material after multiple extrusion oil drainage recycling is guaranteed.
(4) According to the silica gel/PDA/COFs three-layer composite material for oil-water separation and the preparation method thereof, organic ligands R with different C atomic weights can be selected according to the molecular weights of complex pollutants in an oil-water environment, the pore size of the COFs layer of the composite material is controlled according to the length of the organic ligands R, so that good adsorption effects on the pollutants with different sizes are realized, meanwhile, the combination of different pore sizes in the COFs layer can adsorb the pollutants layer by layer, and the purity of the extracted oil is improved; on the other hand, the thickness of the COFs can be controlled by adjusting the number n of the layers of the COFs according to different oil-water environments, so that the required oil-water separation reaction rate is achieved.
(5) The silica gel/PDA/COFs three-layer composite material for oil-water separation and the preparation method thereof have the advantages of simple process, mild reaction conditions and low preparation cost, and are suitable for industrial large-scale production.
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FIG. 1 is a schematic three-dimensional structure diagram of a silica gel/PDA/COFs three-layer composite material for oil-water separation and a preparation method thereof provided by the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a silica gel/PDA/COFs three-layer composite material for oil-water separation and a preparation method thereof, wherein the composite material is compounded by CH 3-silica gel, polydopamine PDA and organic framework material COFs three-layer materials. As shown in fig. 1, the three-dimensional structure diagram of the silicone gel/PDA/COFs three-layer composite material for oil-water separation of the present invention is shown, specifically, the CH 3-silicone gel is coated by PDA to form two-layer core-shell structure CH 3-silicone gel/PDA, the CH 3-silicone gel/PDA is coated by COFs to form three-layer core-shell structure CH 3-silicone gel/PDA/nCOFs-R, wherein the size of n represents the thickness of the outer-coated COFs layer, and R represents an organic ligand for adjusting the pore size structure of the COFs with different numbers of carbon atoms.
The three-layer composite material CH 3-silica gel/PDA/nCOFs-R has excellent oil-water separation effect, and the principle of the three-layer composite material used for oil-water separation is as follows:
the three-layer composite material for separating oil from water is formed by compounding the CH 3-silica gel, the PDA and the COFs, alkylsilane of the COFs layer on the outermost layer has certain hydrophobic property, primary separation of oil and water can be realized, secondary separation of the oil and water is further performed on the oil and water by the CH 3-silica gel on the innermost layer, and compared with pure silica aerogel, the three-layer composite material has a better oil-water separation effect.
Dopamine (DA) is an adhesive polymer with a unique surface modification function, and polydopamine PDA is used as the adhesive polymer to connect CH 3-silica gel and nCOFs-R, so that a three-layer composite material CH 3-silica gel/PDA/nCOFs-R is formed, and the mechanical stability of the structure of the composite material after multiple extrusion oil drainage cycles is guaranteed.
COFs is a novel crystalline porous organic framework material formed by connecting light elements (such as B, C, O and N) through covalent bonds, has good structural flexibility, and has the characteristics of high specific surface area, adjustable porosity, precise periodicity, high chemical stability, low density and the like. The COFs layer is coated on the outermost layer of the composite material, so that the gel can be further protected, and the mechanical strength and stability of the three-layer composite material are improved by utilizing the crosslinking effect of the COFs material. In addition, the thickness of the COFs can be controlled by adjusting the number n of the layers of the COFs according to different oil-water environments, so that the required oil-water separation reaction rate is achieved; the preparation of different sizes of apertures in the COFs can be controlled on the one hand by adjusting the length of the organic ligand R in the COFs, and the organic ligand R can block different other macromolecular pollutants layer by layer according to different apertures, so that the purity of the extracted oil is improved, and on the other hand, the alkyl silane with different C atomic weights can be selected according to the molecular weight of the complex pollutants in the oil-water environment, so that the oil-water separation with higher cost performance is realized. Meanwhile, the alkyl silane has certain hydrophobic property, and can realize primary separation of oil and water.
The preparation method of the silica gel/PDA/COFs three-layer composite material for oil-water separation provided by the invention is explained in detail by a plurality of specific examples. The preparation method of the silica gel/PDA/COFs three-layer composite material for oil-water separation provided by the invention comprises the following steps:
s1: preparing CH 3-silica gel from silicon source containing methyl by sol-gel method
Adding a silicon source containing methyl into an organic solvent, uniformly stirring by magnetic force until the silicon source is completely dissolved, then slowly dropwise adding 10% ammonia water, shaking by hand while dropwise adding, controlling the pH value of the solution to be about 7.5-8.5 under a weak alkaline environment, then stirring by magnetic force for 1-5 min to uniformly disperse the solution, standing for 2-10 min, after the solution is stabilized, moving the solution into a vacuum drying oven for drying, controlling the temperature to be 20-25 ℃, the drying time to be 12-24h, taking out after drying is completed to prepare CH 3-silicon gel, and covering a layer of preservative film for later use after taking out to prevent impurity pollution in the air.
