CN115845813A - Elastic super-hydrophobic oleophylic MOF/SiO 2 Preparation method of composite aerogel - Google Patents
Elastic super-hydrophobic oleophylic MOF/SiO 2 Preparation method of composite aerogel Download PDFInfo
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Abstract
The invention discloses an elastic super-hydrophobic oleophylic MOF/SiO 2 A preparation method of the composite aerogel. The method comprises the following steps: dissolving zinc nitrate hexahydrate and tetrafluoroterephthalic acid in deionized water, and dropwise adding ammonia water to form an MOF precursor; putting the MOF precursor into a tube furnace, carrying out high-temperature pyrolysis in an inert atmosphere, and carrying out acid washing to obtain MOF derived carbon; dissolving a mixture of MOF derived carbon and ethanol and a surfactant in deionized water, ultrasonically oscillating and uniformly stirring to form a mixed solution, which is marked as A; adding methyltrimethoxysilane and dimethyldimethoxysilane into the A as silicon sources, fully stirring, adding an alkali catalyst, and pouring into a mold to wait for gelation; aging and drying the gel to obtain the elastic super-hydrophobic oleophylic MOF/SiO 2 And (3) compounding the aerogel. The invention uses elastic hydrophobic oleophylic SiO 2 Air condensationThe glue is compounded with the MOF derived carbon material, the fragility of the MOF is overcome, and the prepared MOF/SiO 2 The composite aerogel can be restored after being compressed for many times, the water contact angle is as high as 153 degrees, the super-hydrophobic oleophylic performance is shown, and the composite aerogel is beneficial to repeated use.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to elastic super-hydrophobic oleophylic MOF/SiO 2 A preparation method of the composite aerogel.
Background
In recent years, frequent petroleum leakage and discharge of untreated wastewater, farmland sewage and the like cause a large amount of oily substances (including organic substances such as n-alkanes, cycloalkanes, aromatic hydrocarbons and the like) to enter rivers and oceans, which seriously pollutes water quality and ecological environment in areas, causes death of a large amount of aquatic animals, and seriously affects human living environment and physical health.
The common methods for treating oily pollutants in water at present comprise biodegradation, combustion, mechanical oil pumping, oleophilic material oil pumping and the like. The biodegradation method is to artificially culture oil-feeding microorganisms and then put the oil-feeding microorganisms into a polluted water area for biodegradation, but the method has slow degradation speed and long sewage treatment period, and cannot completely avoid the harm caused by oily pollutants. The combustion adopts various combustion improvers to burn a large amount of oily pollutants in a short time, but the oily pollutants can be burnt to generate CO and SO 2 And other harmful gases, and other products of combustion can also influence the growth and reproduction of aquatic animals and plants. The mechanical oil pumping speed is high, but the energy consumption is large, the cost is high, the mechanical oil pumping device is mostly suitable for sea level, and the oil pumping effect is not thorough.
The oleophylic material is used for oil absorption, so that the efficiency is high, the energy consumption is low, the environment is protected, and the policy of double carbon is met. Foams and sponges are lipophilic materials commonly used for oil absorption, but the foams and the sponges absorb part of water while absorbing oily substances, so that the subsequent oil-water separation is inconvenient. The aerogel has the advantages of super-large specific surface, super-high porosity, super-strong oil absorption capacity and the like, is considered as a novel high-efficiency oleophylic oil absorption material, and is particularly suitable for dirty oil treatment. The preparation method comprises the following steps of putting bacterial cellulose in deionized water, performing deacidification, liquid nitrogen freezing, freeze drying and high-temperature pyrolysis treatment to obtain carbon nanofiber aerogel, performing acid catalytic hydrolysis, gel forming and drying treatment to a silicon source containing methyl to obtain silicon dioxide aerogel, extracting cellulose from water hyacinth plants by CN 103333358A and CN 114394600A, preparing cellulose solution, adding a papermaking wet strength agent, uniformly mixing, and performing freeze drying to obtain cellulose aerogel. However, the aerogel prepared by the process has the advantages of small porosity, low specific surface area and insufficient adsorption capacity on oily substances.
