CN114891267A - Preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel - Google Patents
Preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel Download PDFInfo
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Abstract
The invention discloses a preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel, which is characterized in that the graphene/nano-cellulose composite aerogel is prepared by utilizing the high enhancement characteristic of one-dimensional nano-cellulose and by means of the strong hydrogen bond and skeleton supporting action between abundant hydroxyl on the surface of the one-dimensional nano-cellulose and oxygen-containing groups of graphene oxide based on a chemical reduction self-assembly and normal-pressure natural drying method; on the basis, the graphene/nano-cellulose composite aerogel is soaked in a mixed solution of non-polar rubber such as natural rubber, ethylene propylene diene monomer, styrene butadiene rubber, butadiene rubber and the like and a cross-linking agent, the high elasticity effect of the rubber is exerted through high-temperature heating and cross-linking, the high elasticity and the surface hydrophobic oleophylic property of the graphene/nano-cellulose composite aerogel are further enhanced, and the oil-water separation is realized by utilizing the high adsorption property of meshes of the composite aerogel.
Description
Technical Field
The invention relates to a preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel, and belongs to the field of nano-material preparation.
Background
With the development of modern industry, the environmental pollution problem of marine water is becoming more severe, especially the leakage of waste water and waste organic chemical reagents discharged from industries such as petroleum, pesticide, textile and the like, and the oil spill pollution of ships, mail ships and the like pose serious threats to the ecological environment and human health. Realizes the separation and recovery treatment of organic reagents and oil products in the wastewater, realizes the reutilization of resources and energy sources, and has important significance to the environment, the economy and the ecology. At present, the treatment method of the polluted wastewater mainly comprises a chemical precipitation method, an electrolysis method, a membrane separation/filtration method, an ion exchange method, a photocatalytic degradation method and the like, but the methods have certain limitations, such as high cost, complex treatment, low efficiency and the like, and the application is limited. The adsorption method is widely adopted due to the advantages of simple operation, low cost, high efficiency, recyclability, environmental protection and the like, and becomes an important method for oil-water separation.
The graphene aerogel is a light nano porous ultra-light solid material with a continuous three-dimensional network structure, has a nano-scale pore size, extremely low density, high specific surface area and high porosity, and becomes a research hotspot of an oil-water separation material. However, the pore structure of the graphene aerogel collapses and deforms and slag falls due to the capillary action caused by water evaporation in the drying process, the structure is unstable, the mechanical strength and the elasticity are low, the graphene aerogel serving as an adsorption material is easily damaged by mechanics, the realization of the high-efficiency adsorption performance is severely restricted, and the large-scale application of the graphene aerogel is limited. Meanwhile, a freeze drying technology or a supercritical drying technology with high cost and low yield is mostly adopted for preparing the macroscopic body of the graphene aerogel, so that the industrial production and the application and popularization of the graphene aerogel are restricted. The Chinese invention patent CN 109517212A discloses a cellulose-graphene oxide-chitosan ternary composite aerogel, wherein sodium periodate is used for oxidizing cellulose hydroxyl into aldehyde group, then the aldehyde group reacts with chitosan, and the ternary composite aerogel is prepared by freeze drying. The preparation process method is complex in operation and low in efficiency, and cellulose, chitosan and the like contain a large number of hydroxyl groups, so that the hydrophobicity of the composite aerogel is influenced to a certain extent. Chinese invention patent CN 111167414A discloses a grass modified graphene aerogel for efficient oil-water separation and a preparation method thereof, wherein ryegrass is used as a modifier, urea is used as a cross-linking agent, and the grass modified graphene hydrophobic aerogel is prepared through hydrothermal reaction and is used for oil-water separation, but the preparation process needs high temperature and high pressure and is combined with freeze drying, so that the preparation process is complex. Therefore, the method for preparing the high-elasticity graphene aerogel by adopting a simple and efficient method is still challenging when the high-elasticity graphene aerogel is used in the field of oil-water separation.
The cellulose is a natural polymer with the highest abundance in a biosphere on the earth, has the advantages of reproducibility, biodegradation, good biocompatibility, excellent mechanical property and the like, contains abundant hydroxyl groups on the surface, can form a hydrogen bond effect with oxygen-containing functional groups of graphene oxide sheets, and has a special one-dimensional structure which can support a graphene aerogel pore structure and serve as a reinforcing framework. The cross-linked rubber has excellent chemical stability, rebound resilience and hydrophobicity, is introduced into an aerogel system as an elastic component, is favorable for improving the mechanical property and elasticity of the aerogel and further increasing the surface hydrophobicity of the aerogel, and has important practical significance for preparing high-elasticity hydrophobic aerogel. At present, the research report of introducing a graphene aerogel system into rubber is quite lacking.