Preferably, in the invention, MTMS (methyl triethoxysilane) and other silicon sources containing methyl are compounded to be used as a composite silicon source to prepare CH 3-silicon gel by a sol-gel method so as to improve the comprehensive performance of the aerogel. The volume ratio of MTMS to other silicon sources containing methyl in the composite silicon source ranges from 1:1 to 5: 1.
The silicon source containing methyl groups can be selected from: ethyl Orthosilicate (TEOS), methyl orthosilicate (TMOS), Hexamethyldisilazane (HMDS), dimethyldimethoxysilane (DMDMS), Dodecyltrimethoxysilane (DTMS), Trimethylchlorosilane (TMCS), Hexamethyldisilazane (HMDZ), and the like. Due to the addition of MTMS, the prepared gel has super elasticity and super hydrophobicity, high Young modulus and good comprehensive mechanical property, can realize oil-water separation, can also realize continuous oil storage and extrusion oil discharge like a sponge, and realizes the recycling of oil.
Furthermore, melamine or polyurethane can be added into the composite silicon source to further improve the oil storage performance of the composite material, and the amount of the melamine or the polyurethane is not more than 1/5 of the composite silicon source.
S2: adding dopamine DA into CH 3-silica gel while stirring to polymerize dopamine on CH 3-silica gel, standing and curing for a period of time to obtain a two-layer composite material CH 3-silica gel/PDA;
specifically, the prepared CH 3-silica gel is cleaned for 2-8 times by using a cleaning agent, taken out, put into a beaker filled with the cleaning agent, and then a certain amount of Dopamine (DA) is slowly added. Adding Dopamine (DA) while stirring with a glass rod, polymerizing the Dopamine (DA) on CH 3-silica gel to form a stable Polydopamine (PDA) film, finally obtaining two layers of composite material CH 3-silica gel/PDA, standing and curing for 18-24 h, standing for 24h in absolute ethyl alcohol, taking out, extruding out residual solution, repeatedly cleaning with a detergent for 5-10 times, flushing out the ethanol solution, drying in a vacuum drying oven at 25 ℃ for 1-5 h to prevent pollution, taking out and covering a layer of preservative film for later use. The cleaning agent can be one or more of tetrahydrofuran, ethanol, anhydrous methanol, deionized water, etc.
S3: dissolving CH 3-silica gel/PDA and COFs precursor substances in an organic solvent, adding a catalyst, heating for reaction for a period of time, and adjusting the pH to be neutral; then adding alkyl silane R for reaction, and cleaning and drying the reaction product to obtain the three-layer composite material CH 3-silica gel/PDA/nCOFs-R.
Specifically, the prepared CH 3-silica gel/PDA and a precursor substance of COFs are dissolved in a certain amount of organic solvent, and are reacted for 12-24 hours at 120 ℃ by a microwave-assisted heating method under the catalysis of a catalyst, after the reaction is finished, the cleaning agent is used for washing, the PH of the solution is adjusted to be neutral, multilayer nCOFs is obtained, then alkylsilanes R containing different numbers of C atoms are added into the organic solvent and are uniformly stirred, so that the substitution of active sites in the COFs is finished, CH 3-silica gel/PDA/nCOFs is formed, then the obtained solution is taken out of the solution, the solution in the COFs is extruded out, then the obtained solution is repeatedly cleaned by the cleaning agent, and the obtained product is dried for 12-24 hours in a vacuum drying box, so that a three-layer composite material CH 3-silica gel/PDA/nCOFs-R is obtained.
The n value here represents the number of COFs, the number of COFs is different, namely the thickness of COFs is different, the oil absorption rate is different, the thinner the COFs layer is, the shorter the diffusion path of the molecule is, the faster the diffusion is, and the faster the oil absorption is, otherwise, the thicker the COFs layer is, the longer the diffusion path of the molecule is, and the steric effect formed by the multi-level holes is, so that the diffusion is slowed down, and the oil absorption is slowed down.
R represents organic alkyl silane ligands with different carbon atoms and is used for adjusting the pore structure of COFs, the more the carbon atoms of R, the larger the pore diameter of the composite material formed, and the R with different carbon atoms can be selected according to actual requirements. In the invention, two or more than two organic alkyl silane ligands are preferably mixed to form the COFs-R layer, the COFs-R layers with different pore structures can be formed by selecting the organic alkyl silane ligands with different carbon atom numbers, and when the oil-water mixture enters the COFs-R layer for oil-water separation, the oil-water mixture is filtered by the COFs-R layers with different pore structures, so that the effect of layer-by-layer separation is achieved.