Metal Organic Framework (MOF) has larger specific surface, higher porosity and better Hydrophobicity, so that the MOF and the Aerogel have stronger and more Efficient Oil absorption capacity than the Aerogel, and document Hydrophobicity-Adjustable MOF structures Superhydrophic MOF-rGO Aerogel for Efficient Oil Separation reports that a composite Aerogel prepared by compounding pre-prepared MOF microspheres with graphene after surface hydrophobic modification has ultrahigh adsorption capacity on oily pollutants; in patent CN 107215863B, mixing MOF crystal powder with graphene or graphene oxide according to a mass ratio of 1. However, the cost of graphene is too high, which is not beneficial to the large-scale production and application of the graphene/MOF composite aerogel.
Disclosure of Invention
The invention aims to solve the problems and provide an elastic super-hydrophobic oleophylic MOF/SiO with low production cost and convenient operation 2 A preparation method of the composite aerogel.
In order to solve the technical problems, the technical scheme of the invention is as follows: elastic super-hydrophobic oleophylic MOF/SiO 2 The preparation method of the composite aerogel comprises the following steps:
s1, dissolving zinc nitrate hexahydrate and tetrafluoro terephthalic acid in deionized water, and dropwise adding ammonia water to form an MOF precursor;
s2, putting the MOF precursor into a tube furnace, carrying out high-temperature pyrolysis in an inert atmosphere, and then carrying out acid washing to obtain MOF derived carbon;
s3, dissolving a mixture of the MOF derived carbon and ethanol and a surfactant in deionized water, and performing ultrasonic oscillation and uniform stirring to form a mixed solution marked as A;
s4, adding methyltrimethoxysilane and dimethyldimethoxysilane serving as silicon sources into the A, fully stirring, adding an alkali catalyst, and pouring into a mold to wait for gelation;
s5, aging, solvent replacement and drying treatment are carried out on the gel to obtain the elastic super-hydrophobic oleophylic MOF/SiO 2 And (3) compounding the aerogel.
Further, in the step S1, the molar ratio of zinc nitrate hexahydrate to tetrafluoroterephthalic acid is 0.5 to 4.0, and the volume ratio of deionized water to ammonia water is 10 to 60.
Further, the inert gas in the step S2 is Ar gas or N 2 The pyrolysis temperature of the gas is 500-1100 ℃, the pyrolysis time is 0.5-8 h, and the acid is soaked in acid with the concentration of 20% of any one of hydrochloric acid, sulfuric acid and nitric acid for 6-72 h.
Further, the mass ratio of the MOF-derived carbon, ethanol, and surfactant in step S3 is: 0.002-2.0.
Further, in the step S3, the surfactant is at least one of hexadecyl trimethoxy ammonium chloride and hexadecyl trimethoxy ammonium bromide.
Further, in the step S4, the molar ratio of the silane to the surfactant is 0.5 to 2.0.
Further, in the step S4, the alkali catalyst is at least one of sodium hydroxide, potassium hydroxide and ammonia water.
Further, the volume ratio of methyltrimethoxysilane to dimethyldimethoxysilane in step S4 is 0.5 to 2.0
Further, the aging process in the step S5 is carried out at 10-80 ℃.
Further, the drying in the step S5 comprises normal pressure drying, freeze drying and supercritical drying, wherein the temperature of the normal pressure drying is 80-150 ℃, and the time is 24-72 hours; s5, the freeze-drying pre-freezing temperature is-50-0 ℃, the pre-freezing time is 1-12 hours, and the freeze-drying time is 12-72 hours; and S5, the supercritical drying temperature is 35-45 ℃, the pressure is 9-14 MPa, and the time is 8-36 h.
The invention has the beneficial effects that:
1. the invention provides an elastic super-hydrophobic oleophylic MOF/SiO 2 The preparation method of the composite aerogel takes methyl trimethoxy silane and dimethyl dimethoxy silane with low cost as silicon sources and is compounded with MOF derived carbon materials, so that MOF/SiO is prepared 2 And (3) compounding the aerogel. The composite aerogel can be restored after being compressed for many times, and the limitation that the MOF derived carbon material is difficult to reuse due to poor mechanical property is overcome. The composite aerogel has a contact angle with water of 153 degrees, has super-hydrophobicity, can adsorb n-hexane (n-alkane) with the weight being tens of times of the weight of the composite aerogel, is particularly suitable for adsorbing oily pollutants in various water bodies, improves water quality, greens the environment and protects the ecology in an efficient, cheap and environment-friendly manner.
