CN111017911A - Reduced graphene oxide and preparation method and application thereof - Google Patents
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract
The invention relates to the technical field of electrochemical materials, in particular to reduced graphene oxide and a preparation method and application thereof. The preparation method of the reduced graphene oxide provided by the invention comprises the following steps: (1) mixing graphene oxide, an organic solvent and methylimidazole tetrafluoroborate ionic liquid to obtain a graphene oxide dispersion liquid; (2) and (2) taking the graphene oxide dispersion liquid in the step (1) as an electrolyte solution, taking a conductive material as a working electrode, adopting a three-electrode system, and preparing reduced graphene oxide on the surface of the working electrode by using a potentiostatic method. The preparation method provided by the invention has the advantages of simple process and low raw material cost, and the prepared reduced graphene oxide is uniform, uniform in reduction degree, controllable in reduction degree and good in reusability, and is beneficial to practical production and application of the reduced graphene oxide.
Description
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to reduced graphene oxide and a preparation method and application thereof.
Background
At present, the reduction modes of Graphene Oxide (GO) are mainly classified into the following categories:
the first type: chemical method, namely using chemical reducing agent to directly reduce GO, wherein the commonly used chemical reducing agent comprises hydrazine hydrate, sodium borohydride, hydrogen, ammonia gas, vitamin C, potassium hydroxide, dimethylhydrazine, hydroquinone, hydroiodic acid, phenylhydrazine and the like, which can effectively remove oxygen-containing functional groups between carbon atom layers and reduce GO into graphene;
the second type: solid phase thermal reduction method, namely putting GO into a heating furnace under inert atmosphere, heating to over 1000 ℃ in a short time, and releasing CO through decomposition of functional groups on the surface of GO2And H2And O, opening the interlayer spacing, simultaneously achieving the aims of reducing GO and stripping the GO into single-layer graphene, and obtaining the product which is solid-phase graphene. In the process, most of oxygen-containing groups are removed, and C ═ C is recovered, but the defects of Raman analysis still exist, and the graphene obtained by the method is difficult to disperse into most polar or non-polar solvents, so that the processability, the compatibility with other polymers or inorganic materials and the like and the dispersibility are limited, and the further application is not facilitated; in addition, the solid-phase thermal reduction method consumes huge energy, and the quality of the obtained reduced graphene oxide product is poor;
in the third category: the catalytic reduction method is to mix a catalyst into graphene oxide under illumination or high temperature to induce the reduction of the graphene oxide. For example, Williams et al uses titanium dioxide as a catalyst to generate active electrons under ultraviolet irradiation, and the active electrons are transferred to graphene oxide, so that the graphene oxide and the titanium dioxide composite material can be obtained through direct reduction of the active electrons.
Since oxidation-reduction methods such as the Brodie method, staudenmier method, Hummers method and the like have been proposed, the most convenient method for preparing graphene in a laboratory is achieved by a simple and easy process, and the method is favored by vast graphene researchers. The oxidation-reduction method can prepare stable graphene suspension, and solves the problem that graphene is difficult to disperse in a solvent.
However, the oxidation-reduction method is easy to cause waste liquid pollution during macro preparation, and the prepared reduced graphene oxide has certain defects, such as topological defects of five-membered rings, seven-membered rings and the like or structural defects of-OH groups, which result in the loss of partial electrical properties of the reduced graphene oxide, and thus the application of the reduced graphene oxide is limited.
Disclosure of Invention
The invention aims to provide reduced graphene oxide and a preparation method and application thereof, the electrochemical reduction of graphene oxide is adopted, strong oxidizing agents such as strong acid, strong alkali and the like are not needed in the preparation process, waste liquid pollution is not generated, and the problem of secondary pollution in a laboratory is avoided; the graphene oxide subjected to electrochemical reduction has uniform quality, the reduction degree of the graphene oxide can be controlled by the magnitude of potential and current and the length of reduction time, and topological defects of five-membered rings, seven-membered rings and the like or structural defects with-OH groups of the graphene oxide in the reduction process can be improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of reduced graphene oxide, which comprises the following steps:
(1) mixing graphene oxide, an organic solvent and methylimidazole tetrafluoroborate ionic liquid to obtain a graphene oxide dispersion liquid;
(2) and (2) taking the graphene oxide dispersion liquid in the step (1) as an electrolyte solution, taking a conductive material as a working electrode, adopting a three-electrode system, and performing electrodeposition on the surface of the working electrode by using a potentiostatic method to obtain the reduced graphene oxide.