Specifically, the organoalkylsilane ligand R is selected from propyltriethoxysilane containing 9C atoms; octyl trimethoxysilane (KH305) with 11C atoms; octyl triethoxysilane (KH306) containing 14C atoms; dodecyl trimethoxysilane (KH304) containing 14C atoms; dodecyl methyl dimethoxysilane (KH303) containing 15C atoms; octyl triethoxysilane (KH306) containing 14C atoms; hexadecyltrimethoxysilane (KH310) having 19C atoms, and the like.
The mass of R is generally taken to be 5% to 25% of the total solution volume, i.e. if the COFs synthesized are thicker, the dose of silane used is also correspondingly increased.
Precursor species for synthesizing COFs include: 1, 3, 5-tris (4-aminophenyl) benzene, 1, 4-dicarboxyl-2, 5-divinylbenzene, II SERP-COF 2-beta, COF-300-AR, COF-1, 2, 5-dihydroxyterephthalic acid, 2, 3, 5, 6-tetrafluoro-terephthalic acid formaldehyde, 1, 4-phthalaldehyde, 2, 6-diisopropylaniline, tetraphenylmethane, perfluorooctyltriethoxysilane, 3-aminopropyltriethoxy, terephthalic acid, 4' -biphenyldicarboxaldehyde and the like.
The catalyst can be selected from: acetic acid and ammonia water, the dosage of which is 0.1-10% of the total amount of the substance A and the organic solvent.
Specifically, the organic solvents used are: any one or a mixture of more of absolute methanol, absolute ethanol, acetone, N-hexane, ethyl acetate, N-dimethylformamide, N-diethylformamide, dichloromethane, trichloromethane, tetrachloromethane, petroleum ether, tetrahydrofuran, pyridine, pyrrole, acetonitrile, toluene, 1, 4-dioxane, N-butanol, N-hexylether, acetic acid and 1, 2-dichlorobenzene.
In the preparation method of the three-layer composite material CH 3-silica gel/PDA/nCOFs-R for oil-water separation, the addition amount of the silicon source containing methyl, the PDA and the precursor substance of the COFs is specifically determined according to the number n of the layers of the COFs to be synthesized, and preferably, the molar ratio of the silicon source containing methyl, the PDA and the precursor substance of the COFs is (1-1.2): (0.8-1.2): (0.8 to 1.2) n. The following will explain in detail the preparation method of the three-layer composite material for oil-water separation provided by the present invention by data in different specific examples.
EXAMPLE two preparation of CH 3-silica gel/PDA/1 COFs-R
(1) Preparation of CH 3-silica gel by sol-gel method
Dissolving 3.6ml of Methyl Triethoxysilane (MTMS) and 1.2ml of Tetraethoxysilane (TEOS) in a container filled with 25ml of absolute ethyl alcohol, ultrasonically stirring for 5min until the mixture is uniform, then slowly dropping 10% ammonia water, shaking by hand while dropping, controlling the pH of the solution environment to be about 8 under weak alkalinity, then stirring by magnetic force for 1min to uniformly disperse the solution, standing for 2-3 min, after the solution is stable, transferring the solution into a vacuum drying oven for drying, controlling the temperature to be 25 ℃, controlling the drying time to be 18h, taking out after the drying is finished, preparing CH 3-silicon gel, and covering a preservative film after the taking out for later use in order to prevent impurity pollution in the air.
(2) Preparation of two-layer composite CH 3-Silicone gel/PDA
Taking the prepared CH 3-silica gel, washing the gel with deionized water for 2-3 times, taking out the gel, putting the gel into a beaker with 100ml of deionized water, slowly adding 0.1g of Dopamine (DA), stirring the gel with a glass rod while adding the dopamine, polymerizing the gel on the CH 3-silica gel to form a stable Polydopamine (PDA) film, finally forming CH 3-silica gel/PDA, standing and curing the gel for 24 hours, standing the gel in absolute ethyl alcohol for 24 hours, taking out the gel, extruding out residual solution, repeatedly washing the gel with deionized water for 5-10 times, flushing off the ethanol solution, drying the gel in a vacuum drying box for 1 hour at 25 ℃ to prevent pollution, taking out the gel, and covering a layer of preservative film for later use;
(3) preparing three-layer composite material CH 3-silica gel/PDA/nCOFs-R
Dissolving 3ml of CH 3-silica gel/PDA prepared in the steps and 3ml of 1, 3, 5-tri (4-aminophenyl) benzene and 3ml of 1, 4-dialdehyde-2, 5-divinylbenzene which are precursor substances of COFs in 35ml of absolute ethyl alcohol, adding 1.32ml of ammonia water with the catalyst mass fraction of 10%, heating for 12h by adopting a microwave-assisted heating method at 100 ℃, washing by using tetrahydrofuran and ethanol after the reaction is finished, slowly adjusting the pH of the solution to be neutral by using 1mol/L of acetic acid to obtain CH 3-silica gel/PDA/1 COF, adding 1.5ml of each of propyltriethoxysilane and octyltrimethoxysilane which respectively contain 9 and 11C atoms into the organic solvent, magnetically stirring for 5min to finish the substitution of active sites on the 1COF to generate CH 3-silica gel/PDA/1 COFs-R, extruding the solution, washing with tetrahydrofuran, ethanol and deionized water, and drying in a vacuum drying oven for 24h to obtain the target product CH 3-silica gel/PDA/1 COFs-R. .
