CN112852007B - Preparation method and application of ethylenediamine grafted graphene oxide modified polyurethane carrier - Google Patents
Preparation method and application of ethylenediamine grafted graphene oxide modified polyurethane carrier Download PDFInfo
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Abstract
The invention provides a preparation method and application of an ethylenediamine grafted graphene oxide modified polyurethane carrier. The method comprises the following steps: adding the polyurethane carrier subjected to ultraviolet radiation into an ethylenediamine aqueous solution, carrying out heating reaction, washing the product after the reaction with deionized water, and drying to obtain the polyurethane carrier grafted with ethylenediamine; and placing the polyurethane carrier grafted with the ethylenediamine into the graphene oxide dispersion liquid, and carrying out heating reaction to obtain the ethylenediamine-grafted graphene oxide modified polyurethane carrier. According to the preparation method provided by the invention, the graphene oxide modified and reduced by ethylenediamine has a large specific surface area and a porous structure, so that the damage of cells caused by fluid shear force in the attachment growth process of microorganisms can be relieved, the attachment and spreading process of the cells on the surface of a carrier is shortened, and a biological membrane is easy to form quickly; in addition, the preparation method has the characteristics of simple process, stable performance, short membrane hanging time of the modified carrier and the like, and has good application prospect in the field of sewage treatment.
Description
Technical Field
The invention relates to the field of sewage treatment, and mainly relates to a preparation method and application of an ethylenediamine grafted graphene oxide modified polyurethane carrier.
Background
The biomembrane process is a widely used water treatment process, and essentially realizes the purpose of purifying water by integrating a membrane on the surface of a carrier through microorganisms and adsorbing, converting and decomposing pollutants in sewage (waste water) by utilizing the metabolism of the microorganisms, and has the advantages of high concentration of microbial cells for water treatment, high efficiency in keeping the activity of the cells and reutilization. Wherein the adhesion of the microbial cells to the material is the basis and the carrier is the main part of the biofilm process. The factors such as roughness and chemical properties of the surface of the carrier have a crucial decisive significance on the forming speed of the biological membrane, and are also key factors influencing the operation energy consumption, efficiency and stability of the whole treatment process.
In the biochemical treatment process of sewage, the surface of the carrier filler with good hydrophilicity can form homology affinity with the surface of a hydrophilic microbial film, so that the difficulty of attaching microorganisms to the surface of the carrier is reduced; in addition, the surface of the carrier should have certain roughness, on one hand, the increased specific surface area is beneficial to the attachment of more abundant microorganisms on the surface of the carrier, and on the other hand, under the same aeration condition, the rough carrier is more beneficial to the growth and development of a microbial film than the smooth carrier. The carrier which is widely applied is a polyurethane carrier, and has the advantages of large specific surface area, high porosity and the like, but the polyurethane carrier has the problems of low film forming speed, small film forming amount and the like.
Thus, one technical problem that those skilled in the art are eagerly addressing is: how to accelerate the film forming speed of the polyurethane carrier and improve the film forming amount of the polyurethane carrier.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method and application of an ethylenediamine grafted graphene oxide modified polyurethane carrier, so as to improve the biocompatibility of the polyurethane carrier, improve the film forming speed and increase the film forming amount.
The invention provides a preparation method of an ethylenediamine grafted graphene oxide modified polyurethane carrier, which comprises the following steps:
step 1, irradiating the polyurethane carrier subjected to the first post-treatment by an ultraviolet lamp to obtain a first intermediate product;
step 2, adding an ethylenediamine aqueous solution into the first intermediate product, placing the mixture into a reaction kettle, carrying out a first reaction, and cleaning and drying the reacted first intermediate product to obtain a second intermediate product;
step 3, oxidizing graphite powder by potassium permanganate and hydrogen peroxide to obtain graphene oxide;
step 4, ultrasonically and uniformly dispersing the graphene oxide obtained in the step 3 in deionized water under an ice bath condition to prepare a graphene oxide dispersion liquid;
and 5, immersing the second intermediate product into the graphene dispersion liquid, placing the graphene dispersion liquid into a reaction kettle, and carrying out a second reaction to obtain the ethylenediamine grafted graphene oxide modified polyurethane carrier.