2. The invention uses high elasticity SiO 2 Aerogel is used as a carrier to load the MOF derived carbon with high specific surface. Prepared MOF/SiO 2 The composite aerogel has good hydrophobicity and lipophilicity, can adsorb various organic matters with the weight being several times or even tens of times of the weight of the composite aerogel, can still recover the original shape after being extruded for many times, and is beneficial to repeated use.
Drawings
FIG. 1 is a diagram of an elastic superhydrophobic oleophilic MOF/SiO 2 The flow diagram of the preparation method of the composite aerogel;
FIG. 2 is a diagram of the elastic superhydrophobic lipophilic MOF/SiO obtained in one embodiment of the invention 2 Schematic contact angle of complex aerogel and water;
FIG. 3 is the elastic superhydrophobic oleophilic MOF/SiO obtained in example six of the present invention 2 N of composite aerogel 2 A schematic diagram of a gas adsorption desorption curve;
FIG. 4 is the elastic superhydrophobic oleophilic MOF/SiO obtained in example six of the present invention 2 Schematic contact angle of complex aerogel and water;
FIG. 5 is the present inventionElastic super SiO obtained in the comparative example of the invention 2 N of aerogel 2 The gas adsorption and desorption curve is shown schematically.
Detailed Description
The invention is further described with reference to the following figures and specific examples:
example one
As shown in figure 1, the invention provides an elastic super-hydrophobic oleophilic MOF/SiO 2 The preparation method of the composite aerogel comprises the following steps:
s1, dissolving zinc nitrate hexahydrate and tetrafluoroterephthalic acid in deionized water, and dropwise adding ammonia water to form an MOF precursor.
The molar ratio of zinc nitrate hexahydrate to tetrafluoroterephthalic acid in the step S1 is 0.5-4.0, and the volume ratio of deionized water to ammonia water is 10-60.
In this example, 29.7363g of zinc nitrate hexahydrate and 11.9045g of tetrafluoroterephthalic acid were dissolved in 1000ml of deionized water, and 20ml of aqueous ammonia was added dropwise to form an MOF precursor.
S2, putting the MOF precursor into a tube furnace, performing high-temperature pyrolysis in an inert atmosphere, and then performing acid washing to obtain the MOF derived carbon.
In the step S2, the inert gas is Ar gas or N 2 The pyrolysis temperature of the gas is 500-1100 ℃, the pyrolysis time is 0.5-8 h, and the acid is soaked in acid with the concentration of 20% of any one of hydrochloric acid, sulfuric acid and nitric acid for 6-72 h.
In the embodiment, the MOF precursor is put into a tube furnace and pyrolyzed at 800 ℃ for 4h under Ar atmosphere, and then is soaked in hydrochloric acid with 20% concentration for 24h to obtain MOF-derived carbon.
And S3, dissolving the mixture of the MOF derived carbon and the ethanol and the surfactant in deionized water, and performing ultrasonic oscillation and uniform stirring to form a mixed solution, wherein the mixed solution is marked as A.
In the step S3, the mass ratio of the MOF derived carbon to the ethanol to the surfactant is as follows: 0.002 to 2.0. In the step S3, the surfactant is at least one of hexadecyl trimethoxy ammonium chloride and hexadecyl trimethoxy ammonium bromide.
In this example, a mixture of 0.01g of MOF-derived carbon and 0.2ml of ethanol, 1.5g of surfactant, was dissolved in 21.4ml of deionized water, sonicated and stirred uniformly to form a mixed solution, labeled A.
And S4, adding methyltrimethoxysilane and dimethyldimethoxysilane serving as silicon sources into the A, fully stirring, adding an alkali catalyst, and pouring into a mold to wait for gelation.
The molar ratio of the silane to the surfactant in the step S4 is 0.5-2.0. The alkali catalyst is at least one of sodium hydroxide, potassium hydroxide and ammonia water. In the step S4, the volume ratio of methyltrimethoxysilane to dimethyldimethoxysilane is 0.5-2.0.
In this example, 5ml methyltrimethoxysilane and 3.4ml dimethyldimethoxysilane were added as silicon source to A, ammonia was added after stirring well, the solution ph was adjusted to 9, and poured into molds to wait for gelation.
S5, aging, solvent replacement and drying treatment are carried out on the gel to obtain the elastic super-hydrophobic oleophylic MOF/SiO 2 And (3) compounding the aerogel.