Preferably, the graphene oxide in the step (1) is powdery, and the particle size of the graphene oxide is 1-4 μm.
Preferably, the organic solvent in step (1) comprises one or more of N, N-dimethylformamide, dimethyl malonate, dimethyl sulfoxide, benzamide and phthalic anhydride; the methylimidazole tetrafluoroborate ionic liquid comprises 1-ethyl-3-methylimidazole tetrafluoroborate or 1-butyl-3-methylimidazole tetrafluoroborate.
Preferably, the volume ratio of the graphene oxide, the organic solvent and the methylimidazolium tetrafluoroborate ionic liquid in the step (1) is 1:1 (1-3); the purity of the methylimidazole tetrafluoroborate ionic liquid is preferably 99.9%.
Preferably, the mixing in the step (1) is carried out under the ultrasonic condition, the power of the ultrasonic is 10-20 kHz, and the time is 30-90 min.
Preferably, the three-electrode system in step (2) is: the cathode is a working electrode, the reference electrode is Ag/AgCl, and the anode is a platinum wire.
Preferably, the potentiostatic method in step (2) comprises potentiostatic adsorption and potentiostatic reduction; the potential of the constant potential adsorption is 0-1V; the potential of the constant potential reduction is-0.1 to-1.4V.
Preferably, the constant potential adsorption time is 10-40 min, and the constant potential reduction time is 10-40 min.
The invention provides reduced graphene oxide prepared by the preparation method in the technical scheme, and the specific surface area of the reduced graphene oxide is 500-1000 m2A thickness of 0.55 to 3.74 nm.
The invention also provides application of the reduced graphene oxide in the technical scheme in the fields of electrochemistry, high-salt antibiotics and treatment of sewage and wastewater difficult to biodegrade.
The invention provides a preparation method of reduced graphene oxide, which comprises the following steps: (1) mixing graphene oxide, an organic solvent and methylimidazole tetrafluoroborate ionic liquid to obtain a graphene oxide dispersion liquid; (2) and (2) taking the graphene oxide dispersion liquid in the step (1) as an electrolyte solution, taking a conductive material as a working electrode, adopting a three-electrode system, and performing electrodeposition on the surface of the working electrode by using a potentiostatic method to obtain the reduced graphene oxide. According to the invention, graphene oxide dispersed in an organic solvent is taken as a reduction object, methylimidazolium tetrafluoroborate ionic liquid is taken as a conductive medium, and the reduced graphene oxide is prepared by an electrochemical method, compared with a water system dispersion liquid, the N, N-dimethyl formamide organic system dispersion liquid adopted by the invention can not generate hydrolysis hydrogen evolution reaction under a required reduction potential, so that the system is more stable, the reduced graphene oxide is more efficiently loaded on the surface of a working electrode, and a loading method is provided for the reduced graphene oxide with an ion intercalation structure; the energy cost of the reduced graphene oxide is saved to a certain extent, and the prepared reduced graphene oxide has excellent quality.
According to the method, the reduced graphene oxide is prepared in situ by one step of electrochemistry, so that the uniformity and controllability of the reduced graphene oxide are improved, a chemical reduction reagent is not used, the preparation process of the reduced graphene oxide is simplified, and the reduction degree and the thickness of the reduced graphene oxide can be further adjusted by controlling the time and the potential of electrochemical deposition. The preparation method provided by the invention has the advantages of simple process and low raw material cost, and the prepared reduced graphene oxide is uniform, uniform in reduction degree and good in reusability, and is beneficial to practical production and application of the reduced graphene oxide.
Drawings
FIG. 1 is a scanning electron micrograph of reduced graphene oxide prepared in example 1;
FIG. 2 is a scanning electron microscope image of untreated ITO conductive glass;
fig. 3 is an X-ray photoelectron spectrum of the graphene oxide and the reduced graphene oxide prepared in example 1.
Detailed Description
The invention provides a preparation method of reduced graphene oxide, which comprises the following steps:
(1) mixing graphene oxide, an organic solvent and methylimidazole tetrafluoroborate ionic liquid to obtain a graphene oxide dispersion liquid;
(2) and (2) taking the graphene oxide dispersion liquid in the step (1) as an electrolyte solution, taking a conductive material as a working electrode, adopting a three-electrode system, and performing electrodeposition on the surface of the working electrode by using a potentiostatic method to obtain the reduced graphene oxide.