Optionally, in the step 1, the first post-processing includes:
placing polyurethane sponge into an ultrasonic cleaner for vibration washing, and then cleaning with deionized water to obtain a clean polyurethane carrier;
placing the clean polyurethane carrier in an oven for drying to obtain a clean and dry polyurethane carrier;
wherein the shaking washing time is 30-40 min.
Optionally, in the step 1, the irradiation time is 30-60 min.
Optionally, in the step 1, through the irradiation, an amide bond in the polyurethane is cleaved, and a carboxylic acid group is formed, to obtain the first intermediate product.
Optionally, in the step 2, the volume ratio of the ethylenediamine to the deionized water in the ethylenediamine aqueous solution is 30% to 70%.
Optionally, in said step 2,
the reaction temperature of the first reaction is 95 ℃, and the reaction time is 12-24 h;
the cleaning agent comprises deionized water;
the drying temperature is 40-50 ℃.
Optionally, the step 3 includes:
mixing a 9:1 sulfuric acid/phosphoric acid mixed solution with graphite powder to obtain a first mixed solution;
placing the first mixed solution in an ice-water bath, adding potassium permanganate into the first mixed solution, and stirring to obtain a second mixed solution;
placing the second mixed solution at 50 ℃, and stirring for reaction for 12 hours to obtain a first reaction system;
adding ice water into the first reaction system, and placing the mixture in an ice water bath for cooling;
adding a hydrogen peroxide solution into the cooled first reaction system until the mixed solution of the first reaction system becomes bright yellow to obtain a second reaction system;
and carrying out second post-treatment on the second reaction system to obtain the graphene oxide.
Optionally, the mass ratio of the graphite powder to the potassium permanganate is 1: 6;
the volume ratio of the first reaction system to the ice is 1: 1;
the mass fraction concentration of the hydrogen peroxide solution is 0.5%;
the second post-processing includes: and centrifuging the second reaction system at a high speed to obtain a precipitate, centrifuging and washing the precipitate by using deionized water, 10% hydrochloric acid and absolute ethyl alcohol in sequence, and then drying the washed precipitate in vacuum at 50 ℃.
Optionally, in the step 4, the mass ratio of the graphene oxide to the deionized water is 1-25: 5;
in the step 5, heating the second reaction at 95 ℃ for 12-24 hours;
wherein, after the second reaction, the step 5 further comprises:
and (3) placing the carrier after the second reaction into an ultrasonic cleaner, washing for 30min by shaking, cleaning with deionized water, removing impurities on the surface of the carrier, and drying in an oven at 40-50 ℃.
The second aspect of the embodiment of the invention provides an application of an ethylenediamine grafted graphene oxide modified polyurethane carrier, wherein the ethylenediamine grafted graphene oxide modified polyurethane carrier of the first aspect is applied to sewage treatment; or
The ethylenediamine grafted graphene oxide modified polyurethane carrier of the first aspect is applied to microbial curing.
The invention provides a preparation method and application of an ethylenediamine grafted graphene oxide modified polyurethane carrier. The method comprises the following steps: adding the polyurethane carrier subjected to ultraviolet radiation into an ethylenediamine aqueous solution, carrying out heating reaction, washing the product after the reaction with deionized water, and drying to obtain the polyurethane carrier grafted with ethylenediamine; and placing the polyurethane carrier grafted with the ethylenediamine into the graphene oxide dispersion liquid, and carrying out heating reaction to obtain the ethylenediamine-grafted graphene oxide modified polyurethane carrier. Compared with the prior art, the preparation method provided by the invention has the following beneficial effects:
1. in the preparation method provided by the invention, the graphene oxide modified and reduced by ethylenediamine has a large specific surface area and a porous structure, so that the damage of cells caused by fluid shear force in the attachment growth process of microorganisms can be alleviated, the attachment and spreading process of the cells on the surface of a carrier can be shortened, a biological membrane can be easily and rapidly formed, and the membrane hanging speed can be increased.
2. According to the preparation method provided by the invention, the ethylenediamine is used as a cross-linking agent, the graphite oxide is grafted to the polyurethane carrier to obtain the modified polyurethane carrier, and hydrophilic groups such as-OH, -COOH, -O-and the like in the graphene oxide are successfully grafted on the surface of the modified polyurethane carrier, so that the compatibility of the carrier and biomembrane cells in the sewage treatment process is enhanced, the biocompatibility of the modified carrier is improved, the membrane hanging speed of the modified carrier is further improved, and the membrane hanging amount of the modified carrier is increased.