The aging process in the step S5 is carried out at 10-80 ℃, and the drying in the step S5 comprises normal pressure drying, freeze drying and supercritical drying, wherein the temperature of the normal pressure drying is 80-150 ℃, and the time is 24-72 hours; s5, the freeze-drying pre-freezing temperature is-50-0 ℃, the pre-freezing time is 1-12 hours, and the freeze-drying time is 12-72 hours; and S5, the supercritical drying temperature is 35-45 ℃, the pressure is 9-14 MPa, and the time is 8-36 h.
In the actual use process, the atmospheric drying, the freeze drying and the supercritical drying in step S5 may be used sequentially, or only one or a combination of a plurality of drying methods may be selected according to actual needs. So as to be suitable for more using environments and increase the practicability of the invention.
In this example, a small amount of water was added to the gel, which was aged at 40 ℃ for 24h, pre-frozen at-40 ℃ for 5h, and freeze-dried for 48h to give the elastic superhydrophobic oleophilic MOF/SiO 2 Composite aerogel, labeled sample 1. Sample 1 had a contact angle with water of 154.886 deg., and exhibited superhydrophobicity.
The elastic superhydrophobic oleophilic MOF/SiO obtained in this example 2 The contact angles of the complex aerogel and water are shown in fig. 2.
Example two
S1, dissolving 29.7363g of zinc nitrate hexahydrate and 11.9045g of tetrafluoroterephthalic acid in 1000ml of deionized water, and dropwise adding 20ml of ammonia water to form an MOF precursor.
S2, putting the MOF precursor into a tube furnace, pyrolyzing the precursor at 800 ℃ for 4h in Ar atmosphere, and soaking the precursor in hydrochloric acid with the concentration of 20% for 24h to obtain the MOF derived carbon.
S3, dissolving 0.01g of a mixture of MOF derived carbon and 0.2ml of ethanol and 1.5g of a surfactant in 21.4ml of deionized water, and ultrasonically shaking and uniformly stirring to form a mixed solution, wherein the mixed solution is marked as A.
And S4, adding 5ml of methyltrimethoxysilane and 3.4ml of dimethyldimethoxysilane serving as silicon sources into the solution A, fully stirring, adding ammonia water, adjusting the pH of the solution to 9, and pouring the solution into a mold to wait for gelation.
S5, adding a small amount of water into the gel, aging the gel for 24h at 40 ℃, replacing the gel with an ethanol solvent, and performing supercritical drying at 40 ℃ and 14MPa for 12h to obtain the elastic super-hydrophobic oleophylic MOF/SiO 2 The composite aerogel, labeled sample 2.
EXAMPLE III
S1, dissolving 29.7363g of zinc nitrate hexahydrate and 11.9045g of tetrafluoroterephthalic acid in 1000ml of deionized water, and dropwise adding 20ml of ammonia water to form an MOF precursor.
S2, putting the MOF precursor into a tube furnace, pyrolyzing the precursor at 800 ℃ for 4h in Ar atmosphere, and soaking the precursor in hydrochloric acid with the concentration of 20% for 24h to obtain the MOF derived carbon.
S3, dissolving 0.02g of a mixture of MOF derived carbon and 0.4ml of ethanol and 1.5g of a surfactant in 21.4ml of deionized water, and ultrasonically oscillating and uniformly stirring to form a mixed solution, which is marked as A.
And S4, adding 5ml of methyltrimethoxysilane and 3.4ml of dimethyldimethoxysilane serving as silicon sources into the solution A, fully stirring, adding ammonia water, adjusting the pH of the solution to 9, and pouring the solution into a mold to wait for gelation.
S5, adding a small amount of water into the gel, aging the gel for 24 hours at 40 ℃, and then pre-aging the gel at-40 DEG CFreezing for 5h, and freeze-drying for 48h to obtain elastic super-hydrophobic oleophylic MOF/SiO 2 Composite aerogel, labeled sample 3.
Example four
S1, dissolving 29.7363g of zinc nitrate hexahydrate and 11.9045g of tetrafluoroterephthalic acid in 1000ml of deionized water, and dropwise adding 20ml of ammonia water to form an MOF precursor.
S2, putting the MOF precursor into a tube furnace, pyrolyzing the precursor at 800 ℃ for 4h in Ar atmosphere, and soaking the precursor in hydrochloric acid with the concentration of 20% for 24h to obtain the MOF derived carbon.
S3, dissolving 0.05g of a mixture of MOF derived carbon and 1ml of ethanol and 1.5g of a surfactant in 21.4ml of deionized water, and ultrasonically oscillating and uniformly stirring to form a mixed solution, wherein the mixed solution is marked as A.