EXAMPLE III preparation of CH 3-silica gel/PDA/2 COFs-R
(1) Preparation of CH 3-silica gel by sol-gel method
Dissolving 3.6ml of Methyl Triethoxysilane (MTMS) and 1.2ml of methyl orthosilicate (TMOS) in a container filled with 25ml of absolute ethyl alcohol, ultrasonically stirring for 5min until the mixture is uniformly mixed, slowly dropping 10% ammonia water by mass fraction, shaking by hand while dropping, controlling the solution environment to be alkalescent pH about 8, then stirring by magnetic force for 1min to uniformly disperse the solution, standing for 2-3 min, after the solution is stable, transferring the solution into a vacuum drying oven for drying, controlling the temperature to be 25 ℃, controlling the drying time to be 18h, taking out the solution after the drying is finished to prepare CH 3-silicon gel, and in order to prevent impurity pollution in the air, covering a preservative film after the solution is taken out for later use
(2) Preparation of two-layer composite CH 3-Silicone gel/PDA
Taking the prepared CH 3-silica gel, washing the gel with deionized water for 2-3 times, taking out the gel, putting the gel into a beaker with 100ml of deionized water, slowly adding 0.1g of Dopamine (DA), stirring the gel with a glass rod while adding the dopamine, polymerizing the gel on the CH 3-silica gel to form a stable Polydopamine (PDA) film, finally forming CH 3-silica gel/PDA, standing and curing the gel for 24 hours, standing the gel in absolute ethyl alcohol for 24 hours, taking out the gel, extruding out residual solution, repeatedly washing the gel with deionized water for 5-10 times, flushing off the ethanol solution, drying the gel in a vacuum drying box for 1 hour at 25 ℃ to prevent pollution, taking out the gel, and covering a layer of preservative film for later use;
(3) preparation of three-layer composite material CH 3-silica gel/PDA/nCOFs-R
Dissolving 6ml of CH 3-silica gel/PDA prepared in the steps and 6ml of 1, 3, 5-tri (4-aminophenyl) benzene and 1, 4-dialdehyde-2, 5-divinylbenzene in 35ml of absolute ethanol, adding 1.59ml of ammonia water with the mass fraction of 10% of catalyst, heating for 12h by adopting a microwave-assisted heating method at 100 ℃, washing by using tetrahydrofuran and ethanol after the reaction is finished, slowly adjusting the pH of the solution to be neutral by using 1mol/L of acetic acid to obtain CH 3-silica gel/PDA/2 COF, then adding 3ml of each of propyltriethoxysilane and octyltrimethoxysilane containing 9 and 11C atoms respectively into the organic solvent, magnetically stirring for 5min to finish the substitution of active sites on 1 to generate CH 3-silica gel/PDA/1 COF-R, extruding the solution, washing with tetrahydrofuran, ethanol and deionized water, and drying in a vacuum drying oven for 24h to obtain the target product CH 3-silica gel/PDA/2 COFs-R. .
EXAMPLE four preparation of CH 3-silica gel/PDA/3 COFs-R
(1) Preparation of CH 3-silica gel by sol-gel method
Dissolving 3.6ml of Methyl Triethoxysilane (MTMS) and 1.2ml of Hexamethyldisilazane (HMDS) in a container filled with 25ml of absolute ethyl alcohol, ultrasonically stirring for 5min until the mixture is uniformly mixed, slowly dropping 10% ammonia water by mass fraction, shaking by hand while dropping, controlling the solution environment to be alkalescent pH about 8, then stirring by magnetic force for 1min to uniformly disperse the solution, standing for 2-3 min, after the solution is stable, transferring the solution into a vacuum drying oven for drying, controlling the temperature to be 25 ℃, controlling the drying time to be 18h, taking out the solution after the drying is finished to prepare CH 3-silicon gel, and in order to prevent impurity pollution in the air, covering a preservative film after the solution is taken out for later use
(2) Preparation of two-layer composite CH 3-Silicone gel/PDA
Taking the prepared CH 3-silica gel, washing the gel with deionized water for 2-3 times, taking out the gel, putting the gel into a beaker with 100ml of deionized water, slowly adding 0.1g of Dopamine (DA), stirring the gel with a glass rod while adding the dopamine, polymerizing the gel on the CH 3-silica gel to form a stable Polydopamine (PDA) film, finally forming CH 3-silica gel/PDA, standing and curing the gel for 24 hours, standing the gel in absolute ethyl alcohol for 24 hours, taking out the gel, extruding out residual solution, repeatedly washing the gel with deionized water for 5-10 times, flushing off the ethanol solution, drying the gel in a vacuum drying box for 1 hour at 25 ℃ to prevent pollution, taking out the gel, and covering a layer of preservative film for later use;
(3) preparation of three-layer composite material CH 3-silica gel/PDA/nCOFs-R
Dissolving 9ml of CH 3-silica gel/PDA prepared in the steps and 9ml of 1, 3, 5-tri (4-aminophenyl) benzene and 1, 4-dialdehyde-2, 5-divinylbenzene in 35ml of absolute ethyl alcohol, adding 1.86ml of ammonia water with the mass fraction of 10% of catalyst, heating for 12h by adopting a microwave-assisted heating method at 100 ℃, washing by using tetrahydrofuran and ethanol after the reaction is finished, slowly adjusting the pH of the solution to be neutral by using 1mol/L of acetic acid to obtain CH 3-silica gel/PDA/3 COF, then respectively adding 4.5ml of propyltriethoxysilane and octyltrimethoxysilane which respectively contain 9 and 11 carbon atoms into the organic solvent, magnetically stirring for 5min to finish the substitution of active sites on the 1COF to generate CH 3-silica gel/PDA/1 COFs-R, extruding the solution, washing with tetrahydrofuran, ethanol and deionized water, and drying in a vacuum drying oven for 24h to obtain the target product CH 3-silica gel/PDA/3 COFs-R.