In the present invention, reagents used are commercially available products well known in the art unless otherwise specified.
According to the invention, graphene oxide, an organic solvent and methylimidazole tetrafluoroborate ionic liquid are mixed to obtain a graphene oxide dispersion liquid. In the invention, the graphene oxide is preferably powder, and the particle size of the graphene oxide is preferably 1-4 μm, and more preferably 3-4 μm. According to the invention, the graphene oxide is preferably obtained by fully grinding commercially available graphene oxide in an agate mortar. In the present invention, the commercially available graphene oxide is preferably a single-layer graphene oxide, and more preferably a scaly single-layer graphene oxide.
In the present invention, the organic solvent preferably includes one or more of N, N-dimethylformamide, dimethyl malonate, dimethyl sulfoxide, benzamide and phthalic anhydride, and more preferably N, N-dimethylformamide; the methylimidazole tetrafluoroborate-based ionic liquid preferably comprises 1-ethyl-3-methylimidazole tetrafluoroborate or 1-butyl-3-methylimidazole tetrafluoroborate, and more preferably 1-ethyl-3-methylimidazole tetrafluoroborate.
In the invention, the volume ratio of the graphene oxide to the organic solvent to the methylimidazolium tetrafluoroborate ionic liquid is preferably 1:1 (1-3), and particularly preferably 1:1:1, 1:1:2 or 1:1: 3; the purity of the methylimidazole tetrafluoroborate ionic liquid is preferably 99.9%. According to the invention, the dosage ratio of the graphene oxide, the organic solvent and the methylimidazolium tetrafluoroborate ionic liquid is limited within the range, so that the migration and adsorption reduction of the graphene oxide in an electrolyte solution in the electrochemical adsorption reduction process are facilitated.
In the present invention, the mixing preferably comprises: carrying out first mixing on graphene oxide and an organic solvent to obtain a graphene oxide organic dispersion liquid; and secondly, mixing the graphene oxide organic dispersion liquid and methylimidazole tetrafluoroborate ionic liquid to obtain a graphene oxide dispersion liquid.
In the invention, the first mixing and the second mixing are preferably independently carried out under ultrasonic conditions, and the power of the ultrasonic is preferably 10-20 kHz independently, and more preferably 20kHz independently; the ultrasonic time is preferably 30-90 min independently, and more preferably 30 min. In the present invention, during the second mixing, the dispersion liquid is preferably shaken every 10min, and the effect is to uniformly disperse the obtained electrolyte solution.
In the present invention, the color of the graphene oxide dispersion liquid is bright yellow.
After the graphene oxide dispersion liquid is obtained, the reduced graphene oxide is prepared on the surface of the working electrode by using a three-electrode system and using a potentiostatic method by taking a conductive material as the working electrode. In the present invention, the conductive material preferably includes conductive glass, a copper mesh, a stainless steel sheet or a titanium sheet, and more preferably conductive glass. In the present invention, the conductive material is preferably obtained by pretreating a commercially available conductive material, and the pretreatment method is specifically preferably: the method comprises the steps of firstly soaking a commercially available conductive material in acetone for 12-24 hours, then ultrasonically cleaning the conductive material in absolute ethyl alcohol for 20-40 min, then ultrasonically cleaning the conductive material with deionized water for 20-40 min, and air-drying the conductive material for later use. In the invention, the power of the ultrasonic wave is preferably 10-20 kHz independently, and more preferably 20kHz independently. According to the invention, oil stains and other impurities on the surface of the commercially available conductive material are removed through pretreatment, so that the conductive material with a clean surface is obtained, and the subsequent deposition and reduction of graphene oxide are facilitated.
In the present invention, the three-electrode system is preferably: the cathode is a working electrode, the reference electrode is preferably Ag/AgCl, and the anode is preferably a platinum wire. In the invention, the length of the platinum wire is preferably 3-30 cm, and more preferably 4 cm; the diameter of the platinum wire is preferably 0.38-3.8 mm, and more preferably 0.5 mm. In the invention, the distance between the anode and the cathode is preferably 1-5 cm, and more preferably 3.5 cm.
