CN106693898B - Doping-degree-controllable porous reduced graphene oxide oil absorption material and preparation method thereof - Google Patents
Doping-degree-controllable porous reduced graphene oxide oil absorption material and preparation method thereof Download PDFInfo
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- CN106693898B CN106693898B CN201611018003.3A CN201611018003A CN106693898B CN 106693898 B CN106693898 B CN 106693898B CN 201611018003 A CN201611018003 A CN 201611018003A CN 106693898 B CN106693898 B CN 106693898B
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Abstract
The invention discloses a doping-degree-controllable porous reduced graphene oxide oil absorption material and a preparation method thereof. The porous reduced graphene oxide oil absorption material with controllable doping degree is of a multi-level pore structure stacked layer by layer; the method takes reduced graphene oxide aerogel as a substrate, and amino acid is doped in the skeleton of the reduced graphene oxide aerogel. According to the method, firstly, graphene oxide and an amino acid reducing agent solution are mixed, then reduced graphene oxide hydrogel is obtained through a high-pressure hydrothermal method, and finally the hydrogel is washed and frozen at a low temperature to form pores, so that the porous reduced graphene oxide oil absorption material is obtained. The oil absorption material has good hydrophobicity, has good adsorption capacity on oil products and organic pollutants, and realizes the purpose of oil-water separation in an oil-water composite environment; meanwhile, the control of the doping degree can regulate and control the pore size distribution and the pore structure of the material, promote the selective oil absorption of the material and realize the selective adsorption of oil products.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a porous reduced graphene oxide oil absorption material with controllable doping degree and a preparation method thereof.
Background
The graphene aerogel has the characteristics of high specific surface area and multilevel pore structure, and has wide application in the fields of super capacitors, lithium batteries, catalysis and adsorption. The oil absorption material is very effective in treating the ocean oil spill and the organic pollutants through absorption, and is widely applied to emergency treatment of ocean oil spill pollution accidents due to the characteristics of high efficiency, economy, easy recovery of oil products and organic matters and the like. However, the traditional oil-absorbing materials have various disadvantages in practical application due to the characteristics of poor hydrophobicity, low oil-absorbing rate, potential biotoxicity, difficult recovery and the like, so that a need for finding novel oil-absorbing materials to make up for the defects of the materials in application is urgent.
The basic unit of the pi-pi structure endows the graphene material with good hydrophobicity, and the blocky graphene oil absorption material has unusual oil absorption performance, lower density and high recycling and recycling rate. However, although the traditional graphene aerogel oil absorption material has the adsorption capacity of oil products and organic pollutants, the selectivity of the oil products is poor due to the non-uniform pore size and poor repeatability. Amino acid chemicals are rarely reported to the reduction assembly process of graphene oxide, and the doping degree of the prepared reduced graphene oxide aerogel is uncontrollable under the common conditions. The doping degree of the chemical reducing agent influences the oil absorption performance and the mechanical property of the material, so that how to obtain the reduced graphene oxide aerogel with controllable doping degree can well complete the selective oil absorption of the graphene oxide aerogel is still a great challenge.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a porous reduced graphene oxide oil absorption material with controllable doping degree and a preparation method thereof. The preparation method disclosed by the invention has controllable doping degree, and the obtained porous reduced graphene oxide oil absorption material can realize selective adsorption on oil products and organic pollution.
The technical scheme of the invention is specifically introduced as follows.
The invention provides a doping-degree-controllable porous reduced graphene oxide oil absorption material which is of a multi-level pore structure stacked layer by layer; the method takes reduced graphene oxide aerogel as a substrate, and amino acid is doped in the skeleton of the reduced graphene oxide aerogel. Preferably, the amino acid is selected from one or more of phenylalanine, tyrosine or glycine. The pore diameter of the porous membrane is between 1 and 20 mu m.