EXAMPLE V preparation of CH 3-silica gel/PDA/1 COFs-R (molar ratio of the methyl-containing silicon source, PDA, and COFs precursor materials is 1.1: 1: 1)
(1) Preparation of CH 3-silica gel by sol-gel method
Dissolving 1.474ml of methyltriethoxysilane (MTMS) and 0.814ml of Tetraethoxysilane (TEOS) in a container filled with 25ml of absolute ethyl alcohol, ultrasonically stirring for 5min until the mixture is uniformly mixed, slowly dropping 10% ammonia water by mass fraction, shaking by hand while dropping, controlling the pH value of the solution environment to be about 8 under weak alkalinity, then stirring by magnetic force for 1min to uniformly disperse the solution, standing for 2-3 min, after the solution is stable, moving the solution into a vacuum drying oven for drying, controlling the temperature to be 25 ℃, controlling the drying time to be 18h, taking out after the drying is finished, preparing CH 3-silica gel, and in order to prevent impurity pollution in the air, covering a preservative film after taking out for later use;
(2) preparation of two-layer composite CH 3-Silicone gel/PDA
Taking the CH 3-silica gel prepared in the above step, cleaning with deionized water for 2-3 times, taking out, putting into a beaker containing 100ml of deionized water, slowly adding 0.01g of Dopamine (DA), stirring with a glass rod while adding, polymerizing on CH 3-silica gel to form a stable Polydopamine (PDA) film, finally forming CH 3-silica gel/PDA, standing and curing for 24h, standing in absolute ethyl alcohol for 24h, taking out, extruding out residual solution, repeatedly cleaning with deionized water for 5-10 times, flushing away the ethyl alcohol solution, drying in a vacuum drying oven for 1h at 25 ℃, preventing pollution, taking out and covering a preservative film for later use;
(3) preparation of three-layer composite material CH 3-silica gel/PDA/nCOFs-R
Dissolving 1.15ml of CH 3-silica gel/PDA prepared in the steps and 0.45ml of 1, 3, 5-tri (4-aminophenyl) benzene as a precursor of COFs together in 35ml of absolute ethanol, adding 0.732ml of 10% ammonia water serving as a catalyst mass fraction, heating for 12 hours at 100 ℃ by adopting a microwave-assisted heating method, washing with tetrahydrofuran and ethanol after the reaction is finished, slowly adjusting the pH of the solution to be neutral by using 1mol/L acetic acid to obtain CH 3-silica gel/PDA/1 COF, adding 0.34ml and 0.39ml of propyltriethoxysilane and octyltrimethoxysilane which respectively contain 9 and 11 carbon atoms into the organic solvent, magnetically stirring for 5min to finish the substitution of active sites on the 1COF to generate CH 3-silica gel/PDA/1 COFs-R, extruding out the solution inside, washing with tetrahydrofuran, ethanol and deionized water, and drying in a vacuum drying oven for 24h to obtain the target product.