3. In the preparation method provided by the invention, the ethylenediamine is accompanied with a certain grafting reaction in the process of reducing the graphene oxide, and based on the grafting reaction, the steric hindrance between graphene oxide lamella is increased, so that the agglomeration phenomenon of the graphene oxide in the reduction process can be improved, and the modification cost is favorably reduced; meanwhile, due to the fact that steric hindrance between graphene oxide sheet layers is increased, hydrophilic groups in each layer of graphene oxide can be fully contacted with biological membrane cells, and therefore membrane hanging amount of the modified carrier is further increased.
4. According to the method provided by the invention, ethylenediamine is used as a cross-linking agent between the graphene oxide and the polyurethane carrier, and the obtained ethylenediamine grafted graphene oxide modified polyurethane carrier has high structural stability and is not easily damaged by external force in a water environment.
In conclusion, the preparation method provided by the invention has the advantage of simple process, and the ethylenediamine grafted graphene oxide modified polyurethane carrier prepared by the preparation method provided by the invention has the characteristics of stable performance, short film formation time, large film formation amount of the modified carrier and the like, and has a good application prospect in the field of sewage treatment.
Drawings
Fig. 1 shows a flow chart of a method for preparing an ethylenediamine grafted graphene oxide modified polyurethane carrier in an embodiment of the present invention;
FIG. 2 shows a main reaction process diagram of an ethylenediamine grafted graphene oxide modified polyurethane carrier in an embodiment of the present invention;
FIG. 3 shows an SEM image (x 650) of an unmodified polyurethane support;
fig. 4 shows an SEM image (× 850) of the ethylenediamine-grafted graphene oxide-modified polyurethane support prepared in this example 1;
FIG. 5 shows SEM images (x 1200) of unmodified polyurethane carrier biofilm culture experiments;
FIG. 6 shows an SEM image (magnification 450) of the modified carrier prepared in example 1 after the biofilm culturing test;
FIG. 7 shows an SEM image (. times.1300) of the modified carrier prepared in example 1 after the biofilm culture test.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The specific experimental procedures or conditions not specified in this example can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the art. The reagents and other instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The common polyurethane carrier has the advantages of large specific surface area, high porosity and the like, but has the problems of poor hydrophilic performance, low film forming speed, small film forming amount and the like.
Graphene oxide as a monoatomic layer carbon sheet has large specific surface area, good water dispersion capacity and biocompatibility, and the surface of the graphene oxide contains a large number of modifiable active oxygen functional groups, such as carbonyl, hydroxyl, epoxy and the like, so that the graphene oxide is active in chemical property and easy to modify. Therefore, in order to solve the above technical problems, the present invention provides a technical concept of modifying a polyurethane carrier based on the physicochemical properties of graphene oxide, so as to improve the hydrophilicity and biocompatibility of the polyurethane carrier.
In order to achieve the above purpose, according to the preparation method of the ethylenediamine grafted graphene oxide modified polyurethane carrier provided by the embodiment of the invention, the polyurethane carrier is modified by graphene oxide through the crosslinking of ethylenediamine, on one hand, the structural characteristics of the surface of the polyurethane carrier are changed by grafting graphene oxide on the surface of the carrier, and the influence of fluid shear force on the washing and stripping of microorganisms is relieved; on the other hand, the surface of the graphene oxide contains a large number of hydrophilic groups such as hydroxyl (-OH), epoxy (-C (O) C- ], carboxyl (-COOH) and the like, and the hydrophilicity of the carrier is enhanced by using the graphene oxide modified polyurethane, so that cells are easy to attach to the surface of the carrier, the growth of microbial cells is effectively promoted, the membrane hanging time is favorably shortened, and the advantage of treating sewage (wastewater) by a biomembrane process can be more fully exerted.
In a first aspect, the invention provides a preparation method of an ethylenediamine grafted graphene oxide modified polyurethane carrier, the method uses ethylenediamine as a cross-linking agent, and utilizes the graphene oxide modified polyurethane biological carrier, as shown in fig. 1, and comprises the following steps:
step 1(S11), the first post-treated polyurethane carrier is irradiated by an ultraviolet lamp to obtain a first intermediate product.