Disclosure of Invention
The invention aims to provide a preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel aiming at the defects of the prior art, which is characterized in that graphene oxide dispersion liquid is used as a precursor, nano-cellulose is used as a structure supporting unit, a graphene aerogel preparation process is optimized based on simple chemical reduction self-assembly, and the graphene/nano-cellulose composite aerogel is prepared by a normal-pressure natural drying method; on the basis, the composite aerogel is soaked in a rubber/cross-linking agent mixed solution, and the graphene/nano-cellulose composite aerogel with high elasticity and hydrophobic surface is obtained by utilizing the hydrophobic property and high elasticity of the composite aerogel and can be used as an oil-water separation adsorption material.
The invention aims to provide a preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel, which is implemented according to the following steps:
(1) preparing graphene/nano-cellulose composite hydrogel;
(2) preparing graphene/nano-cellulose composite aerogel; and
(3) and (3) preparing the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel.
Further, the step (1) comprises the following steps: preparing graphene/nano-cellulose composite hydrogel based on chemical reduction self-assembly, firstly preparing graphene oxide aqueous dispersion with a certain concentration, then adding a certain amount of nano-cellulose, ultrasonically dispersing and uniformly mixing, adding a reducing agent, stirring, pouring the mixed solution into a mould, placing the mould into a blast oven with a certain temperature for reaction, and dialyzing by adopting an absolute ethyl alcohol/water mixed solvent after the reaction is finished to obtain the graphene/nano-cellulose composite hydrogel.
Preferably, in the step (1), the concentration of the graphene oxide is 3-10 mg/mL, the nanocellulose is one of cellulose nanocrystal and cellulose nanofiber, the mass ratio of the graphene oxide to the nanocellulose is (1-5): 1-10, the ultrasonic dispersion time is 10-90 min, the reducing agent is one of ascorbic acid, ethylenediamine, hydrazine hydrate and sodium sulfite, and the mass of the reducing agent is 50-300% of the mass of the graphene oxide.
Preferably, the reducing agent is one of ascorbic acid, ethylenediamine, hydrazine hydrate and sodium sulfite.
Preferably, the temperature of the blast oven is 70-120 ℃, the reaction time is 30-120 min, the volume ratio of the absolute ethyl alcohol to the water is (80-99): (20-1), the dialysis soaking time is 24 h, and the absolute ethyl alcohol/water mixed solvent is replaced every 12 h.
Further, in the step (2), the graphene/nano-cellulose composite aerogel is prepared by adopting freezing-unfreezing circulation and normal-pressure natural drying conditions.
Preferably, the freezing temperature is-50 to-20 ℃, the freezing time is 6 to 18 hours, the thawing temperature is room temperature, the thawing time is 6 hours, the freezing-thawing cycle times are 1 to 4 times, and the drying condition is that the natural state is dried for 24 to 72 hours under room temperature and normal pressure.
Further, the step (3) comprises the following steps: and (3) placing the rubber in a beaker, adding an organic solvent, heating in a water bath at 60-90 ℃, stirring until the rubber is completely dissolved, adding a cross-linking agent, uniformly stirring, wherein the mass of the cross-linking agent is 0.5-3wt% of that of the rubber, soaking the graphene/nano-cellulose composite aerogel obtained in the step (2) in the mixed solution for 1-10 min, and heating and crosslinking at 100-170 ℃ for 40-120 min to obtain the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel.
Preferably, the rubber is one of natural rubber, ethylene propylene diene monomer, butadiene rubber and styrene butadiene rubber, the organic solvent is one of cyclohexane, toluene and xylene, and the concentration of the rubber solution is 2 wt%.
Preferably, the crosslinking agent is one of dicumyl peroxide, sulfur, 2, 5-dimethyl-2, 5-dihexyl and di-tert-butylperoxy-diisopropylbenzene, and dicumyl peroxide is preferred.
The invention provides a preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel.
According to the invention, the nano-cellulose from biomass is used as a structural support unit, the hydrogen bonding effect of the nano-cellulose and graphene oxide is utilized, the graphene/nano-cellulose composite aerogel is prepared by adopting a chemical reduction self-assembly method, and the rubber/cross-linking agent mixed solution is further impregnated to obtain the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel which can be used for oil-water separation.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the hydrogen bond effect of the one-dimensional nano-cellulose and the graphene oxide is utilized to structurally support the graphene aerogel, the mechanical strength of the graphene aerogel is improved, the agglomeration of the graphene in the chemical reduction assembly process is inhibited, the collapse deformation of the graphene aerogel in the drying process is reduced, the nano-cellulose is rich in source, environment-friendly and non-toxic, the specific surface area of the graphene aerogel can be improved due to the introduction of the nano-cellulose, and the adsorption performance of the graphene aerogel can be enhanced.