S4, adding 5ml of methyltrimethoxysilane and 3.4ml of dimethyldimethoxysilane serving as silicon sources into the A, fully stirring, adding ammonia water, adjusting the ph of the solution to 9, pouring the solution into a mold, and waiting for gelation.
S5, adding a small amount of water into the gel, aging the gel for 24 hours at 40 ℃, pre-freezing the gel for 5 hours at-40 ℃, and freeze-drying the gel for 48 hours to obtain the elastic super-hydrophobic oleophylic MOF/SiO 2 Composite aerogel, labeled sample 4.
EXAMPLE five
S1, dissolving 29.7363g of zinc nitrate hexahydrate and 11.9045g of tetrafluoroterephthalic acid in 1000ml of deionized water, and dropwise adding 20ml of ammonia water to form an MOF precursor.
S2, putting the MOF precursor into a tube furnace, pyrolyzing the precursor at 800 ℃ for 4h in Ar atmosphere, and soaking the precursor in hydrochloric acid with the concentration of 20% for 24h to obtain the MOF derived carbon.
S3, dissolving 0.1g of a mixture of MOF derived carbon and 2ml of ethanol and 1.5g of a surfactant in 21.4ml of deionized water, and ultrasonically oscillating and uniformly stirring to form a mixed solution, wherein the mixed solution is marked as A.
And S4, adding 5ml of methyltrimethoxysilane and 3.4ml of dimethyldimethoxysilane serving as silicon sources into the solution A, fully stirring, adding ammonia water, adjusting the pH of the solution to 9, and pouring the solution into a mold to wait for gelation.
S5, adding a small amount of water into the gel, aging the gel for 24 hours at 40 ℃, pre-freezing the gel for 5 hours at-40 ℃, and freeze-drying the gel for 48 hours to obtain the gelElastic super-hydrophobic oleophilic MOF/SiO 2 Composite aerogel, labeled sample 5.
EXAMPLE six
S1, dissolving 29.7363g of zinc nitrate hexahydrate and 11.9045g of tetrafluoroterephthalic acid in 1000ml of deionized water, and dropwise adding 20ml of ammonia water to form an MOF precursor.
S2, putting the MOF precursor into a tube furnace, pyrolyzing the precursor at 800 ℃ for 4h under Ar atmosphere, and soaking the precursor in hydrochloric acid with the concentration of 20% for 24h to obtain MOF derived carbon, which is marked as a sample 6. The specific surface area of sample 6 was 1251.7139m 2 The contact angle with water is 152.652 DEG, which shows super-hydrophobicity.
EXAMPLE six N of MOF-derived carbons obtained 2 The gas adsorption desorption curve is shown in fig. 3, and the contact angle of the MOF-derived carbon and water is shown in fig. 4.
EXAMPLE seven
S1, dissolving 29.7363g of zinc nitrate hexahydrate and 11.9045g of tetrafluoroterephthalic acid in 1000ml of deionized water, and dropwise adding 20ml of ammonia water to form an MOF precursor.
S2, putting the MOF precursor into a tube furnace, pyrolyzing the precursor for 4 hours at 800 ℃ under Ar atmosphere, and soaking the precursor for 24 hours by using hydrochloric acid with the concentration of 20% to obtain the MOF derived carbon.
S3, dissolving 0.02g of a mixture of MOF derived carbon and 0.4ml of ethanol and 1.5g of a surfactant in 21.4ml of deionized water, and ultrasonically oscillating and uniformly stirring to form a mixed solution, which is marked as A.
And S4, adding 5ml of methyltrimethoxysilane and 3.4ml of dimethyldimethoxysilane serving as silicon sources into the solution A, fully stirring, adding ammonia water, adjusting the pH of the solution to 9, and pouring the solution into a mold to wait for gelation.
S5, adding a small amount of water into the gel, aging the gel for 24 hours at 40 ℃, replacing the gel by an ethanol solvent, and performing supercritical drying for 12 hours at 40 ℃ and 14MPa to obtain the elastic super-hydrophobic oleophylic MOF/SiO 2 Composite aerogel, labeled sample 7.
Example eight
S1, dissolving 29.7363g of zinc nitrate hexahydrate and 11.9045g of tetrafluoroterephthalic acid in 1000ml of deionized water, and dropwise adding 20ml of ammonia water to form an MOF precursor.