As an embodiment of the invention, the reduced graphene oxide is prepared by adopting an electrodeposition device, the graphene oxide dispersion liquid is added into a reactor, cathode ITO conductive glass is arranged on one side of the reactor, an anode platinum wire is arranged on the other side of the reactor, the distance between the cathode ITO conductive glass and the anode platinum wire is 3.5cm, and a reference electrode Ag/AgCl is arranged2Is arranged in the middle of the reactor; the cathode ITO conductive glass and the anode platinum wire are completely immersed in the graphene oxide dispersion liquid, and the reference electrode Ag/AgCl2Partially immersed in the graphene oxide dispersion.
In the present invention, the potentiostatic method preferably includes potentiostatic adsorption and potentiostatic reduction; the constant potential adsorption potential is preferably 0-1V, more preferably 0.5-0.7V, and most preferably 0.6V; the time for constant potential adsorption is preferably 10-40 min, and more preferably 30 min; the sweeping speed of constant potential adsorption is preferably 10-80 mV/s, and more preferably 50 mV/s.
In the present invention, the potential of the potentiostatic reduction is preferably-0.1 to-1.4V, more preferably-1.2V; the time for constant potential reduction is preferably 10-40 min, and more preferably 30 min; the sweep rate of the constant potential reduction is preferably 10-80 mV/s, and more preferably 50 mV/s.
The reduced graphene oxide is prepared by a potentiostatic method, so that the method is low in operation temperature and low in operation condition requirement, and is suitable for popularization and application; in addition, the method reduces the complexity of the graphene oxide reduction method by in-situ electrochemical adsorption-reduction of graphene oxide in an organism system, can control the thickness of the graphene oxide layer deposited on the surface of the conductive material by controlling the constant potential adsorption time, and can control the reduction degree of the graphene oxide by controlling the constant potential reduction time.
In the present invention, the potentiostatic adsorption and the potentiostatic reduction are preferably carried out alternately periodically. According to the invention, the reduced graphene oxide with the ion intercalation structure can be obtained by periodically and alternately carrying out constant potential adsorption and constant potential reduction.
The invention provides reduced graphene oxide deposited on the surface of an electrode, which is prepared by the preparation method. In the invention, the reduced graphene oxide exists in a thin film form, and the specific surface area of the reduced graphene oxide is preferably 500-1000 m2(ii) g, more preferably 900m2(ii)/g; the thickness is preferably 0.55 to 3.74nm, and more preferably 1.67 nm. According to the invention, the reduced graphene oxide is prepared in situ by one step of electrochemistry, so that the uniformity and controllability of the reduced graphene oxide can be improved, and the prepared reduced graphene oxide is uniform, has few defects, uniform reduction degree, good reusability and excellent electrical properties.
The invention also provides application of the reduced graphene oxide in the field of electricity, and particularly relates to the field of electrochemistry and the field of treatment of high-salt antibiotics and sewage and wastewater difficult to biodegrade.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Fully grinding 60mg of scaly single-layer graphene oxide into fine powder with the particle size of 1-4 mu m in an agate mortar, transferring the powder into a beaker, adding 40mL of N, N-dimethylformamide, and carrying out ultrasonic treatment at 25 ℃ for 30min with the ultrasonic power of 20kHz to obtain a graphene oxide organic dispersion liquid;
(2) adding the graphene oxide organic dispersion liquid obtained in the step (1) into 40mL of 1-ethyl-3-methylimidazole tetrafluoroborate (with the purity of 99.9%), carrying out ultrasonic treatment at 25 ℃ for 30min, wherein the ultrasonic power is 99%, and taking out a beaker at every 10min during the ultrasonic treatment and lightly oscillating to obtain the graphene oxide dispersion liquid;
(3) soaking ITO conductive glass in acetone for 24h, taking out, putting into a beaker, adding absolute ethyl alcohol until the ITO conductive glass is immersed, carrying out ultrasonic treatment for 30min at 25 ℃ with the ultrasonic power of 99%, pouring out the absolute ethyl alcohol, adding deionized water until the ITO conductive glass is immersed, carrying out ultrasonic treatment for 30min at 25 ℃ with the ultrasonic power of 99%, taking out, and air-drying for later use;
(4) taking the graphene oxide dispersion liquid obtained in the step (2) as an electrolyte solution, taking out 8mL of the graphene oxide dispersion liquid, adding the graphene oxide dispersion liquid into an electrodeposition device, and placing the cathode ITO conductive glass obtained in the step (3), the reference electrode Ag/AgCl and an anode platinum wire into the graphene oxide dispersion liquid, wherein the length of the platinum wire is 4cm, and the diameter of the platinum wire is 0.5 mm; the distance between the platinum wire and the ITO conductive glass is 3.5 cm; setting the initial potential to be 0.6V and the running time to be 30min by utilizing a potentiostatic method in Chenghua electrochemical workstation (CHI 660D) in a three-electrode system; setting the initial potential to be-1.2V after the deposition is finished and the running time is 30 min;
(5) and taking out the ITO conductive glass, slightly washing the ITO conductive glass with deionized water, and then air-drying the ITO conductive glass to obtain the reduced graphene oxide on the surface of the ITO conductive glass.