2. According to the invention, a normal-pressure natural drying method is adopted to convert the graphene/nano-cellulose hydrogel into the graphene/nano-cellulose aerogel, and the preparation method is simple, convenient and efficient, and is beneficial to large-scale production.
3. In the preparation method of the graphene/nano-cellulose composite aerogel, the introduction of the cross-linked rubber further increases the mechanical property, resilience and surface hydrophobicity of the graphene/nano-cellulose composite aerogel, and is beneficial to expanding the application range of the graphene/nano-cellulose composite aerogel.
Drawings
Fig. 1 is a diagram of a high-elasticity hydrophobic graphene/nanocellulose composite aerogel sample.
Fig. 2 is a diagram of elastic recovery of a high-elasticity hydrophobic graphene/nanocellulose composite aerogel.
Fig. 3 is a surface hydrophobicity diagram of a high-elasticity hydrophobic graphene/nanocellulose composite aerogel.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be merely illustrative and not to be construed as limiting the scope of the invention, and that insubstantial modifications and variations of the invention can be made by those skilled in the art in light of the above teachings.
Example 1
A preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel comprises the following steps:
(1) preparing the graphene/nano-cellulose composite hydrogel: preparing 5 mg/mL graphene oxide aqueous dispersion from 0.1 g graphene oxide and 20 mL deionized water, adding 0.2 g cellulose nanocrystal, performing ultrasonic dispersion for 30 min, uniformly mixing, adding 0.1 g ethylenediamine, stirring, pouring the mixed solution into a circular mold, placing the circular mold in a blowing oven at 85 ℃ for reaction for 2 h, and then soaking the circular mold in an absolute ethyl alcohol/water mixed solvent with a volume ratio of 95:5 for dialysis for 24 h to obtain the graphene/nanocellulose composite hydrogel.
(2) Preparing the graphene/nano-cellulose composite aerogel: and (3) freezing the prepared graphene/nano-cellulose composite hydrogel at-30 ℃ for 12 h, unfreezing the graphene/nano-cellulose composite hydrogel at room temperature for 6 h, circulating for 2 times of freezing and unfreezing, and drying the graphene/nano-cellulose composite hydrogel at room temperature under normal pressure for 48 h in a natural state to obtain the graphene/nano-cellulose composite aerogel.
(3) Preparing the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel: putting 1 g of natural rubber into a beaker filled with 49 g of dimethylbenzene, heating in a 70 ℃ water bath, stirring until the natural rubber is completely dissolved, adding 0.01 g of dicumyl peroxide, stirring uniformly, soaking the obtained graphene/nano-cellulose composite aerogel in the solution for 1 min, and heating and crosslinking at 130 ℃ for 60 min to obtain the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel. Drop the distillation water droplet on the graphite alkene of this embodiment preparation/compound aerogel surface of nanometer cellulose, it is 136 to measure the contact angle, and compound aerogel compressive strength is 113 kPa, and 50% compressive strain rebound resilience is 92%.
Example 2
A preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel comprises the following steps:
(1) preparing the graphene/nano-cellulose composite hydrogel: preparing graphene oxide aqueous dispersion with the concentration of 6 mg/mL by 0.12 g of graphene oxide and 20 mL of deionized water, adding 0.12 g of cellulose nanocrystal, performing ultrasonic dispersion for 60 min, uniformly mixing, adding 0.24 g of ascorbic acid, stirring, pouring the mixed solution into a round mold, placing the round mold in a 95 ℃ blast oven for reaction for 1 h, and then soaking the round mold in an absolute ethyl alcohol/water mixed solvent with the volume ratio of 99:1 for dialysis for 24 h to obtain the graphene/nanocellulose composite hydrogel.
(2) Preparing the graphene/nano-cellulose composite aerogel: and (3) freezing the prepared graphene/nano-cellulose composite hydrogel at-20 ℃ for 10 h, unfreezing the graphene/nano-cellulose composite hydrogel at room temperature for 6 h, circulating for 3 times through freezing and unfreezing, and drying the graphene/nano-cellulose composite hydrogel at room temperature under normal pressure for 48 h in a natural state to obtain the graphene/nano-cellulose composite aerogel.
