CN117181188B - Three-dimensional graphene oxide composite material and preparation method and application thereof - Google Patents
Three-dimensional graphene oxide composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 6
- 239000004642 Polyimide Substances 0.000 claims abstract description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 6
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a three-dimensional graphene oxide composite material, a preparation method and application thereof, and relates to the technical field of sewage treatment. In addition, the hydroxyl at the end of the graphene oxide is subjected to oxidation reaction in a microwave reactor under alkaline conditions to become carboxyl, a large amount of gas is generated in the oxidation process, meanwhile, the forming agent adopts polyacrylonitrile, carboxymethyl cellulose, polyimide and other resin materials which are easy to carbonize, the carbonization temperature is low, low-temperature carbonization is carried out before the graphene oxide is subjected to oxidation reaction, a large amount of gas is generated in the carbonization process, a three-dimensional porous network structure is formed in the material, the adsorption effect of the three-dimensional graphene oxide composite material is improved, and the adsorption performance of the three-dimensional graphene oxide composite material in unit volume is also improved after the forming agent is carbonized.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a three-dimensional graphene oxide composite material and a preparation method and application thereof.
Background
The sewage recycling means that sewage reaches a specific water quality standard through innocent treatment, is used as reclaimed water to replace conventional water resources, is used for industrial production, municipal miscellaneous use, resident life, ecological water supplement, agricultural irrigation, recharging groundwater and the like, extracts other resources and energy sources from the sewage, and has important significance in optimizing a water supply structure, increasing water resource supply, relieving contradiction between supply and demand, reducing water pollution and guaranteeing water ecological safety. The sewage contains a large amount of organic matters, the concentration level of the sewage is uneven, the distribution range is wider (from trace organic matters to dissolved state, colloid state and particle state), and the degradation difficulty is higher. The common methods include physical, chemical and biological methods. Adsorption is one of the common methods, and plays a great role in sewage treatment and recycling. For example, activated carbon is commonly used for adsorption, the pore size distribution range of the activated carbon is wide, and the scholars propose to divide the pore size of the activated carbon into three types: the aperture is smaller than 2nm and is micro-aperture, the aperture is 2-50 nm and is meso-aperture, the aperture is larger than 50nm and is macro-aperture, wherein the micro-aperture specific surface area accounts for more than 95% of the specific surface area of the active carbon, the aperture is small, the adsorption capacity of the active carbon to organic matters is weak, saturation phenomenon is easy to occur in adsorption, the adsorption of the organic matters is mainly based on size effect, the non-differential adsorption is realized, the consumption of the active carbon is large, the adsorption period is long, and the treatment time and the economic cost are greatly increased.
Chinese patent CN105622028B discloses an organic-inorganic composite porous sewage treatment material and a preparation method thereof, wherein the sewage treatment material is made porous by utilizing the water absorption self-expansion effect of clay, and then the obtained sewage treatment material has different pore diameters by utilizing the strong adsorptivity and ion exchange property of macroporous resin, agriculture and forestry waste and clay, and the pore channels are mutually communicated, so that the problems of poor sewage treatment effect on complex components, environmental pollution and the like of the traditional sewage treatment material can be solved. However, macroporous adsorption resin has high price, large usage amount and no selective adsorption, so that the production cost of the product is high, the use cost is high, and the requirement of industrial application is difficult to adapt.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows: aiming at the defects existing in the prior art, the three-dimensional graphene oxide composite material is provided, and the three-dimensional graphene oxide frame structure with rich mesoporous structure is prepared by selectively reducing graphene oxide in a customized way, so that the preparation method is simple and convenient, has low production cost, is suitable for industrial production, and can be widely applied to the fields of liquid and gas separation and adsorption.
In order to solve the first technical problem, the technical scheme of the invention is as follows:
the preparation method of the three-dimensional graphene oxide composite material comprises the following steps:
s01, dissolving a forming agent in a polar solvent to obtain a solution A, wherein the forming agent is one of polyacrylonitrile, carboxymethyl cellulose and polyimide;
s02, adding graphene oxide into the same polar solvent as that in the step S01, stirring and dissolving to obtain a graphene oxide solution, adding alkali into the graphene oxide solution, and stirring and dissolving to obtain a solution B;
s03, slowly adding the solution A into the solution B under the stirring condition to obtain a solution C, wherein the mass ratio of the forming agent to the graphene oxide is 0.1-1:1;
s04: transferring the solution C into a baking oven, controlling the baking temperature to be 50-95 ℃ and the baking time to be 0.5-24 hours, and removing the polar solvent to obtain a baked material;
s05: and transferring the dried material into a crucible, placing the crucible in a microwave reactor for reaction at 290-900 ℃, and cleaning and drying the product to obtain the three-dimensional graphene oxide composite material.