EXAMPLE sixthly preparation of CH 3-silica gel/PDA/1 COFs-R (molar ratio of the silicon source containing methyl, PDA and the precursor substance of COFs is 1: 0.8: 0.8)
(1) Preparation of CH 3-silica gel by sol-gel method
Dissolving 1.34ml of Methyl Triethoxysilane (MTMS) and 0.74ml of Tetraethoxysilane (TEOS) in a container filled with 25ml of absolute ethyl alcohol, ultrasonically stirring for 5min until the mixture is uniform, then slowly dropping 10% ammonia water by mass fraction, shaking by hand while dropping, controlling the pH of the solution environment to be about 8 under weak alkalinity, then stirring by magnetic force for 1min to uniformly disperse the solution, standing for 2-3 min, after the solution is stabilized, moving the solution into a vacuum drying oven for drying, controlling the temperature to be 25 ℃, controlling the drying time to be 18h, taking out the solution after the drying is finished, preparing CH 3-silica gel, and in order to prevent impurity pollution in the air, covering a preservative film after the solution is taken out for later use;
(2) preparation of two-layer composite CH 3-Silicone gel/PDA
Taking the prepared CH 3-silica gel, washing the gel with deionized water for 2-3 times, taking out the gel, putting the gel into a beaker with 100ml of deionized water, slowly adding 0.008g of Dopamine (DA), stirring the gel with a glass rod while adding the dopamine, polymerizing the gel on the CH 3-silica gel to form a stable Polydopamine (PDA) film, finally forming CH 3-silica gel/PDA, standing and curing the gel for 24 hours, standing the gel in absolute ethyl alcohol for 24 hours, taking out the gel, extruding out residual solution, repeatedly washing the gel with deionized water for 5-10 times, flushing off the ethanol solution, drying the gel in a vacuum drying oven for 1 hour at 25 ℃ to prevent pollution, taking out the gel, and covering a layer of preservative film for later use;
(3) preparation of three-layer composite material CH 3-silica gel/PDA/nCOFs-R
Dissolving 0.92ml of CH 3-silica gel/PDA prepared in the above steps and 0.36ml of 1, 3, 5-tri (4-aminophenyl) benzene as a precursor of COFs together in 35ml of absolute ethanol, adding 0.727ml of ammonia water with the mass fraction of 10% as a catalyst, heating for 12h by adopting a microwave-assisted heating method at 100 ℃, washing with tetrahydrofuran and ethanol after the reaction is finished, slowly adjusting the pH of the solution to be neutral by using 1mol/L acetic acid to obtain CH 3-silica gel/PDA/1 COF, adding 0.272ml of propyltriethoxysilane and 0.312ml of octyltrimethoxysilane which respectively contain 9 and 11 carbon atoms into the organic solvent, magnetically stirring for 5min to finish the substitution of active sites on the 1COF to generate CH 3-silica gel/PDA/1 COFs-R, extruding out the solution inside, washing with tetrahydrofuran, ethanol and deionized water, and drying in a vacuum drying oven for 24h to obtain the target product.
EXAMPLE seventhly, CH 3-silica gel/PDA/1 COFs-R (methyl group-containing silicon source, PDA, and COFs precursor substance in a molar ratio of (1.2: 1: 1.2) was prepared
(1) Preparation of CH 3-silica gel by sol-gel method
Dissolving 1.608ml of Methyl Triethoxysilane (MTMS) and 0.888ml of Tetraethoxysilane (TEOS) in a container filled with 25ml of absolute ethyl alcohol, ultrasonically stirring for 5min until the mixture is uniform, then slowly dropping ammonia water with the mass fraction of 10%, shaking by hand while dropping, controlling the pH of the solution environment to be about 8 under weak alkalinity, then stirring by magnetic force for 1min to uniformly disperse the solution, standing for 2-3 min, after the solution is stabilized, moving the solution into a vacuum drying oven for drying, controlling the temperature to be 25 ℃, controlling the drying time to be 18h, taking out after the drying is finished, preparing CH 3-silica gel, and in order to prevent impurity pollution in the air, covering a preservative film after taking out for later use;
(2) preparation of two-layer composite CH 3-Silicone gel/PDA
Taking the prepared CH 3-silica gel, washing the gel with deionized water for 2-3 times, taking out the gel, putting the gel into a beaker with 100ml of deionized water, slowly adding 0.01g of Dopamine (DA), stirring the gel with a glass rod while adding the dopamine, polymerizing the gel on the CH 3-silica gel to form a stable Polydopamine (PDA) film, finally forming CH 3-silica gel/PDA, standing and curing the gel for 24 hours, standing the gel in absolute ethyl alcohol for 24 hours, taking out the gel, extruding out residual solution, repeatedly washing the gel with deionized water for 5-10 times, flushing off the ethanol solution, drying the gel in a vacuum drying box for 1 hour at 25 ℃ to prevent pollution, taking out the gel, and covering a layer of preservative film for later use;
(3) preparation of three-layer composite material CH 3-silica gel/PDA/nCOFs-R
Dissolving 1.38ml of CH 3-silica gel/PDA prepared in the above steps and 1, 3, 5-tri (4-aminophenyl) benzene as a precursor of COFs, and 0.54ml of 1, 4-dialdehyde-2, 5-divinylbenzene in 35ml of absolute ethanol, adding 0.7384ml of 10% ammonia water serving as a catalyst mass fraction, heating for 12 hours at 100 ℃ by adopting a microwave-assisted heating method, washing with tetrahydrofuran and ethanol after the reaction is finished, slowly adjusting the pH of the solution to be neutral by using 1mol/L acetic acid to obtain CH 3-silica gel/PDA/1 COF, adding 0.408ml and 0.468ml of propyltriethoxysilane and octyltrimethoxysilane containing 9 and 11C atoms respectively into the organic solvent, magnetically stirring for 5min to finish the substitution of active sites on the 1COF to generate CH 3-silica gel/PDA/1 COFs-R, extruding out the solution inside, washing with tetrahydrofuran, ethanol and deionized water, and drying in a vacuum drying oven for 24h to obtain the target product.
