CN114314576A - Method for modifying carboxyl functionalization of graphene oxide - Google Patents
Method for modifying carboxyl functionalization of graphene oxide Download PDFInfo
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Abstract
The invention provides a method for modifying carboxyl functionalization of graphene oxide, which takes graphene oxide as a raw material, reduces the graphene oxide by alkali, generates a defect site in a basal plane of the graphene oxide, oxidizes the graphene oxide generating the defect site by an oxidant, and obtains carboxyl at the defect site of the graphene oxide; the oxidant is potassium permanganate and concentrated sulfuric acid, or potassium permanganate and perchloric acid. According to the method, according to the reduction mechanism of graphene oxide, a simple alkali reduction reaction is adopted, edge carboxyl is kept not to be reduced, and hole-shaped defect sites are formed on the basal plane of the graphene at the same time, and the formation sites of the carboxyl are increased by the defects. Through further oxidation, a new carboxyl directly connected with the graphene carbon atom is obtained at the defect position, and the carboxylation degree of the graphene oxide is integrally improved while hydroxyl and epoxy groups are reduced.
Description
Technical Field
The invention belongs to the technical field of graphene oxide, relates to graphene oxide modification, and particularly relates to a method for modifying carboxyl of graphene oxide in a functionalized manner.
Background
Graphene Oxide (GO) is an oxygen-containing derivative of graphene, and its widely accepted structural model is that hydroxyl and epoxy groups are distributed on the basal plane of graphene oxide, and carboxyl and carbonyl groups are distributed on the edge. The graphene oxidation mechanism is as follows: in the oxidation process, a large number of hydroxyl groups are firstly generated on the surface and the edge of the graphene, and simultaneously, C ═ C double bonds connected with the hydroxyl groups are converted into C-C single bonds; as oxidation proceeds, some of the hydroxyl groups on the surface of the graphene dehydrate to epoxy groups, while hydroxyl groups at the edges or basal plane defects of the graphene are oxidized to adjacent ketone groups and then to carboxyl groups. Although the original highly conjugated structure of graphene is destroyed in the oxidation process, the graphene oxide still maintains excellent optical, electrical, mechanical and other unique physical and chemical properties. The oxygen-containing functional group weakens strong intermolecular force among graphene sheet layers, improves the problem that graphene is easy to agglomerate, and enables the graphene to keep good dispersibility and stability in polar solvents such as water, alcohol and the like. In addition, the oxygen-containing functional groups provide abundant modification sites for basal planes and edges of the graphene oxide, and are easy to further synthesize various graphene-based composite materials. The type and number of the oxygen-containing functional groups can also be used for regulating and controlling the performances of the graphene oxide such as conductivity, band gap and the like, so that the controllable modification of the functional groups is an important means for modifying the graphene oxide.
