CN112547016B - Graphene oxide composite material and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of composite materials. A graphene oxide composite material and a preparation method and application thereof are provided, wherein the graphene oxide composite material with stable structure and good selectivity is prepared by effectively and covalently coupling oxygen/nitrogen-enriched organic molecules 1, 3-di [ tris (hydroxymethyl) methylamino ] propane with graphene oxide. Esterification and amidation reactions are carried out on graphene oxide and 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane under the catalysis condition, so that a composite product with stable chemical bonding is obtained. The bonding to a certain degree ensures that the graphene oxide composite material has different adsorption capacities on various substances due to different adsorption mechanisms, shows adsorption selectivity on organic matters and adsorption rejection on certain metal ions, and can realize high-efficiency adsorption of organic matters in aqueous solution and effective separation of inorganic and organic pollutant mixtures; and the composite material has good recycling performance.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a graphene oxide composite material, and a preparation method and application thereof.
Background
Rare earth elements are indispensable in many advanced technical and energy applications, and global demand for rare earth elements has proliferated in the past two decades. Because of the geographical maldistribution of rare earth elements, recovery of rare earth is one method of supplementing mining to maintain sustainable supplies. However, the rare earth elements that are industrially separated from mineral ores require further purification, and the aqueous environment contains a large amount of other elements and contaminants, such as lead, copper, and organic contaminants, which often interfere with the enrichment, recovery, and detection of the rare earth elements. Meanwhile, most organic compounds, such as phenol and derivatives thereof, are widely used in pharmaceutical, textile, wood and other industries, and heavy metal ions and dyes are also common elements in environmental pollutants. Studies have shown that many toxic metal ions, such as zinc, copper, nickel, mercury, cadmium, lead and chromium, are detected in industrial wastewater. In addition, due to the high biotoxicity, mutagenesis and carcinogenesis of dyes, their release into the environment without proper treatment poses serious problems, presenting a hazard to humans, aquatic organisms and wild life. To solve these problems and minimize the hazards thereof, water treatment is required, and existing water treatment methods include chemical processes, membrane separation, organic solvent extraction, ion exchange methods, sedimentation methods, and adsorption.
The adsorption method is one of the important methods for water treatment, has the characteristics of wide application range, good treatment effect, reusable adsorbent and the like, and is characterized by applying a proper adsorbent. The prior commonly used adsorbents have small surface active site density, small adsorption activation energy in a heterogeneous system, slow reaction kinetics and unbalanced adsorption, and slow mass transfer rate on the surface of the adsorbent, and in recent years, various adsorbents such as clay mineral materials, carbon nano tubes, silicon dioxide, cellulose-graphene oxide aerogel, chitosan, titanium dioxide, beta-cyclodextrin and the like have been widely used for adsorbing and separating various rare earth, heavy metal and organic substances.
Graphene oxide has rich oxygen-containing functional groups and aromatic functional groups, and can interact with various particles through pi-pi stacking interaction, lewis acid-base interaction, intermolecular interaction such as hydrogen bond, electrostatic attraction and the like. And the graphene oxide has the advantages of high mechanical strength, large specific surface area, high chemical stability, thermal stability and the like, and the graphene oxide material is widely applied to adsorption separation of inorganic metal ions and organic pollutants in aqueous solution. Graphene oxide is used as a substrate material, and is subjected to chemical modification by using novel molecules, so that the obtained functionalized graphene oxide has a relatively wide application prospect in the field of adsorption separation.
At present, researchers aim at efficient enrichment, selective separation and repeated utilization of materials in water treatment, and three-dimensional composite materials are mostly synthesized through a simple hydrothermal self-assembly method, but the three-dimensional materials assembled by hydrothermal physics are loose and porous, have small selectivity and are easy to fall off, and have the defects of complex operation, poor separation effect and lower adsorption capacity in the adsorption separation process. Therefore, it is now urgent to explore an adsorbent which is stable in structure, good in selective separation performance and good in adsorption capacity.
Disclosure of Invention
The invention provides a graphene oxide composite material and a preparation method and application thereof, and aims to provide a composite material with stable structure, good selectivity, good separation performance and strong adsorption capacity, and a preparation method thereof, so as to realize effective adsorption separation of inorganic ions and organic pollutants in an aqueous solution.