In this example, the first post-treated polyurethane carrier had clean, dry characteristics. In specific implementation, a clean and dry polyurethane carrier is laid under an ultraviolet lamp and irradiated for 30-60 min, in the irradiation process of the ultraviolet lamp, amido bonds in polyurethane are broken, carboxylic acid groups are formed, and a first intermediate product is obtained.
Optionally, in step 1 of this embodiment, the first post-processing includes:
placing the polyurethane sponge into an ultrasonic cleaner, washing for 30-40 min in a shaking way, and then cleaning with deionized water to obtain a clean polyurethane carrier; and (3) placing the clean polyurethane carrier in an oven for drying to obtain the clean and dry polyurethane carrier.
And 2(S12), adding an ethylene diamine aqueous solution into the first intermediate product, placing the mixture into a reaction kettle for a first reaction, and cleaning and drying the reacted first intermediate product to obtain a second intermediate product.
In specific implementation, the ethylenediamine aqueous solution is added into the first intermediate product, the mixture is placed in a reaction kettle, heated at the temperature of 95 ℃, reacted for 12-24 hours, then the reacted first intermediate product is taken out, washed by deionized water in a shaking way for 1-3 times, and then placed in an oven at the temperature of 40-50 ℃ for drying, and a second intermediate product is obtained.
Optionally, in the step 2, the volume ratio of the ethylenediamine to the deionized water in the ethylenediamine aqueous solution is 30% to 70%.
And step 3(S13), oxidizing the graphite powder by potassium permanganate and hydrogen peroxide to obtain graphene oxide.
In specific implementation, adding graphite powder into a 9:1 sulfuric acid/phosphoric acid mixed solution, uniformly stirring to obtain a first mixed solution, and placing the first mixed solution into an ice-water bath; slowly adding potassium permanganate into the first mixed solution under the stirring state, stirring until the potassium permanganate is uniformly mixed, performing magnetic stirring reaction at the temperature of 50 ℃ for 12 hours, and obtaining a first reaction system after the reaction is finished; adding ice water into the first reaction system, and placing the mixture in an ice water bath for cooling; adding a hydrogen peroxide solution into the cooled first reaction system until the mixed solution (namely the first reaction system) becomes bright yellow to obtain a second reaction system; and (3) centrifuging the second reaction system at a high speed, taking the residual precipitate, centrifuging and washing the precipitate by using deionized water, 10% hydrochloric acid and absolute ethyl alcohol in sequence, and drying the washed precipitate in a vacuum drying oven to obtain the graphene oxide. Wherein the temperature required for drying may be 50 ℃.
Optionally, in the step 3, the mass ratio of the graphite powder to the potassium permanganate can be 1: 6; the volume ratio of the first reaction system to the added ice water can be 1: 1; the hydrogen peroxide solution may have a mass fraction concentration of 0.5%.
And 4(S14), ultrasonically and uniformly dispersing the graphene oxide obtained in the step 3 in deionized water under an ice bath condition to prepare a graphene oxide dispersion liquid.
In specific implementation, the graphene oxide obtained in the step 3 is uniformly dispersed in deionized water by ultrasonic under an ice bath condition, so as to prepare a graphene oxide dispersion liquid.
Optionally, in the step 4, the mass ratio of the graphene oxide to the deionized water is 1-25: 5.
And 5(S15), immersing the second intermediate product into the graphene dispersion liquid, placing the graphene dispersion liquid into a reaction kettle, and carrying out a second reaction to obtain the ethylenediamine grafted graphene oxide modified polyurethane carrier.
And in specific implementation, the second intermediate product obtained in the step 2 is immersed into the graphene oxide dispersion liquid obtained in the step 4, the graphene oxide dispersion liquid is placed in a reaction kettle, the heating is carried out at 95 ℃, the carrier is taken out after the reaction is carried out for 12-24 hours, the carrier is placed in an ultrasonic cleaner and is washed by shaking for 30min, the deionized water is used for cleaning, the surface impurities of the carrier are removed, and the ethylene diamine grafted graphene oxide modified polyurethane carrier with high affinity is obtained after the carrier is placed in an oven at 40-50 ℃ and is dried.