Selecting heavy oil: dichloromethane, chloroform, light oil: the performance of the oil-water separation composite materials prepared in the second embodiment to the fourth embodiment is tested by using four different organic solvents, namely ethyl acetate and n-hexane, and the test indexes comprise:
n1: the adsorption capacity of the CH 3-silica gel/PDA/nCOFs-R composite material to oil for the first time is expressed as a multiple of the mass of the material.
The following formula was used for calculation:
wherein M1 is the mass of the CH 3-silica gel/PDA/nCOFs-R composite material before oil absorption, and M2 is the mass of the CH 3-silica gel/PDA/nCOFs-R composite material after oil absorption.
N2: shows that the adsorption capacity of the CH 3-silica gel/PDA/nCOFs-R composite material to oil accounts for the multiple of the mass of the material after the composite material is repeatedly extruded for 25 times to absorb and discharge oil, a calculation formula and N1The calculation formula of (2) is the same.
K: the oil-water separation ratio is expressed and calculated by the following formula:
K1is the organic carbon content of the oil-water mixture before separation, K2The organic carbon content of the oil-water mixture after separation by using a CH 3-silica gel/PDA/nCOFs-R composite material; the method comprises the following steps of (1) determining the oil content in an oil-water system by using a total organic carbon content tester: the oil-water mixture was injected into the instrument, and the instrument read the organic carbon content of the oil-water mixture.
Θ: the contact angle of the material surface and water is measured by a water contact angle tester.
Vn: the adsorption rates corresponding to different n values in the CH 3-silica gel/PDA/nCOFs-R composite material are represented, and the adsorption rates are calculated by the ratio of the oil quantity capable of being absorbed in unit time of 1s to the self mass.
TABLE 1 test results of the relevant indices in example II
| Methylene dichloride | Chloroform | Ethyl acetate | N-hexane | |
| N1 | 62.34 | 80.17 | 56.44 | 54.08 |
| N2 | 61.58 | 79.88 | 56.07 | 53.87 |
| K | 98.64％ | 99.10％ | 97.45％ | 98.20％ |
| Θ | 151.8 | 154.3 | 149.7 | 150.9 |
| Vn | 6.6 | 6.3 | 6.8 | 6.5 |
TABLE 2 test results of the related indices in the third example
| Methylene dichloride | Chloroform | Ethyl acetate | N-hexane | |
| N1 | 62.45 | 79.46 | 58.32 | 56.69 |
| N2 | 60.97 | 80.38 | 57.29 | 54.92 |
| K | 98.86％ | 98.17％ | 98.53％ | 99.11％ |
| Θ | 152.3 | 150.4 | 153 | 150.6 |
| Vn | 5.4 | 5.25 | 5.4 | 5.18 |
Table 3 test results of the related indexes in the fourth example
| Methylene dichloride | Chloroform | Ethyl acetate | N-hexane | |
| N1 | 61.59 | 80.12 | 59.17 | 56.77 |
| N2 | 61.23 | 79.78 | 58.36 | 57.42 |
| K | 99.30％ | 97.66％ | 97.93％ | 98.82％ |
| Θ | 150.7 | 149.4 | 152.1 | 150.6 |
| Vn | 4.56 | 4.47 | 4.5 | 4.29 |
Table 4 test results of the relevant indices in example five
| Methylene dichloride | Chloroform | Ethyl acetate | N-hexane | |
| N1 | 61.07 | 78.54 | 54.16 | 53.27 |
| N2 | 60.15 | 77.99 | 53.98 | 53.02 |
| K | 99.56％ | 99.35％ | 99.14％ | 99.27％ |
| Θ | 152.1 | 154.1 | 150.3 | 150.9 |
| Vn | 6.47 | 6.13 | 6.50 | 6.41 |
Table 5 test results of the relevant indices in the six examples
| Methylene dichloride | Chloroform | Ethyl acetate | N-hexane | |
| N1 | 62.01 | 78.94 | 55.41 | 53.44 |
| N2 | 60.76 | 78.45 | 54.87 | 53.26 |
| K | 99.48％ | 99.26％ | 99.00％ | 99.09％ |
| Θ | 151.3 | 153.9 | 149.2 | 150.1 |
| Vn | 6.51 | 6.23 | 6.55 | 6.42 |
TABLE 6 test results of the seventh related index of example
| Methylene dichloride | Chloroform | Ethyl acetate | N-hexane | |
| N1 | 62.15 | 79.01 | 55.12 | 54.29 |
| N2 | 61.18 | 78.87 | 54.90 | 53.65 |
| K | 99.55％ | 99.47％ | 99.29％ | 99.30％ |
| Θ | 150.8 | 154.7 | 151.0 | 151.4 |
| Vn | 6.44 | 6.28 | 6.52 | 6.57 |