The invention also provides a preparation method of the porous reduced graphene oxide oil absorption material with controllable doping degree, which comprises the following specific steps:
(1) preparing graphene oxide aqueous dispersion, and mixing a reducing agent and the graphene oxide aqueous dispersion; wherein: the reducing agent is amino acid;
(2) mixing the mixed solution obtained in the step (1) with a reducing agent solution; wherein: the reducing agent dissolving solution is an acid solution or an alkaline solution; the acidic substance in the acidic solution is selected from any one or more of formic acid, acetic acid or oxalic acid; the alkaline substance in the alkaline solution is selected from any one or more of ammonia water, sodium hydroxide or sodium bicarbonate;
(3) carrying out hydrothermal reaction on the mixed solution obtained in the step (2) to obtain reduced graphene oxide hydrogel;
(4) and washing the reduced graphene oxide hydrogel, and freeze-drying under a vacuum condition to obtain the amino acid-doped porous graphene aerogel oil-absorbing material.
In the invention, in the step (1), the amino acid is selected from one or more of phenylalanine, tyrosine or glycine.
In the invention, the mass ratio of the reducing agent to the graphene oxide is 1: 2-5: 1.
in the invention, in the step (3), the temperature of the hydrothermal reaction is between 90 and 180 ℃, and the reaction time is 8 to 48 hours.
In the invention, in the step (4), the reduced graphene oxide hydrogel is washed by ethanol and water; before freeze drying, soaking the reduced graphene oxide hydrogel in 1-5 wt% dilute ammonia water.
In the present invention, in the step (4), the temperature of the freeze-drying is from-48 ℃ to-60 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the porous reduced graphene oxide oil absorption material with controllable doping degree provided by the invention is an adjustable functional nano material with amino acid as a reducing agent and reduced graphene oxide aerogel as a substrate and having good oil absorption performance. Because a reducing agent dissolving solution (a cosolvent and pH value control are introduced in the preparation process, and the reducing agent is prepared by an acidic or alkaline medium with good cosolvent and a reducing agent according to a certain proportion), under different pH conditions and the action of different cosolvents, the reduction action of the reducing agent is promoted or inhibited, so that the doping amount of the reducing agent is further controlled, the doping degree of the prepared reduced graphene oxide aerogel can be well controlled, the control of the doping degree can regulate and control the pore size distribution and the pore structure of the material, the selective oil absorption of the material is promoted, and the selective adsorption of an oil product is realized;
(2) because the introduced amino acid reducing agent has no toxic or harmful effect, the material can be put into a water body for use without further reduction of biotoxicity after being completely prepared;
(3) the surface of the reduced graphene oxide aerogel oil absorption material is provided with more hydrophobic surfaces formed by pi-pi conjugation, and meanwhile, the graphene oxide can generate a large number of pore structures in the assembly process of reduction induction, and the pore structures provide a large amount of space for the adsorption of oil products and the graphene oxide, so that the oil products and organic pollutants have better adsorption capacity;
(4) the obtained reduced graphene oxide aerogel oil absorption material has low density and high hydrophobicity;
(5) the reaction condition is green and pollution-free, and the preparation is simple and easy to repeat.
Drawings
Fig. 1 is a scanning electron micrograph of an oil absorbing material in example 1 of the present invention.
Fig. 2 is a raman scan of an oil absorbing material in an example of the present invention.
FIG. 3 is a schematic diagram showing the adsorption capacity of the oil-absorbing material in the embodiment of the present invention to different oils and organic pollutants.