Preferably, the mass fraction of the solution A in the step S01 is 1 to 30wt%.
Preferably, the polar solvent in step S01 and step S02 is one of dimethylacetamide, dimethylformamide, and N-methylpyrrolidone.
Preferably, the alkali in the step S02 is one of sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide, and the mass ratio of the alkali to the graphene oxide is 0.1-2:1.
Preferably, the mass fraction of the graphene oxide solution in step S02 is 1 to 10wt%.
Preferably, the stirring speed in step S03 is 150 to 1500r/min.
Preferably, the dropping speed of the solution A in the step S03 is 10-1000 ml/min.
Preferably, the stirring time in step S03 is 0.5 to 4 hours.
Preferably, the reaction time in step S05 is 10 to 60 minutes.
Preferably, the oxygen content of the graphene oxide is between 30 and 40 percent, the size of the microchip is between 0.5 and 3 mu m, and the thickness is between 0.55 and 1.2 nm.
The second technical problem to be solved by the invention is as follows: aiming at the defects existing in the prior art, the three-dimensional graphene oxide composite material is provided, the aperture is large, and the adsorption effect on organic matters is good.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
the specific surface area of the three-dimensional graphene oxide composite material is more than 1700m 2 The ratio of the pore diameter to the pore diameter of more than 5 mu m is more than 79 percent, and the iodine value is more than 1600mg/g.
The third technical problem to be solved by the invention is that: aiming at the defects existing in the prior art, the application of the three-dimensional graphene oxide composite material in sewage treatment is provided.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the preparation method of the three-dimensional graphene oxide composite material is simple, low in cost and suitable for industrial production.
2. Specific surface area of three-dimensional graphene oxide composite material is more than 1700m 2 The ratio of the aperture of more than 5 mu m is more than 79 percent, the iodine value is more than 1600mg/g, the adsorption effect on organic matters is good, and the method can be widely applied to the field of sewage treatment.
3. The forming agent can accelerate the formation of graphene oxide, and can play a role in reducing the excessive expansion of the graphene oxide during microwave high-temperature reaction, so that the density of the three-dimensional graphene oxide material is improved, and the obtained three-dimensional graphene oxide composite material is higher in strength.
4. The alkali is used for reacting with hydroxyl-terminated groups in the graphene oxide to generate hydroxyl sodium salt, the terminal oxygen is protected from being reduced during the high-temperature microwave reaction, and the epoxy structure of the graphene oxide is reduced to perform selective reduction of the composite material, so that the three-dimensional graphene oxide framework structure with rich mesoporous structure is prepared in a customized mode. In addition, water generated in the process of generating the hydroxy sodium salt becomes gas in the microwave, meanwhile, the forming agent adopts resin materials which are easy to carbonize, such as polyacrylonitrile, carboxymethyl cellulose, polyimide and the like, the carbonization temperature is low, low-temperature carbonization is carried out before the graphene oxide is subjected to oxidation reaction, a large amount of gas is generated in the carbonization process, a three-dimensional porous reticular structure is formed in the material, the adsorption effect of the three-dimensional graphene oxide composite material is improved, and the adsorption performance of the three-dimensional graphene oxide composite material in unit volume is also improved after the forming agent is carbonized.
Drawings
FIG. 1 is an electron microscopic view of a three-dimensional graphene oxide composite material according to example 1 of the present invention;
FIG. 2 is an electron microscopic view of graphene oxide raw material in example 1 of the present invention;
FIG. 3 is a graph showing the molecular weight distribution of the three-dimensional graphene oxide composite material of example 1 of the present invention before and after adsorption of effluent from biological wastewater treatment.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
Polyacrylonitrile is dissolved in dimethylformamide to prepare a solution A with the mass fraction of 20 wt%;
adding graphene oxide into dimethylformamide to prepare a graphene oxide solution with the weight percent of 10%, and adding sodium carbonate into the graphene oxide solution, wherein the adding amount of the sodium carbonate is 0.3 times of the mass of the graphene oxide to obtain a solution B;
under the stirring condition, the rotating speed of a stirrer is 300r/min, the solution A is slowly added into the solution B, the mass ratio of polyacrylonitrile to graphene oxide is 0.2:1, and the solution C is obtained after stirring for 1 h;
transferring the solution C into an oven, wherein the temperature of the oven is set to 65 ℃, and the drying time is 2 hours;
and (3) placing the dried material in a microwave reactor, setting the heating temperature of the microwave reactor to 450 ℃, setting the reaction time to 15min, cleaning and drying the product, and thus obtaining the three-dimensional graphene oxide composite material.