Test results show that the adsorption capacity of the CH 3-silica gel/PDA/nCOFs-R composite material prepared in each embodiment of the invention to heavy oil is as much as 80 times of the self weight of the composite material, the adsorption capacity to light oil is as high as 60 times of the self weight of the composite material, the oil absorption capacity of the composite material is basically not reduced after circulating oil absorption for 25 times, the water contact angle of each embodiment reaches or approximately reaches super-hydrophobicity, the oil-water separation rate is over 97.5 percent, the introduced group on the R realizes primary separation of oil and water and the hydrophobic effect of the CH 3-silica gel CH3 realizes secondary re-hydrophobic effect, and simultaneously, V is used for realizing secondary re-hydrophobic effect through V-silica gelnIt can be understood that the oil-water separation rate can be controlled by changing the thickness n value of the COFs to meet the actual production requirement.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a silica gel/PDA/COFs three-layer composite material for oil-water separation is characterized by comprising the following steps:
s1: preparing a silicon source containing methyl into CH 3-silica gel by a sol-gel method;
s2: adding dopamine into CH 3-silicon gel to polymerize the dopamine on CH 3-silicon gel to form a polydopamine film, standing for curing for a period of time, and then cleaning and drying to obtain a two-layer composite material;
s3: dissolving the two layers of composite materials and a precursor substance of COFs in an organic solvent, adding a catalyst, and heating and reacting for a period of time under the environment that the PH is neutral; and adding alkyl silane for reaction, and cleaning and drying a reaction product to obtain the three-layer composite material.
2. The method for preparing the silica gel/PDA/COFs three-layer composite material for oil-water separation according to claim 1, wherein the step S1 comprises:
adding a silicon source containing methyl into an organic solvent, stirring uniformly to fully dissolve the silicon source, adjusting the solution environment to be alkalescent, standing until the solution is stable, and then carrying out vacuum drying to obtain CH 3-silica gel, wherein the vacuum drying temperature is 20-25 ℃, and the vacuum drying time is 12-24 hours.
3. The preparation method of the silica gel/PDA/COFs three-layer composite material for oil-water separation as claimed in claim 1, wherein the standing and curing time in the step S2 is 18-24 h, the reaction product after standing and curing is kept standing in absolute ethyl alcohol for 24h, and the CH 3-silica gel/PDA is obtained after washing and drying.
4. The method as claimed in claim 1, wherein the heating temperature in step S3 is 100-120 deg.C, and the reaction time is 12-24 h.
5. The method of claim 1, wherein the catalyst in step S3 is acetic acid or ammonia water.
6. The method of claim 1, wherein in step S2, the methyl-containing silicon source comprises methyl triethoxysilane mixed with one or more other methyl-containing silicon sources.
7. The method of claim 1, wherein the precursor of the COFs is one or more selected from 1, 3, 5-tris (4-aminophenyl) benzene, 1, 4-dialdehyde-2, 5-divinylbenzene, IISERP-COF 2-beta, COF-300-AR, COF-1, 2, 5-dihydroxyterephthalic acid, 2, 3, 5, 6-tetrafluoro-terephthalaldehyde, 1, 4-phthalaldehyde, 2, 6-diisopropylaniline, tetraphenylmethane, perfluorooctyltriethoxysilane, 3-aminopropyltriethoxy group, terephthalic acid, 4' -biphenyldicarboxaldehyde, etc. in step S3.
8. The method for preparing the silica gel/PDA/COFs three-layer composite material for oil-water separation according to claim 1, wherein the organic solvents used in the steps S1 and S3 are: any one or a mixture of more of absolute methanol, absolute ethanol, acetone, N-hexane, ethyl acetate, N-dimethylformamide, N-diethylformamide, dichloromethane, trichloromethane, tetrachloromethane, petroleum ether, tetrahydrofuran, pyridine, pyrrole, acetonitrile, toluene, 1, 4-dioxane, N-butanol, N-hexylether, acetic acid and 1, 2-dichlorobenzene.
9. The method of claim 1, wherein the alkylsilane is a mixture of two or more selected from propyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecylmethyldimethoxysilane, octyltriethoxysilane, and hexadecyltrimethoxysilane.
10. A silica gel/PDA/COFs three-layer composite material for oil-water separation, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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