The carboxyl of the graphene oxide can further undergo amidation, esterification, neutralization and other reactions, and becomes an important functional group in modification research. However, due to the limitation of the edge sites, the number of carboxyl functional groups in graphene oxide is limited, which affects the subsequent carboxyl-based functionalization application. In recent years, much research has been carried out on carboxylation modification. There is a report in the literature that the oxidation degree is adjusted by adjusting the content of potassium permanganate serving as an oxidant in the oxidation step of raw material graphite to obtain graphene oxides with different carboxyl contents (determination of carboxyl functional group content of graphene oxide by infrared spectroscopy, chinese test, 2016, 42, 38); there is also literature on treating graphene oxide with NaOH and chloroacetic acid to convert the hydroxyl groups on the basal plane into alkoxy carboxyl groups to increase the carboxyl group content (Nano-graphene oxide for cellular imaging and drug delivery, Nano Res, 2008, 1, 203); or carrying out free radical addition on a C ═ C bond on a graphene oxide basal plane by succinic acid acyl peroxide, and grafting a carboxyl group to the graphene oxide basal plane through an ethyl group (surface carboxylation and characterization of graphene oxide, package science and report, 2018, 2, 30); application publication No. CN104445163A discloses a preparation method of carboxylated graphene, which comprises the steps of sequentially treating graphene oxide by hydrazine hydrate, aminophenyl acid, isoamyl nitrite alcoholic solution, strong base and strong acid to obtain carboxylated graphene; the patent of the publication No. CN102433032B discloses a method for controllably synthesizing carboxylated graphene oxide and a prepared nano material, firstly, cyano-group modification is carried out on graphene through azo initiators, and then, cyano-group is converted into carboxyl by alcoholic solution of alkali; application publication No. CN108862268A discloses a 'macro preparation device and method of carboxyl functionalized graphene', which is characterized in that graphite oxide is treated by NaOH, chloroacetic acid, aminoacetic acid and the like under the protection of nitrogen to obtain the carboxyl functionalized graphene. However, these prior methods have a large number of synthetic steps and are still limited by the edge sites of the carboxyl groups. In the reports, although carboxyl is introduced on the basal plane of graphene, according to the reaction principle, alkyl chains or alkoxy chains with different lengths need to be added between the carboxyl and the basal plane, which causes larger steric hindrance on two sides of the basal plane and brings uncertain influence factors on the subsequent functionalization of the carboxyl. Therefore, it is of great significance to find a carboxylation modification method which overcomes the limitation of edge sites and has carboxyl directly connected to the carbon atom of the graphene oxide. There are reports in the literature that graphene oxide can be reduced by alkali treatment, and the carboxyl group in the reduction process is hardly affected (deoxidation of exfoliated graphite oxide units: green route to graphene regeneration, adv. Mater.2008,20,4490); in addition, it is reported in literature that many hole-shaped defects are formed on the graphene basal plane after the reduction of graphene oxide (characterization of defects generated in the reduction process of graphene oxide, carbon technology, 2016, 3, 12). However, the above document does not mention that such a defective graphene oxide is oxidized again. The characteristics of graphene oxide known from the above analysis provide possibility for increasing carboxyl modification sites in the basal plane of graphene oxide.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for modifying the carboxyl function of graphene oxide, and solve the technical problem that the carboxylation degree of graphene oxide in the prior art needs to be further improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for modifying carboxyl functionalization of graphene oxide is characterized in that graphene oxide is used as a raw material, alkali is used for reducing the graphene oxide, a defect site is generated in a basal plane of the graphene oxide, an oxidant is used for oxidizing the graphene oxide generating the defect site, and carboxyl is obtained at the defect site of the graphene oxide;
the oxidant is potassium permanganate and concentrated sulfuric acid, or potassium permanganate and perchloric acid.
The invention also has the following technical characteristics:
in the oxidant, the using amount of potassium permanganate is 0.1-3 times of the mass of the graphene oxide.
In the oxidant, concentrated sulfuric acid or perchloric acid is added into a reaction system, and then potassium permanganate is added.
In the oxidant, the dosage of concentrated sulfuric acid is 6mL of concentrated sulfuric acid added to every 40mg of graphene oxide; or in the oxidant, the dosage of perchloric acid is 3mL of perchloric acid added for every 40mg of graphene oxide.
In the adding process of the oxidant, the temperature of the reaction system is 0-10 ℃,
the oxidation reaction time is 10 minutes to 2 hours, and the reaction temperature is 0 to 40 ℃.
And after the oxidation, adding water into the reaction system, heating for reaction, and adding a terminator to terminate the reaction.
6mL of water is added to each 40mg of graphene oxide, and the temperature is raised to 95 ℃ to react for 15 minutes.
The alkali is LiOH, NaOH, KOH, RbOH, CsOH or hydrazine hydrate.
The amount of the base is added in excess relative to the amount of the graphene oxide.
The reduction reaction time is 0.5-6 hours, and the reaction temperature is 40-90 ℃.