(3) Preparing the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel: putting 1 g of ethylene propylene diene monomer rubber into a beaker filled with 49 g of cyclohexane, heating in a water bath at 60 ℃, stirring until the ethylene propylene diene monomer rubber is completely dissolved, adding 0.03 g of di-tert-butylperoxydiisopropylbenzene, stirring uniformly, soaking the obtained graphene/nano-cellulose composite aerogel in the solution for 3 min, and heating and crosslinking at 150 ℃ for 90 min to obtain the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel. The distilled water drops on the surface of the graphene/nano-cellulose composite aerogel prepared by the embodiment, the measured contact angle is 142 degrees, the compressive strength of the composite aerogel is 136 kPa, and the 50% compressive strain rebound rate is 96%.
Example 3
A preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel comprises the following steps:
(1) preparing the graphene/nano-cellulose composite hydrogel: preparing graphene oxide aqueous dispersion with the concentration of 8 mg/mL by 0.16 g of graphene oxide and 20 mL of deionized water, adding 0.08 g of cellulose nanocrystal for ultrasonic dispersion for 45 min, uniformly mixing, then adding 0.16 g of hydrazine hydrate for stirring, pouring the mixed solution into a circular mold, placing the circular mold in a blowing oven at 100 ℃ for reaction for 45 min, and then soaking the circular mold in an absolute ethyl alcohol/water mixed solvent with the volume ratio of 90:10 for dialysis for 24 h to obtain the graphene/nanocellulose composite hydrogel.
(2) Preparing the graphene/nano-cellulose composite aerogel: and (3) freezing the prepared graphene/nano-cellulose composite hydrogel at-40 ℃ for 18 h, unfreezing the graphene/nano-cellulose composite hydrogel at room temperature for 6 h, circulating for 2 times of freezing and unfreezing, and drying the graphene/nano-cellulose composite hydrogel at room temperature under normal pressure for 72 h in a natural state to obtain the graphene/nano-cellulose composite aerogel.
(3) Preparing the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel: putting 1 g of butadiene rubber into a beaker filled with 49 g of toluene, heating in a water bath at 80 ℃, stirring until the butadiene rubber is completely dissolved, adding 0.02 g of 2, 5-dimethyl-2, 5-dihexyl, stirring uniformly, soaking the obtained graphene/nano-cellulose composite aerogel in the solution for 5 min, and heating and crosslinking at 160 ℃ for 100 min to obtain the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel. The distilled water drops on the surface of the graphene/nano-cellulose composite aerogel prepared in the embodiment, the measured contact angle is 140 degrees, the compressive strength of the composite aerogel is 126 kPa, and the 50% compressive strain rebound rate is 94%.
Example 4
A preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel comprises the following steps:
(1) preparing the graphene/nano-cellulose composite hydrogel: preparing graphene oxide aqueous dispersion with the concentration of 10 mg/mL by 0.2 g of graphene oxide and 20 mL of deionized water, adding 0.5 g of cellulose nanocrystal, performing ultrasonic dispersion for 90 min, uniformly mixing, adding 0.5 g of ascorbic acid, stirring, pouring the mixed solution into a circular mold, placing the circular mold in a blowing oven at 110 ℃ for reaction for 1 h, and then soaking the circular mold in an absolute ethyl alcohol/water mixed solvent with the volume ratio of 99:1 for dialysis for 48 h to obtain the graphene/nanocellulose composite hydrogel.
(2) Preparing the graphene/nano-cellulose composite aerogel: and (3) freezing the prepared graphene/nano-cellulose composite hydrogel at-25 ℃ for 16 h, unfreezing the graphene/nano-cellulose composite hydrogel at room temperature for 6 h, circulating for 3 times through freezing and unfreezing, and drying the graphene/nano-cellulose composite hydrogel at room temperature under normal pressure for 72 h in a natural state to obtain the graphene/nano-cellulose composite aerogel.
(3) Preparing the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel: putting 1 g of ethylene propylene diene monomer rubber into a beaker filled with 49 g of cyclohexane, heating in a water bath at 75 ℃, stirring until the ethylene propylene diene monomer rubber is completely dissolved, adding 0.015 g of dicumyl peroxide, stirring uniformly, soaking the obtained graphene/nano-cellulose composite aerogel in the solution for 2 min, and heating and crosslinking at 170 ℃ for 120 min to obtain the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel. The distilled water drops on the surface of the graphene/nano-cellulose composite aerogel prepared in the embodiment, the measured contact angle is 148 degrees, the compressive strength of the composite aerogel is 145 kPa, and the 50% compressive strain rebound rate is 95%.