In order to achieve the above purpose, the invention provides a preparation method of a graphene oxide composite material, comprising the following steps:
s1: preparing graphene oxide by taking crystalline flake graphite as a raw material, and freeze-drying to obtain dried graphene oxide;
s2: and (3) dissolving the graphene oxide obtained in the step (S1) by using anhydrous N, N-dimethylformamide to obtain a graphene oxide solution, uniformly mixing the graphene oxide solution with 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane, carrying out esterification and amidation reaction under the condition of anhydrous catalyst, and drying to obtain the composite material.
Preferably, in the S1, the graphene oxide is prepared by using crystalline flake graphite as a raw material and adopting a modified Hummers method.
Preferably, in the S2, the concentration of the graphene oxide solution is 2.5-75 mg/mL, and the mass ratio of the graphene oxide to the 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane is 1:1-1:10.
Preferably, in the step S2, the mass ratio of the catalyst to the graphene oxide is 1:5-20, the catalyst is combined by N, N '-dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and the mass ratio of the N, N' -dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 5:1-1:5.
Preferably, in the step S2, a moisture-proof reflux device is adopted as the reaction equipment, the reaction temperature is 150-180 ℃, and the reaction time is 4-12 hours.
Preferably, in the step S2, the reaction is always performed under magnetic stirring, the reaction is naturally cooled to room temperature after the completion of the reaction, the obtained product is decompressed and filtered, filter residues are repeatedly washed with ethanol and deionized water in sequence, and after impurities are removed, the filter residues are collected and dried.
The invention also provides a graphene oxide composite material prepared by the preparation method.
The invention also provides application of the graphene oxide composite material in selective adsorption separation of inorganic ions and organic pollutants in an aqueous solution.
Preferably, the inorganic ions comprise chloride, sulfate and nitrate, the organic pollutants comprise tertiary butyl hydroquinone, m-nitrophenol, p-nitrophenol, alizarin red S and neutral red, and the concentration of the adsorbate is 10-100 mg/L.
Preferably, the inorganic ions include rare earth ions and heavy metal ions.
The scheme of the invention has the following beneficial effects:
according to the invention, the graphene oxide and the 1, 3-di [ tris (hydroxymethyl) methylamino ] propane are subjected to esterification and amidation reaction under the condition of a catalyst, secondary amine on the 1, 3-di [ tris (hydroxymethyl) methylamino ] propane and rich hydroxyl groups and rich carboxyl groups on the graphene oxide are subjected to amidation and esterification to synthesize the composite material with stable structure, and bonding is performed to a certain extent, so that the composite material shows different adsorption capacities to different substances due to different adsorption mechanisms, the composite material has excellent selective adsorption and enrichment performances to different substances, and effective adsorption separation is realized.
The graphene oxide composite material adsorbent provided by the invention has an adsorption effect on heavy metals and organic pollutants, and has almost no adsorption capacity on rare earth ions, so that the graphene oxide composite material adsorbent can be applied to separation of heavy metals and organic pollutants from rare earth ions. Meanwhile, the graphene oxide composite material adsorbent provided by the invention shows a remarkable difference in adsorption capacity of heavy metal and organic pollutants, is beneficial to practical application in separating inorganic and organic pollutant mixtures, and has higher efficiency on adsorption of organic pollutants. And the composite material can realize good recycling performance and can greatly reduce the cost of the adsorbent.