S2, putting the MOF precursor into a tube furnace, pyrolyzing the precursor at 800 ℃ for 4h in Ar atmosphere, and soaking the precursor in hydrochloric acid with the concentration of 20% for 24h to obtain the MOF derived carbon.
S3, dissolving 0.02g of a mixture of MOF derived carbon and 0.4ml of ethanol and 1.5g of a surfactant in 21.4ml of deionized water, and ultrasonically oscillating and uniformly stirring to form a mixed solution, which is marked as A.
And S4, adding 5ml of methyltrimethoxysilane and 3.4ml of dimethyldimethoxysilane serving as silicon sources into the solution A, fully stirring, adding ammonia water, adjusting the pH of the solution to 9, and pouring the solution into a mold to wait for gelation.
S5, adding a small amount of water into the gel, aging the gel for 24h at 40 ℃, performing solvent replacement by using ethanol, drying the gel for 12h at 80 ℃ under normal pressure, and drying the gel for 48h at 120 ℃ under normal pressure to obtain the elastic super-hydrophobic oleophylic MOF/SiO 2 Composite aerogel, labeled sample 8.
Example nine
S1, dissolving 29.7363g of zinc nitrate hexahydrate and 11.9045g of tetrafluoroterephthalic acid in 1000ml of deionized water, and dropwise adding 20ml of ammonia water to form an MOF precursor.
S2, putting the MOF precursor into a tube furnace, pyrolyzing the precursor for 4 hours at 800 ℃ under Ar atmosphere, and soaking the precursor for 24 hours by using hydrochloric acid with the concentration of 20% to obtain the MOF derived carbon.
S3, dissolving 0.1g of a mixture of MOF derived carbon and 2ml of ethanol and 1.5g of a surfactant in 21.4ml of deionized water, and performing ultrasonic oscillation and uniform stirring to form a mixed solution marked as A;
and S4, adding 5ml of methyltrimethoxysilane and 3.4ml of dimethyldimethoxysilane serving as silicon sources into the solution A, fully stirring, adding ammonia water, adjusting the pH of the solution to 9, and pouring the solution into a mold to wait for gelation.
S5, adding a small amount of water into the gel, aging the gel for 24h at 40 ℃, replacing the gel with an ethanol solvent, and performing supercritical drying at 40 ℃ and 14MPa for 12h to obtain the elastic super-hydrophobic oleophylic MOF/SiO 2 Composite aerogel, labeled sample 9.
EXAMPLE ten
S1, dissolving 29.7363g of zinc nitrate hexahydrate and 11.9045g of tetrafluoroterephthalic acid in 1000ml of deionized water, and dropwise adding 20ml of ammonia water to form an MOF precursor.
S2, putting the MOF precursor into a tube furnace, pyrolyzing the precursor at 800 ℃ for 4h in Ar atmosphere, and soaking the precursor in hydrochloric acid with the concentration of 20% for 24h to obtain the MOF derived carbon.
S3, dissolving 0.1g of a mixture of MOF-derived carbon and 2ml of ethanol and 1.5g of a surfactant in 21.4ml of deionized water, and ultrasonically oscillating and uniformly stirring to form a mixed solution, wherein the mixed solution is marked as A.
And S4, adding 5ml of methyltrimethoxysilane and 3.4ml of dimethyldimethoxysilane serving as silicon sources into the solution A, fully stirring, adding ammonia water, adjusting the pH of the solution to 9, and pouring the solution into a mold to wait for gelation.
S5, adding a small amount of water into the gel, aging the gel at 40 ℃ for 24 hours, replacing the solvent with ethanol, drying the gel at 80 ℃ for 12 hours, and drying the gel at 120 ℃ for 48 hours to obtain the elastic super-hydrophobic oleophylic MOF/SiO 2 Composite aerogel, labeled sample 10.
In the actual use process, the following method was used as a control:
in the first step, 1.5g of surfactant was dissolved in 21.4ml of deionized water, sonicated and stirred uniformly to form a mixed solution, labeled as A.
And secondly, adding 5ml of methyltrimethoxysilane and 3.4ml of dimethyldimethoxysilane serving as silicon sources into the solution A, fully stirring, adding ammonia water, adjusting the pH of the solution to 9, and pouring the solution into a mold to wait for gelation.