According to the preparation method of the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel, the biomass nano-cellulose is adopted to support the graphene aerogel structurally, the mechanical property of the graphene aerogel is improved, the graphene/nano-cellulose hydrogel is converted into the graphene/nano-cellulose aerogel through a high-efficiency, simple and convenient normal-pressure natural drying method, a cross-linked rubber component is further introduced, the high elasticity and the surface hydrophobicity of the graphene/nano-cellulose hydrogel are further endowed, and the graphene/nano-cellulose composite aerogel can be used in the field of oil-water separation. The preparation process of the composite aerogel is simple, convenient and feasible, and has wide practicability and popularization value.
The above description is only a preferred embodiment of the present invention, and it is within the scope of the appended claims to cover all modifications of the present invention which may be affected by the above description and the accompanying drawings.
Claims (10)
1. A preparation method of high-elasticity hydrophobic graphene/nano-cellulose composite aerogel is characterized by mainly comprising the following steps:
(1) preparing graphene/nano-cellulose composite hydrogel;
(2) preparing graphene/nano-cellulose composite aerogel; and
(3) and (3) preparing the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel.
2. The preparation method of the highly elastic hydrophobic graphene/nanocellulose composite aerogel according to claim 1, wherein step (1) comprises: preparing graphene/nano-cellulose composite hydrogel based on chemical reduction self-assembly, firstly preparing graphene oxide aqueous dispersion with a certain concentration, then adding a certain amount of nano-cellulose, ultrasonically dispersing and uniformly mixing, adding a certain amount of reducing agent for stirring, pouring the mixed solution into a mould, placing the mould in a forced air oven at a certain temperature for reaction, and dialyzing by adopting an absolute ethyl alcohol/water mixed solvent after the reaction is finished to obtain the graphene/nano-cellulose composite hydrogel.
3. The preparation method of the high-elasticity hydrophobic graphene/nanocellulose composite aerogel according to claim 2, wherein in the step (1), the concentration of graphene oxide is 3-10 mg/mL, the nanocellulose is one of cellulose nanocrystals and cellulose nanofibers, the mass ratio of graphene oxide to nanocellulose is (1-5): (1-10), the ultrasonic dispersion time is 10-90 min, the reducing agent is one of ascorbic acid, ethylenediamine, hydrazine hydrate and sodium sulfite, and the mass of the reducing agent is 50-300% of the mass of graphene oxide.
4. The preparation method of the highly elastic hydrophobic graphene/nanocellulose composite aerogel according to claim 2, wherein in step (1), the reducing agent is one of ascorbic acid, ethylenediamine, hydrazine hydrate and sodium sulfite.
5. The preparation method of the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel according to claim 2, wherein in the step (1), the temperature of a blast oven is 70-120 ℃, the reaction time is 30-120 min, the volume ratio of absolute ethyl alcohol/water is (80-99): (20-1), the dialysis soaking time is 24 h, and the absolute ethyl alcohol/water mixed solvent is replaced every 12 h.
6. The preparation method of the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel according to claim 1, wherein in the step (2), the graphene/nano-cellulose composite aerogel is prepared by adopting a freezing-thawing cycle and natural drying conditions under normal pressure.
7. The preparation method of the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel according to claim 6, wherein in the step (2), the freezing temperature is-50 to-20 ℃, the freezing time is 6 to 18 hours, the thawing temperature is room temperature, the thawing time is 6 hours, the number of freezing-thawing cycles is 1 to 4, and the drying condition is room temperature and normal pressure natural drying for 24 to 72 hours.
8. The preparation method of the highly elastic hydrophobic graphene/nanocellulose composite aerogel according to claim 1, wherein step (3) comprises: and (3) placing the rubber in a beaker, adding an organic solvent, heating in a water bath at 60-90 ℃, stirring until the rubber is completely dissolved, adding a cross-linking agent, uniformly stirring, wherein the mass of the cross-linking agent is 0.5-3wt% of that of the rubber, soaking the graphene/nano-cellulose composite aerogel obtained in the step (2) in the mixed solution for 1-10 min, and heating and crosslinking at 100-170 ℃ for 40-120 min to obtain the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel.
9. The preparation method of the high-elasticity hydrophobic graphene/nano-cellulose composite aerogel according to claim 8, wherein in the step (3), the rubber is one of natural rubber, ethylene propylene diene monomer, butadiene rubber and styrene butadiene rubber, the organic solvent is one of cyclohexane, toluene and xylene, and the concentration of the rubber solution is 2 wt%.
10. The preparation method of the high-elasticity hydrophobic graphene/nanocellulose composite aerogel according to claim 8, wherein in the step (3), the cross-linking agent is one of dicumyl peroxide, sulfur, 2, 5-dimethyl-2, 5-dihexyl and di-tert-butylperoxydiisopropylbenzene, and is preferably dicumyl peroxide.
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