Drawings
FIG. 1 is a graph showing the adsorption capacity of rare earth ions (lanthanum and erbium), heavy metal ions (copper and lead), organic phenols (tertiary butyl hydroquinone, m-nitrophenol and p-nitrophenol) and dyes (alizarin red S and neutral red) of the graphene oxide composite material according to the invention; 1, 3-bis [ tris (hydroxymethyl) methylamino ]]Propane (BTP), graphene Oxide (GO), graphene oxide composite (GO-BTP), and graphene oxide composite after adsorption (GO-BTP-n, n=pb) 2+ Fourier transform infrared spectrum of NR, PNP) (fig. 1 b);
FIG. 2 is an X-ray photoelectron Spectrometry (XPS) of graphene oxide, graphene oxide composite, and composite after adsorption of lead ions, respectively (FIG. 2 a); peak-split fitting of oxygen element (O) of graphene oxide (fig. 2 b); peak-split fitting map of oxygen element (O) of graphene oxide composite (fig. 2 c); peak-split fitting map of nitrogen element (N) of graphene oxide composite (fig. 2 d);
FIG. 3 is a graph of peak-split fit of oxygen element (O) of the graphene oxide composite material after adsorption of lead ions, p-nitrophenol and neutral red, respectively (FIGS. 3a-3 c); peak-split fitting map of carbon element (C) of graphene oxide composite (fig. 3 d); peak-split fitting graphs of carbon element (C) of the graphene oxide composite material after respectively adsorbing p-nitrophenol and neutral red (fig. 3e,3 f).
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
Example 1
The preparation method of the graphene oxide composite material in the example is as follows:
s1, preparing graphene oxide by using crystalline flake graphite as a raw material through a modified Hummers method, and freeze-drying for later use;
s2, measuring 60 mL anhydrous N, N-dimethylformamide treated by a molecular sieve in a 250 mL round-bottomed flask, adding 1 g of graphene oxide obtained by S1, carrying out ultrasonic treatment for 30 min, stirring in a proper amount to enable the graphene oxide to be fully dissolved, and sealing for later use;
sequentially weighing 2 g of 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane, 0.1 g of N, N' -dicyclohexylcarbodiimide and 0.1 g of 4-dimethylaminopyridine in the round-bottomed flask, sealing, carrying out ultrasonic treatment for 30 minutes, and stirring and mixing uniformly to obtain a mixed reaction solution;
transferring the mixed reaction solution into a moistureproof reflux device, heating to 160 ℃, and heating and refluxing for reaction for 8 hours under continuous magnetic stirring;
and naturally cooling to room temperature after the reaction is finished, decompressing and filtering the obtained product, repeatedly flushing filter residues with 60 mL ethanol for 6 times, repeatedly flushing the filter residues with deionized water for 6 times, removing impurities, and then collecting the filter residues for drying to obtain the graphene oxide composite material.
Example 2
The preparation method of the graphene oxide composite material in the example is as follows:
s1, preparing graphene oxide by using crystalline flake graphite as a raw material through a modified Hummers method, and freeze-drying for later use;
s2, measuring 90 mL anhydrous N, N-dimethylformamide treated by a molecular sieve, adding 1.5 g of graphene oxide obtained by S1 into a 250 mL round-bottom flask, carrying out ultrasonic treatment for 30 min, stirring in a proper amount to enable the graphene oxide to be fully dissolved, and sealing for later use;
sequentially weighing 3 g of 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane, 0.15 g of N, N' -dicyclohexylcarbodiimide and 0.15 g of 4-dimethylaminopyridine in the round-bottomed flask, sealing, carrying out ultrasonic treatment for 30 minutes, and stirring and mixing uniformly to obtain a mixed reaction solution;
transferring the mixed reaction solution into a moistureproof reflux device, heating to 160 ℃, and heating and refluxing for reaction for 10 hours under continuous magnetic stirring;
and naturally cooling to room temperature after the reaction is finished, decompressing and filtering the obtained product, repeatedly flushing filter residues with 70 mL ethanol for 7 times, repeatedly flushing the filter residues with deionized water for 7 times, removing impurities, and then collecting the filter residues for drying to obtain the graphene oxide composite material.
Example 3
The preparation method of the graphene oxide composite material in the example is as follows:
s1, preparing graphene oxide by using crystalline flake graphite as a raw material through a modified Hummers method, and freeze-drying for later use;
s2, measuring 30 mL anhydrous N, N-dimethylformamide treated by a molecular sieve, adding 22.5 g of graphene oxide obtained by S1 into a 250 mL round-bottom flask, carrying out ultrasonic treatment for 30 min, stirring in a proper amount to enable the graphene oxide to be fully dissolved, and sealing for later use;
sequentially weighing 22.5 g of 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane, 1.8 g of N, N' -dicyclohexylcarbodiimide and 2.7 g of 4-dimethylaminopyridine in the round-bottomed flask, sealing, carrying out ultrasonic treatment for 30 minutes, and stirring and mixing uniformly to obtain a mixed reaction solution;
transferring the mixed reaction solution into a moistureproof reflux device, heating to 180 ℃, and heating and refluxing for reaction for 12 hours under continuous magnetic stirring;
and naturally cooling to room temperature after the reaction is finished, decompressing and filtering the obtained product, repeatedly flushing filter residues with 80 mL ethanol for 8 times, repeatedly flushing the filter residues with deionized water for 8 times, removing impurities, and then collecting the filter residues for drying to obtain the graphene oxide composite material.