And thirdly, adding a small amount of water into the gel, aging the gel for 24 hours at 40 ℃, and finally performing freeze drying treatment to obtain the elastic SiO2 aerogel which is marked as a sample 11. The specific surface of sample 11 was 10.1706m2/g.
The N2 gas adsorption and desorption curve of the elastic hydrophobic oleophilic SiO2 aerogel obtained is shown in fig. 5. By comparison, the MOF/SiO prepared in the examples of the present invention 2 The composite aerogel has better hydrophobicity, lipophilicity and adsorbability.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (10)
1. Elastic super-hydrophobic oleophylic MOF/SiO 2 The preparation method of the composite aerogel is characterized by comprising the following steps:
s1, dissolving zinc nitrate hexahydrate and tetrafluoro terephthalic acid in deionized water, and dropwise adding ammonia water to form an MOF precursor;
s2, putting the MOF precursor into a tube furnace, performing high-temperature pyrolysis in an inert atmosphere, and then performing acid washing to obtain MOF derived carbon;
s3, dissolving a mixture of MOF derived carbon and ethanol and a surfactant in deionized water, and performing ultrasonic oscillation and uniform stirring to form a mixed solution marked as A;
s4, adding methyltrimethoxysilane and dimethyldimethoxysilane serving as silicon sources into the A, fully stirring, adding an alkali catalyst, and pouring into a mold to wait for gelation;
s5, aging, solvent replacement and drying treatment are carried out on the gel to obtain the elastic super-hydrophobic oleophylic MOF/SiO 2 And (3) compounding the aerogel.
2. The elastic superhydrophobic oleophilic MOF/SiO of claim 1 2 The preparation method of the composite aerogel is characterized by comprising the following steps: the molar ratio of zinc nitrate hexahydrate to tetrafluoroterephthalic acid in the step S1 is 0.5-4.0, and the volume ratio of deionized water to ammonia water is 10-60.
3. The elastic superhydrophobic oleophilic MOF/SiO of claim 1 2 The preparation method of the composite aerogel is characterized by comprising the following steps: the inert gas in the step S2 is Ar gas or N 2 The pyrolysis temperature of the gas is 500-1100 ℃, the pyrolysis time is 0.5-8 h, and the acid is soaked in acid with the concentration of 20% of any one of hydrochloric acid, sulfuric acid and nitric acid for 6-72 h.
4. An elastic article according to claim 1Super-hydrophobic oleophilic MOF/SiO 2 The preparation method of the composite aerogel is characterized by comprising the following steps: in the step S3, the mass ratio of the MOF derived carbon to the ethanol to the surfactant is as follows: 0.002 to 2.0.
5. An elastic superhydrophobic lipophilic MOF/SiO according to claim 1 2 The preparation method of the composite aerogel is characterized by comprising the following steps: and in the step S3, the surfactant is at least one of hexadecyl trimethoxy ammonium chloride and hexadecyl trimethoxy ammonium bromide.
6. The elastic superhydrophobic oleophilic MOF/SiO of claim 1 2 The preparation method of the composite aerogel is characterized by comprising the following steps: the molar ratio of the silane to the surfactant in the step S4 is 0.5-2.0.
7. An elastic superhydrophobic lipophilic MOF/SiO according to claim 1 2 The preparation method of the composite aerogel is characterized by comprising the following steps: and in the step S4, the alkali catalyst is at least one of sodium hydroxide, potassium hydroxide and ammonia water.
8. The elastic superhydrophobic oleophilic MOF/SiO of claim 1 2 The preparation method of the composite aerogel is characterized by comprising the following steps: the volume ratio of methyltrimethoxysilane to dimethyldimethoxysilane in the step S4 is 0.5-2.0.
9. The elastic superhydrophobic oleophilic MOF/SiO of claim 1 2 The preparation method of the composite aerogel is characterized by comprising the following steps: the aging process in the step S5 is carried out at 10-80 ℃.
10. The elastic superhydrophobic oleophilic MOF/SiO of claim 1 2 The preparation method of the composite aerogel is characterized by comprising the following steps: the drying in the step S5 comprises normal pressure drying, freeze drying and supercritical drying, wherein the temperature of the normal pressure drying is 80-150 ℃, and the time isIs 24 to 72 hours; s5, pre-freezing at-50-0 ℃ for 1-12 h, and freeze-drying for 12-72 h; and S5, the supercritical drying temperature is 35-45 ℃, the pressure is 9-14 MPa, and the time is 8-36 h.
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