Scanning electron microscope and X-ray photoelectron spectroscopy characterization are carried out on the prepared reduced graphene oxide finished product, the scanning electron microscope result is shown in figure 1, a membranous substance is deposited on the surface of the ITO conductive glass, and the membranous substance is reduced graphene oxide compared with untreated ITO conductive glass (figure 2). In order to determine the reduction degree of the graphene oxide, as shown in an X-ray photoelectron spectrum shown in fig. 3, the carbon-oxygen atomic ratio of unreduced Graphene Oxide (GO) is 2.1, and the carbon-oxygen atomic ratio of Reduced Graphene Oxide (RGO) after reduction is 3.7, as can be known from a reference, the content of oxygen-containing groups in the graphene oxide is obviously reduced, and thus the graphene oxide is proved to be effectively reduced.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of reduced graphene oxide is characterized by comprising the following steps:
(1) mixing graphene oxide, an organic solvent and methylimidazole tetrafluoroborate ionic liquid to obtain a graphene oxide dispersion liquid;
(2) and (2) taking the graphene oxide dispersion liquid in the step (1) as an electrolyte solution, taking a conductive material as a working electrode, adopting a three-electrode system, and performing electrodeposition on the surface of the working electrode by using a potentiostatic method to obtain the reduced graphene oxide.
2. The preparation method according to claim 1, wherein the graphene oxide in the step (1) is in a powder form, and the particle size of the graphene oxide is 1-4 μm.
3. The preparation method according to claim 1, wherein the organic solvent in step (1) comprises one or more of N, N-dimethylformamide, dimethyl malonate, dimethyl sulfoxide, benzamide and phthalic anhydride; the methylimidazole tetrafluoroborate ionic liquid comprises 1-ethyl-3-methylimidazole tetrafluoroborate or 1-butyl-3-methylimidazole tetrafluoroborate.
4. The preparation method according to any one of claims 1 to 3, wherein the volume ratio of the graphene oxide, the organic solvent and the methylimidazole tetrafluoroborate ionic liquid in the step (1) is 1:1 (1-3); the purity of the methylimidazole tetrafluoroborate ionic liquid is preferably 99.9%.
5. The preparation method according to claim 1, wherein the mixing in step (1) is performed under ultrasonic conditions, wherein the ultrasonic power is 10-20 kHz, and the ultrasonic time is 30-90 min.
6. The method according to claim 1, wherein the three-electrode system of step (2) is: the cathode is a working electrode, the reference electrode is Ag/AgCl, and the anode is a platinum wire.
7. The method according to claim 1, wherein the potentiostatic method of step (2) comprises potentiostatic adsorption and potentiostatic reduction; the potential of the constant potential adsorption is 0-1V; the potential of the constant potential reduction is-0.1 to-1.4V.
8. The method according to claim 7, wherein the potentiostatic adsorption time is 10 to 40min, and the potentiostatic reduction time is 10 to 40 min.
9. The reduced graphene oxide prepared by the preparation method of any one of claims 1 to 8, wherein the specific surface area of the reduced graphene oxide is 500-1000 m2A thickness of 0.55 to 3.74 nm.
10. The application of the reduced graphene oxide in the fields of electrochemistry and treatment of high-salt antibiotics and sewage and wastewater difficult to biodegrade as claimed in claim 9.
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| CN104034778A (en) * | 2014-06-18 | 2014-09-10 | 武汉工程大学 | Chitosan-ionic liquid-graphene-enzyme composite membrane modified electrode and preparation method thereof |
| CN106483172A (en) * | 2016-09-22 | 2017-03-08 | 华中科技大学 | Method and product and application using ionic liquid electrodeposition graphene/carbon fiber |
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| CN104034778A (en) * | 2014-06-18 | 2014-09-10 | 武汉工程大学 | Chitosan-ionic liquid-graphene-enzyme composite membrane modified electrode and preparation method thereof |
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