The graphene oxide composite material prepared in example 1 is used for adsorbing inorganic ions and organic pollutants in an aqueous solution, and lanthanum ions (La), erbium ions (Er), copper ions (Cu), lead ions (Pb), tertiary Butyl Hydroquinone (TBHQ), m-nitrophenol (MNP), p-nitrophenol (PNP), alizarin Red S (ARS) and Neutral Red (NR) are used for respectively carrying out adsorption experiments. And (3) carrying out analysis on the chemical composition and bonding mode of the material by adopting Fourier infrared spectroscopy and X-ray photoelectron spectroscopy. The material adsorption results and material characterization are shown in fig. 1-3.
From fig. 1a, it can be seen that the graphene oxide composite material has an obvious adsorption effect on heavy metals and organic pollutants, and has little adsorption capacity on rare earth ions, so that the graphene oxide composite material can be applied to separation of heavy metals and organic pollutants from rare earth ions. Meanwhile, the composite material shows remarkable difference in adsorption capacity of heavy metal and organic pollutants, is beneficial to practical application of the composite material in separating inorganic and organic pollutant mixtures, and has higher efficiency on adsorption of organic pollutants.
From fig. 1b, it can be seen that the synthesis of the graphene oxide composite material was successful, and that due to the esterification and amidation between the 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane molecule and the graphene oxide functional group, a distinct new characteristic absorption peak appears compared with the characteristic absorption peak of graphene oxide alone. Meanwhile, the graphene oxide composite material has new characteristic peaks after absorbing p-nitrophenol, neutral red and lead ions respectively, which shows that the composite material has better absorption to the p-nitrophenol, neutral red and lead ions.
It can be further seen from fig. 2 that esterification and amidation of graphene oxide composites was successful. From fig. 2a, it is apparent that the binding energy of nitrogen (N) newly appeared in the composite material and the binding energy of lead (Pb) newly appeared after adsorption of lead ions. The peak-splitting fitting is carried out on oxygen (O) elements of the graphene oxide composite material respectively, as shown in fig. 2b and 2c, a new ester group peak appears in the composite material at 532.22 eV, and the peak-splitting fitting is carried out on nitrogen (N) elements of the graphene oxide composite material, as shown in fig. 2d, the nitrogen of the composite material is found to exist in the form of amide, so that successful esterification and amidation of the graphene oxide composite material are demonstrated.
It can be seen from fig. 3 that the composite material has different adsorption mechanisms for inorganic ions and organic matters. Compared with the oxygen (O) element of the graphene oxide composite material before adsorption, after adsorption of lead ions, as shown in fig. 3a, a new peak of a-Pb-O bond appears at 530.7 eV, and carboxyl, carbonyl and ester group peaks respectively move from 532.92, 531.82 and 532.22 eV to 533.3, 531.37 and 532.36 eV, which shows that the adsorption mechanism of the graphene oxide composite material on the lead ions is the complexation of free electrons of a small amount of oxygen of the composite material with the lead ions. After the graphene oxide composite material adsorbs the p-nitrophenol and the neutral red, the adsorption mechanism of the graphene oxide composite material to the p-nitrophenol and the neutral red is pi-pi action, hydrophobic action and hydrogen bond action through peak-splitting fitting (see figures 3 b-3 f) of the oxygen (O) element and the carbon (C) element of the graphene oxide composite material.