According to the preparation method provided by the embodiment of the invention, the hydrophilic groups of-OH, -COOH, -O-and the like on the surface layer of the graphene oxide of the obtained modified polyurethane carrier can enhance the biocompatibility of the polyurethane carrier and improve the biocompatibility, and the graphene oxide grafted on the surface of the polyurethane carrier is beneficial to accelerating the film forming process of organisms on the surface of the carrier, so that a biological film on the surface of the carrier can be easily and quickly formed. Therefore, the preparation method provided by the embodiment of the invention is simple and easy to implement in the preparation process, and improves the hydrophilicity and the biological affinity of the polyurethane carrier and the formation speed of the biological membrane on the surface of the carrier.
In order to make those skilled in the art better understand the present invention, the following examples are provided to illustrate the preparation method of the ethylenediamine grafted graphene oxide modified polyurethane support provided by the present invention.
Example 1 (preparation of Ethylenediamine grafted graphene oxide modified polyurethane Carrier)
1) Cutting polyurethane sponge into spheres with the diameter of about 1cm, placing the spheres into an ultrasonic cleaner, vibrating and washing the spheres for 30min, cleaning the spheres with deionized water, and placing the spheres in an oven to dry the spheres to obtain clean polyurethane sponge;
2) spreading clean and dry polyurethane sponge under an ultraviolet lamp for irradiating for 60min to obtain a first intermediate product;
3) adding the first intermediate product into an ethylenediamine aqueous solution with the volume fraction of 22%, placing the mixture into a reaction kettle, heating at 95 ℃, taking out after reacting for 24 hours, washing with deionized water, and drying in a 45 ℃ oven to obtain a second intermediate product;
4) preparing graphene oxide: adding graphite powder into a 9:1 sulfuric acid/phosphoric acid mixed solution, uniformly stirring, and placing in an ice-water bath; slowly adding potassium permanganate, stirring to mix uniformly, and reacting for 12h under magnetic stirring at 50 ℃; after the reaction is finished, adding ice water into the mixed solution, and placing the mixed solution in an ice water bath for cooling; adding a hydrogen peroxide solution with the mass fraction concentration of 0.5% until the mixed solution turns into bright yellow; centrifuging the mixed solution at a high speed, taking the residual precipitate, sequentially centrifuging and washing with deionized water, 10% hydrochloric acid and absolute ethyl alcohol, and drying the precipitate in a vacuum drying oven at 50 ℃ to obtain graphene oxide;
5) uniformly dispersing the prepared graphene oxide in deionized water by ultrasonic under an ice bath condition, and preparing 1.0mg/mL graphene oxide dispersion liquid;
6) and (3) immersing the second intermediate product into the prepared 1.0mg/mL graphene oxide dispersion liquid, placing the second intermediate product into a reaction kettle, heating at 95 ℃, reacting for 24 hours, taking out the carrier, placing the carrier into an ultrasonic cleaner, vibrating and washing for 30min, cleaning with deionized water, removing impurities on the surface of the carrier, and placing the carrier into a 45 ℃ oven for drying to obtain the high-affinity ethylenediamine grafted graphene oxide modified polyurethane carrier.
Fig. 3 shows an SEM image of an unmodified polyurethane support, and fig. 4 shows an SEM image of an ethylenediamine-grafted graphene oxide-modified polyurethane support prepared in this example 1. As shown in fig. 3 and 4, compared to the unmodified polyurethane carrier control, the surface of the modified carrier prepared in example 1 was uniformly coated with a layer of graphene oxide, and the surface became significantly rough.
Example 2 (immobilization of microorganism)
A biofilm formation test was performed using the graphene oxide-modified polyurethane carrier prepared in example 1. The biological immobilization carrier is soaked by nutrient solution, and is placed in a 500mL glass triangular flask, and the nutrient solution of 200m L is added into the flask. The microbial inoculum is added according to 4 g/L. The cells were incubated in a constant temperature shaker at a temperature of 30 ℃.
At the time of culturing to day 21, fig. 5 shows SEM images of the unmodified polyurethane carrier biofilm culturing test, fig. 6 shows SEM images of the modified carrier prepared in example 1 after the biofilm culturing test, and fig. 7 shows SEM images of the modified carrier prepared in example 1 after the biofilm culturing test. Fig. 7 is an SEM image obtained by enlarging the SEM image shown in fig. 6, and shows the biofilm formation at a more clear angle, where the magnification in fig. 6 is 450, and the magnification in fig. 7 is 1300.