Detailed Description
The invention is further illustrated by the following examples, which are intended only for a better understanding of the invention and do not limit the scope of the invention:
examples 1 to 6
(1) Weighing 750mg of graphene oxide solid in a beaker, adding 100ml of deionized water to prepare 7.5mg/ml graphene oxide dispersion liquid, and uniformly dispersing by ultrasonic;
(2) measuring 10ml of the dispersion liquid obtained in the step 1) and transferring the measured 10ml of the dispersion liquid into a 30ml straight-tube reaction bottle;
(3) weighing 75mg of tyrosine reducing agent, and adding into the dispersion liquid obtained in the step 2);
(4) adding a formic acid aqueous solution with the pH value of 2, which is prepared by taking formic acid as a cosolvent and formic acid as an acidic medium, into the solution obtained in the step 3), filling the mixture to the height of 80%, and performing ultrasonic dispersion uniformly after full oscillation;
(5) putting the reaction bottle obtained in the step 4) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at the temperature of 120 ℃ for 32 hours;
(6) and after the reaction liquid is naturally cooled, washing the obtained gel with deionized water, washing with ethanol, soaking in dilute ammonia water, and then freeze-drying at the temperature of-55 ℃ under a vacuum condition to obtain the amino acid-doped porous graphene aerogel oil absorption material.
The tyrosine reduced graphene oxide aerogel obtained in the above environment with formic acid (2) is recorded as example 1. Fig. 1 is a scanning electron microscope (FE-SEM, S-4800, Hitachi, Japan) image of the oil absorbing material in example 1 of the present invention, which shows that the prepared reduced graphene oxide has a relatively rich and disordered pore structure, and the pore diameter is about 2um to 10 um.
Examples 2-6 the experimental procedure was the same as in example 1, and the differences in the reducing agent co-solvent formulated were as follows:
| examples | pH | Acid-base control medium |
| Example 1 | 2 | Formic acid |
| Example 2 | 4 | Formic acid |
| Example 3 | 6 | Formic acid |
| Example 4 | 8 | Ammonia monohydrate |
| Example 5 | 10 | Ammonia monohydrate |
| Example 6 | 12 | Ammonia monohydrate |
The amino acid-doped reduced graphene oxide aerogel is prepared according to the embodiment, and the doping of the reduced graphene oxide aerogel to a reducing agent can be controlled through the synergistic effect of the cosolvent and the pH of the dispersion liquid, so that the oil absorption performance is further regulated and controlled; the lower doping level is shown when the pH is 2, and one of the best oil absorption properties.
Fig. 2 is a raman scan of the oil absorbing material in examples 1 to 6 of the present invention, and the results show the raman scan of the oil absorbing material in the examples of the present invention; the results show that the doping degree of the amino acid of the obtained oil absorption material is different under different acid and alkali conditions. Specifically, under the action of taking ammonia water as an alkaline controller, the doping degree of the material is reduced along with the increase of alkalinity (the proportion of ammonia gas in the reduction action is increased); under the action of taking formic acid as an acid controller, the doping degree of the material shows randomness, and has the maximum doping degree when the pH value is 4.
FIG. 3 is a schematic diagram of the adsorption capacity of the oil-absorbing materials of examples 1-6 of the present invention for different oils and organic pollutants. Indicating the selective adsorption capacity of the material.
The specific oil absorption method comprises the following steps:
1. the mass of the fully dried aerogel sample weighed by the analytical balance was Wa；
2. Completely immersing the aerogel sample weighed in the step 1) in adsorbate (pure organic pollutant or oil product), and standing for 30min to ensure that the aerogel is fully adsorbed;
3. taking out the graphene gel fully adsorbed in the step 2), and wiping the residual adsorbate on the surface by qualitative filter paper;
4. placing the aerogel in the step 3) on an analytical balance for weighing to obtain the mass Wb
The adsorption amount of the material is calculated by the formula (W)b–Wa)/WaUnit g g-1。
The result shows that when the concentration of the reducing agent dissolving solution is controlled to be the pH value of 2, the adsorption capacity of the obtained oil absorption material on dichloromethane and petroleum ether is strongest compared with that under other pH control; when the pH value of the reducing agent dissolving solution is controlled to be 2, the adsorption capacity of the obtained oil absorption material to dichloromethane and petroleum ether is the highest compared with that under other pH control; when the concentration of the reducing agent dissolving solution is controlled to be pH 4, the obtained oil absorption material has high adsorption capacity on dichloromethane, but has the lowest adsorption capacity on petroleum ether, so that good oil absorption selectivity is shown.