Example 2
Polyacrylonitrile is dissolved in dimethylformamide to prepare a solution A with the mass fraction of 1 wt%;
adding graphene oxide into dimethylformamide to prepare a graphene oxide solution with the weight percent of 1%, and adding sodium hydroxide into the graphene oxide solution, wherein the adding amount of the sodium hydroxide is 0.1 time of the mass of the graphene oxide to obtain a solution B;
under the stirring condition, the rotating speed of a stirrer is 150r/min, the solution A is slowly added into the solution B, the mass ratio of polyacrylonitrile to graphene oxide is 0.1:1, and the solution C is obtained after stirring for 0.5h;
transferring the solution C into an oven, wherein the temperature of the oven is set to 80 ℃, and the drying time is 0.5h;
and (3) placing the dried material in a microwave reactor, wherein the heating temperature of the microwave reactor is set to 290 ℃, the reaction time is set to 60 minutes, and cleaning and drying the product to obtain the three-dimensional graphene oxide composite material.
Example 3
Carboxymethyl cellulose is dissolved in dimethylacetamide to prepare a solution A with the mass fraction of 10 wt%;
adding graphene oxide into dimethylacetamide to prepare a graphene oxide solution with the weight percent of 5%, and adding potassium carbonate into the graphene oxide solution, wherein the adding amount of the potassium carbonate is 1.5 times of the mass of the graphene oxide, so as to obtain a solution B;
under the stirring condition, the rotating speed of a stirrer is 800r/min, the solution A is slowly added into the solution B, the mass ratio of the carboxymethyl cellulose to the graphene oxide is 0.7:1, and the solution C is obtained after stirring for 3 hours;
transferring the solution C into an oven, wherein the temperature of the oven is set to be 70 ℃, and the drying time is 2 hours;
and (3) placing the dried material in a microwave reactor, wherein the heating temperature of the microwave reactor is 680 ℃, the reaction time is 20min, and cleaning and drying the product to obtain the three-dimensional graphene oxide composite material.
Example 4
Polyimide is dissolved in N-methyl pyrrolidone to prepare a solution A with the mass fraction of 30 wt%;
adding graphene oxide into N-methyl pyrrolidone to prepare 8wt% graphene oxide solution, and adding sodium carbonate into the graphene oxide solution, wherein the adding amount of the sodium carbonate is 2 times of the mass of the graphene oxide to obtain solution B;
under the stirring condition, the rotating speed of a stirrer is 1500r/min, the solution A is slowly added into the solution B, the mass ratio of polyimide to graphene oxide is 1:1, and the solution C is obtained after stirring for 4 hours;
transferring the solution C into an oven, wherein the temperature of the oven is set to 95 ℃, and the drying time is 24 hours;
and (3) placing the dried material in a microwave reactor, setting the heating temperature of the microwave reactor to 900 ℃, setting the reaction time to 10min, cleaning and drying the product, and thus obtaining the three-dimensional graphene oxide composite material.
Comparative example 1
Sodium carbonate was not added and the remaining reaction conditions and process parameters were exactly the same as in example 1.
Comparative example 2
The microwave reaction is not carried out, the other reaction conditions and process parameters are completely the same as those of the embodiment 1, and the obtained dried material is the final product.
Experiment 1:
the composite materials obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to performance tests, and the results are shown in Table 1, wherein the specific surface area and pore size distribution were tested according to the specification of the specific surface area of the solid substance measured by the GB/T19587-2017 gas adsorption BET method, and the iodine value was tested according to the method of measuring the iodine adsorption value of the graphene material of T/CGIA 011-2019.
TABLE 1
Experiment 2:
in the current sewage recycling process, the existence of small molecular organic matters causes more and more extensive attention in academia and industry, and the organic matters tend to have low concentration level and larger hazard, influence the water body safety and the health of human beings, and cannot be removed through membrane interception such as biological treatment, ultra-micro filtration and the like. Therefore, the adsorption method is more economical and effective. Taking the effluent of a biological treatment unit of a sewage plant as an experimental water sample, and carrying out a sequencing batch experiment. Taking 1L of experimental water sample, adding 1mg of the three-dimensional graphene oxide composite material in the example 1 into the experimental water sample, oscillating for 10-15min, standing for 1h, and testing the molecular weight distribution characteristics of the organic matters before and after adsorption, wherein the result is shown in figure 3.