As shown in FIGS. 4, 5, 6 and 7, independent cocci are observed on the surface of the unmodified filler, and similar EPS structures exist nearby the cocci (the EPS structures refer to extracellular polymeric structures); the biomass on the surface of the modified carrier is obviously increased compared with the surface of the unmodified carrier, a biological membrane develops and matures, the biological membrane is mainly coccus, and microorganisms are found to grow and aggregate near the graphene sheet layer to form a thick and compact blocky structure. Extracting DNA of microorganisms attached to the surfaces of the filler spheres in the biofilm culturing process, and performing quantitative PCR analysis on the abundance of the 16S rDNA of the total bacteria to find that the abundance of the 16S rDNA on the surface of the unmodified polyurethane filler is 1.42 multiplied by 10 from the 5 th day of culture9copies/g carrier increased to 1.22X 10 on day 2110copies/g carrier, and the abundance of 16S rDNA on the modified polyurethane filler ranged from 3.24X 10 on day 5 of culture9Increased to 2.03X 10 at day 2110copies/g carrier, modifiedThe biofilm amount on the surface of the sexual carrier is 1.6 times of that of the unmodified carrier, and the development of the biological membrane is fast.
Wherein "copies/g carrier" is a unit, representing: copy number of microbial gene abundance per gram of filler.
It should be noted that the steps and methods in the embodiments of the present application are not limited to the corresponding embodiments, and the details of the operations and the cautions of the embodiments are all corresponding to each other.
The second aspect of the embodiment of the invention provides an application of an ethylenediamine grafted graphene oxide modified polyurethane carrier, wherein the ethylenediamine grafted graphene oxide modified polyurethane carrier of the first aspect is applied to sewage treatment; or
The ethylenediamine grafted graphene oxide modified polyurethane carrier of the first aspect is applied to microbial curing.
For simplicity of explanation, the method embodiments are described as a series of acts or combinations, but those skilled in the art will appreciate that the present invention is not limited by the order of acts, as some steps may occur in other orders or concurrently in accordance with the invention. Further, those skilled in the art will appreciate that the embodiments described in the specification are preferred embodiments and that the acts and elements referred to are not necessarily required to practice the invention.
The preparation method and the application of the ethylenediamine grafted graphene oxide modified polyurethane carrier provided by the invention are described in detail, specific examples are applied in the description to explain the principle and the implementation mode of the invention, and the description of the examples is only used for helping to understand the method and the core concept of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (8)
1. A preparation method of an ethylenediamine grafted graphene oxide modified polyurethane carrier is characterized by comprising the following steps:
step 1, irradiating a first post-treated polyurethane carrier by an ultraviolet lamp, wherein amide bonds in the polyurethane are broken and carboxylic acid groups are formed by the irradiation to obtain a first intermediate product;
wherein the first post-processing comprises: placing polyurethane sponge into an ultrasonic cleaner for vibration washing, and then cleaning with deionized water to obtain a clean polyurethane carrier; placing the clean polyurethane carrier in an oven for drying to obtain a clean and dry polyurethane carrier;
step 2, adding an ethylenediamine aqueous solution into the first intermediate product, placing the mixture into a reaction kettle, carrying out a first reaction, and cleaning and drying the reacted first intermediate product to obtain a second intermediate product;
wherein the volume ratio of the ethylenediamine to the deionized water in the ethylenediamine aqueous solution is 30-70%; the reaction temperature of the first reaction is 95 ℃, and the reaction time is 12-24 h;
step 3, oxidizing graphite powder by potassium permanganate and hydrogen peroxide to obtain graphene oxide;
step 4, ultrasonically and uniformly dispersing the graphene oxide obtained in the step 3 in deionized water under an ice bath condition to prepare a graphene oxide dispersion liquid; wherein the mass ratio of the graphene oxide to the deionized water is 1-25: 5;
step 5, immersing the second intermediate product into the graphene dispersion liquid, placing the graphene dispersion liquid into a reaction kettle, and carrying out a second reaction to obtain an ethylenediamine grafted graphene oxide modified polyurethane carrier; wherein the reaction temperature of the second reaction is 95 ℃, and the reaction time is 12-24 h.