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (7)
1. The application of the porous reduced graphene oxide oil absorption material with controllable doping degree in the aspect of organic pollutant adsorption is characterized in that: the porous reduced graphene oxide oil absorption material with controllable doping degree is of a multi-level pore structure stacked layer by layer; the method comprises the following steps of taking reduced graphene oxide aerogel as a substrate, wherein amino acid is doped in a framework of the reduced graphene oxide aerogel; the preparation method of the porous reduced graphene oxide oil absorption material with controllable doping degree comprises the following specific steps:
(1) preparing graphene oxide aqueous dispersion, and mixing a reducing agent and the graphene oxide aqueous dispersion; wherein: the reducing agent is amino acid;
(2) mixing the mixed solution obtained in the step (1) with a reducing agent solution; wherein: the reducing agent dissolving solution is an acid solution or an alkaline solution; the acidic substance in the acidic solution is formic acid; the alkaline substance in the alkaline solution is ammonia water;
(3) carrying out hydrothermal reaction on the mixed solution obtained in the step (2) to obtain reduced graphene oxide hydrogel;
(4) and washing the reduced graphene oxide hydrogel, and freeze-drying under a vacuum condition to obtain the amino acid-doped porous graphene aerogel oil-absorbing material.
2. Use according to claim 1, characterized in that: the pore diameter of the porous membrane is between 1 and 20 mu m.
3. The use according to claim 1, wherein in step (1), the amino acid is selected from one or more of phenylalanine, tyrosine or glycine.
4. The use according to claim 1, wherein the mass ratio of the reducing agent to the graphene oxide is 1: 2-5: 1.
5. the use of claim 1, wherein in the step (3), the temperature of the hydrothermal reaction is between 90 ℃ and 180 ℃, and the reaction time is 8-48 h.
6. The use according to claim 1, wherein in step (4), the reduced graphene oxide hydrogel is washed with ethanol and water; before freeze drying, soaking the reduced graphene oxide hydrogel in 1-5 wt% dilute ammonia water.
7. The use according to claim 1, wherein in step (4), the temperature of freeze-drying is from-48 ℃ to-60 ℃.
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| CN107331530A (en) * | 2017-06-26 | 2017-11-07 | 中国科学技术大学 | A kind of low-temperature-doped graphene and preparation method thereof and ultracapacitor |
| CN107539980A (en) * | 2017-09-07 | 2018-01-05 | 马鞍山中粮生物化学有限公司 | A kind of novel graphite alkene aerogel material and preparation method thereof |
| CN107792901A (en) * | 2017-12-05 | 2018-03-13 | 苏州贝多环保技术有限公司 | A kind of novel oil absorption cotton |
| CN108212083A (en) * | 2017-12-28 | 2018-06-29 | 西南石油大学 | A kind of oil suction carbon sponge and preparation method thereof |
| CN108461309B (en) * | 2018-04-25 | 2019-09-24 | 山西大学 | A kind of preparation method of graphene film electrode material |
| CN110156432B (en) * | 2019-06-27 | 2021-11-26 | 中素新科技有限公司 | Carbon fiber composite graphene aerogel and preparation method and application thereof |
| CN110327851B (en) * | 2019-06-27 | 2021-07-27 | 中素新科技有限公司 | Elastic graphene aerogel and preparation method and application thereof |
| CN110155993B (en) * | 2019-06-27 | 2021-01-26 | 中素新科技有限公司 | Hydrophobic graphene aerogel and preparation method and application thereof |
| CN112079349B (en) * | 2020-08-25 | 2022-04-22 | 中国科学院兰州化学物理研究所 | Method for preparing nitrogen-doped porous graphene nano material through limited-area combustion and application |
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