The graphene oxide composite material prepared by the method disclosed by the invention is stable in structure, good in recycling property, good in adsorption selectivity on organic matters and adsorption rejection on certain metal ions, and capable of realizing efficient adsorption of organic matters in aqueous solution and effective separation of inorganic and organic pollutant mixtures.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the graphene oxide composite material is characterized by comprising the following steps of:
s1: preparing graphene oxide by taking crystalline flake graphite as a raw material, and freeze-drying to obtain dried graphene oxide;
s2: dissolving graphene oxide obtained in the step S1 by using anhydrous N, N-dimethylformamide to obtain a graphene oxide solution, adding 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane, uniformly mixing, carrying out esterification and amidation reaction under the condition of an anhydrous catalyst, and drying to obtain a composite material; the mass ratio of the anhydrous catalyst to the graphene oxide is 1:5-20, the anhydrous catalyst is combined by N, N '-dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and the mass ratio of the N, N' -dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 5:1-1:5.
2. The method for preparing the graphene oxide composite material according to claim 1, wherein in S1, the graphene oxide is prepared by using crystalline flake graphite as a raw material and adopting a modified Hummers method.
3. The preparation method of the graphene oxide composite material according to claim 1, wherein in the S2, the concentration of the graphene oxide solution is 2.5-75 mg/mL, and the mass ratio of graphene oxide to 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane is 1:1-1:10.
4. The preparation method of the graphene oxide composite material according to claim 1, wherein in the step S2, a moisture-proof reflux device is adopted as reaction equipment, the reaction temperature is 150-180 ℃, and the reaction time is 4-12 h.
5. The method for preparing the graphene oxide composite material according to claim 1, wherein in S2, the reaction is always performed under magnetic stirring, the reaction is naturally cooled to room temperature after the completion of the reaction, the obtained product is subjected to vacuum filtration, filter residues are repeatedly washed with ethanol and deionized water in sequence, and the filter residues are collected and dried after impurities are removed.
6. A graphene oxide composite material, characterized in that it is produced by the production method according to any one of claims 1 to 5.
7. Use of the graphene oxide composite material according to claim 6 for selectively adsorbing and separating inorganic ions and organic pollutants in an aqueous solution.
8. The use according to claim 7, wherein the inorganic ions comprise at least one of chloride, sulfate, nitrate; the organic pollutants comprise at least one of tertiary butyl hydroquinone, m-nitrophenol, p-nitrophenol, alizarin red S and neutral red; the concentration of the adsorbate is 10-100 mg/L.
9. The use according to claim 7, wherein the inorganic ions comprise heavy metal ions.
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| CN106423072A (en) * | 2016-09-21 | 2017-02-22 | 广东环境保护工程职业学院 | Graphene oxide-sulfhydryl compound composite capable of adsorbing heavy metal ions and preparation method of graphene oxide-sulfhydryl compound composite |
| CN107141226A (en) * | 2017-06-15 | 2017-09-08 | 温州大学 | The method that six arm initiators or eight arm initiators are synthesized based on 1,3 2 [three (methylol) methylaminos] propane |
| CN107497404B (en) * | 2017-10-18 | 2020-12-18 | 中南林业科技大学 | Preparation method of modified graphene oxide adsorption material |
| CN107840971A (en) * | 2017-10-27 | 2018-03-27 | 华南理工大学 | It is a kind of that from adhering to, wearable power is quick to sense composite aquogel and preparation method thereof |
| CN107930607A (en) * | 2017-11-23 | 2018-04-20 | 湖南大学 | A kind of method that tetracycline and Ciprofloxacin single and binary-combined contamination water body are handled using modified graphene oxide |
| CN108435134B (en) * | 2018-05-10 | 2019-10-18 | 中南大学 | Egg white-graphene oxide self-assembled compound material preparation and its application |
| CN111004390B (en) * | 2018-10-08 | 2022-07-08 | 惠州学院 | Preparation method of graphene/polyaniline composite material |
| US20200149178A1 (en) * | 2018-11-13 | 2020-05-14 | Nanjing Graphene Research Institute Corporation | Method for forming electroplated copper on surface of non-metal material by graphene-based ink |
| CN110937598A (en) * | 2019-11-08 | 2020-03-31 | 宁波锋成先进能源材料研究院 | Modified graphene oxide and preparation method and application thereof |
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