2. The method as claimed in claim 1, wherein in the step 1, the placing the polyurethane sponge into an ultrasonic cleaner for shaking washing comprises:
the shaking and washing time is 30-40 min.
3. The method according to claim 1, wherein in the step 1, the irradiation time is 30 to 60 min.
4. The method of claim 1, wherein, in the step 2,
the cleaning agent comprises deionized water;
the drying temperature is 40-50 ℃.
5. The method of claim 1, wherein the step 3 comprises:
mixing a 9:1 sulfuric acid/phosphoric acid mixed solution with graphite powder to obtain a first mixed solution;
placing the first mixed solution in an ice-water bath, adding potassium permanganate into the first mixed solution, and stirring to obtain a second mixed solution;
placing the second mixed solution at 50 ℃, and stirring for reaction for 12 hours to obtain a first reaction system;
adding ice water into the first reaction system, and placing the mixture in an ice water bath for cooling;
adding a hydrogen peroxide solution into the cooled first reaction system until the mixed solution of the first reaction system becomes bright yellow to obtain a second reaction system;
carrying out second post-treatment on the second reaction system to obtain graphene oxide;
wherein the second post-processing comprises: and centrifuging the second reaction system at a high speed to obtain a precipitate, centrifuging and washing the precipitate by using deionized water, 10% hydrochloric acid and absolute ethyl alcohol in sequence, and then drying the washed precipitate in vacuum at 50 ℃.
6. The method according to claim 5, wherein the mass ratio of the graphite powder to the potassium permanganate is 1: 6;
the volume ratio of the first reaction system to the ice is 1: 1;
the mass fraction concentration of the hydrogen peroxide solution is 0.5%.
7. The method of claim 1, wherein after the second reaction, the step 5 further comprises:
and (3) placing the carrier after the second reaction into an ultrasonic cleaner, washing for 30min by shaking, cleaning with deionized water, removing impurities on the surface of the carrier, and drying in an oven at 40-50 ℃.
8. An application of the ethylenediamine grafted graphene oxide modified polyurethane carrier is characterized in that the ethylenediamine grafted graphene oxide modified polyurethane carrier prepared by the preparation method of any one of claims 1 to 7 is applied to sewage treatment; or
The ethylenediamine grafted graphene oxide modified polyurethane carrier prepared by the preparation method of any one of claims 1 to 7 is applied to microbial curing.
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| CN102604137A (en) * | 2012-03-12 | 2012-07-25 | 烟台大学 | Method for preparing anti-aging high-transparent polyurethane and graphene oxide composite microporous membrane material |
| CN104610728A (en) * | 2015-01-29 | 2015-05-13 | 苏州大学 | Graphene oxide-polyurethane compound foam as well as preparation method and application thereof |
| CN109054349A (en) * | 2018-09-05 | 2018-12-21 | 四川力智久创知识产权运营有限公司 | A kind of modified graphene oxide material and preparation method thereof for polyurethane material |
| CN110180514A (en) * | 2019-06-27 | 2019-08-30 | 中素新科技有限公司 | Graphene oxide composite sponge and its preparation method and application |
| CN111320257A (en) * | 2020-03-02 | 2020-06-23 | 陕西科技大学 | Polyether polyurethane-graphene oxide foam and preparation method and application thereof |
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| CN102604137A (en) * | 2012-03-12 | 2012-07-25 | 烟台大学 | Method for preparing anti-aging high-transparent polyurethane and graphene oxide composite microporous membrane material |
| CN104610728A (en) * | 2015-01-29 | 2015-05-13 | 苏州大学 | Graphene oxide-polyurethane compound foam as well as preparation method and application thereof |
| CN109054349A (en) * | 2018-09-05 | 2018-12-21 | 四川力智久创知识产权运营有限公司 | A kind of modified graphene oxide material and preparation method thereof for polyurethane material |
| CN110180514A (en) * | 2019-06-27 | 2019-08-30 | 中素新科技有限公司 | Graphene oxide composite sponge and its preparation method and application |
| CN111320257A (en) * | 2020-03-02 | 2020-06-23 | 陕西科技大学 | Polyether polyurethane-graphene oxide foam and preparation method and application thereof |
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