Experimental results show that the three-dimensional graphene oxide composite material has a good selective adsorption effect on small molecular organic matters in water discharged from a biological treatment unit, and the treated water has good practical significance and value in the field of sewage recycling.
Experiment 3:
the current chemical wastewater treatment has the problems of exceeding COD (chemical oxygen demand) and exceeding phenol content, and the water is treated by biochemical treatment and the like, and organic matters in the water are mostly organic matters difficult to biodegrade, such as phenol with low concentration, so that the adsorption method is most efficient and economical. Taking effluent of a chemical plant as an experimental water sample, preparing three 500ml beakers with the marks 1, 2 and 3, adding 200ml pure water into the 500ml beakers with the marks 1, 2 and 3, respectively adding 200ml of the experimental water sample into the 2 and 3, and photographing and recording; 0.2g, 0.2g and 0.5g of the three-dimensional graphene oxide composite material synthesized in the example 1 are respectively added into three beakers according to the serial numbers, the three beakers are kept stand for 1h after vibrating for 10-15min, photographing, recording and filtering are carried out, and COD and phenol contents in water after filtering are tested, wherein the results are shown in Table 2:
TABLE 2
Remarks: the experiment No. 1 is a blank experiment, and the data No. 2 and No. 3 are required to be blanked (the COD is dissolved out).
The experimental result shows that the three-dimensional graphene oxide composite material has a good removal effect on COD and trace phenols in chemical wastewater, the COD adsorption capacity of the material under the feeding condition of 0.1wt% (the ratio of the feeding amount of the three-dimensional graphene oxide composite material to the sum of the weights of an experimental water sample and the three-dimensional graphene oxide composite material) is 67.79mg/g, and the phenol adsorption capacity is 0.18mg/g, so that the three-dimensional graphene oxide composite material can be used for removing trace organics in the chemical wastewater, and has certain social significance and popularization value.
It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (7)
1. The preparation method of the three-dimensional graphene oxide composite material is characterized by comprising the following steps of:
s01, dissolving a forming agent in a polar solvent to obtain a solution A, wherein the forming agent is one of polyacrylonitrile, carboxymethyl cellulose and polyimide;
s02, adding graphene oxide into the same polar solvent as that in the step S01, stirring and dissolving to obtain a graphene oxide solution, adding alkali into the graphene oxide solution, and stirring and dissolving to obtain a solution B;
the polar solvent in the step S01 and the step S02 is one of dimethylacetamide, dimethylformamide and N-methylpyrrolidone;
the alkali in the step S02 is one of sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide, and the mass ratio of the alkali to the graphene oxide is 0.1-2:1;
s03, slowly adding the solution A into the solution B under the stirring condition to obtain a solution C, wherein the mass ratio of the forming agent to the graphene oxide is 0.1-1:1;
s04: transferring the solution C into a baking oven, controlling the baking temperature to be 50-95 ℃ and the baking time to be 0.5-24 hours, and obtaining a baked material;
s05: transferring the dried material into a crucible, placing the crucible in a microwave reactor, reacting for 10-60 min at 290-900 ℃, and cleaning and drying the product to obtain the three-dimensional graphene oxide composite material.
2. The method for preparing the three-dimensional graphene oxide composite material according to claim 1, wherein the method comprises the following steps: the mass fraction of the solution A in the step S01 is 1-30wt%.
3. The method for preparing the three-dimensional graphene oxide composite material according to claim 1, wherein the method comprises the following steps: the mass fraction of the graphene oxide solution in the step S02 is 1-10wt%.
4. The method for preparing the three-dimensional graphene oxide composite material according to claim 1, wherein the method comprises the following steps: the stirring rotation speed in the step S03 is 150-1500 r/min.
5. The method for preparing the three-dimensional graphene oxide composite material according to claim 1, wherein the method comprises the following steps: in the step S03, the stirring time is 0.5-4 h.
6. A three-dimensional graphene oxide composite material prepared by the preparation method according to any one of claims 1 to 5, wherein: the specific surface area of the three-dimensional graphene oxide composite material is more than 1700m 2 The ratio of the pore diameter to the pore diameter of more than 5 mu m is more than 79 percent, and the iodine value is more than 1600mg/g.
7. Use of the three-dimensional graphene oxide composite material according to claim 6, characterized in that: the method is used for the selective adsorption of organic matters, the adsorption of inorganic matters and the application related to the adsorption and separation in liquid separation and gas separation.
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