Compared with the prior art, the invention has the following technical effects:
according to the reduction mechanism of graphene oxide, the invention adopts simple alkali reduction reaction, and forms hole-shaped defect sites on the basal plane of graphene while keeping edge carboxyl groups from being reduced, and the defects increase the formation sites of carboxyl groups. Through further oxidation, a new carboxyl directly connected with the graphene carbon atom is obtained at the defect position, and the carboxylation degree of the graphene oxide is integrally improved while hydroxyl and epoxy groups are reduced.
The method can increase defect sites in the graphene oxide base plane under the condition of retaining the existing carboxyl groups at the edge, further oxidize carbon atoms at the defect sites and generate new carboxyl groups, and the carboxyl groups are directly connected with the graphene oxide carbon atoms.
(III) by adopting the modification of the method, the obtained carboxylated graphene oxide is characterized by an infrared spectrum (figure 1) and an X-ray photoelectron spectrum (figure 2), and the content of the carboxyl is obviously improved.
(IV) in order to further verify the effect of improving the content of carboxyl, cesium atoms are loaded on the carboxyl of the graphene oxide before and after modification, and then the carboxyl is used as an electron transport layer to respectively prepare organic photovoltaic cell devices, and the result shows that the improvement of the carboxyl can improve the open-circuit voltage (V) of the devices by 44%. The method disclosed by the invention is simple to operate, has low cost and is beneficial to carboxyl functional application of graphene oxide.
Drawings
Fig. 1 is a comparison graph of fourier transform infrared spectra of modified graphene oxide obtained in example 1 of the present invention and graphene oxide before modification.
Fig. 2 is a comparison graph of X-ray photoelectron spectra of the modified graphene oxide obtained in example 1 of the present invention and the modified graphene oxide.
Fig. 3 is a J-V curve of the modified graphene oxide obtained in example 1 and the modified graphene oxide loaded with cesium atoms before modification, which are used in an electron transport layer of an organic photovoltaic device.
The present invention will be explained in further detail with reference to examples.
Detailed Description
It is to be noted that all the raw materials in the present invention, unless otherwise specified, may be those known in the art.
According to the method for modifying the carboxyl functionalization of the graphene oxide, the graphene oxide is directly used as a raw material and is reduced by alkali, a certain defect site is generated in a basal plane, and then the graphene oxide is oxidized by an oxidant, so that a new carboxyl is obtained at the defect site, and the carboxylation degree of the graphene oxide is integrally improved.
Specifically, in the method, oxygen-containing groups in the graphene oxide planes are reduced under the treatment of alkali, and carboxyl groups at the edges are not reduced. By adjusting the type of alkali, the time and the temperature of the reduction reaction, certain structural defects are generated on the basal plane of the reduced graphene oxide, the hole-shaped defects can be regarded as 'edges' in the basal plane, and new carboxyl groups are obtained at the defect sites by oxidizing the basal plane to a proper degree by an oxidizing agent.
Specifically, the process of the method is carried out according to the following reaction processes:
the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
Example 1:
the embodiment provides a method for modifying carboxyl functionalization of graphene oxide, which is carried out according to the following steps:
adding 100mg of graphene oxide and 100mL of deionized water into a round-bottom flask, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cell crusher under the power of 600W to obtain a uniform and stable graphene oxide aqueous dispersion. Slowly adding 1g of KOH into the dispersion liquid under magnetic stirring, heating to 90 ℃, keeping the temperature, stirring and reacting for 1 hour, cooling to room temperature, centrifuging for 10 minutes at the rotating speed of 9000 r/min, pouring out supernatant alkali liquor, washing the solid with deionized water, filtering with a water system membrane with the pore diameter of 0.45 mu m, repeatedly washing and filtering for 5 times, and removing the residual KOH.
Adding 40mg of the obtained reduced graphene oxide and 6mL of concentrated sulfuric acid (the mass concentration is 98%) into a round-bottom flask, carrying out ultrasonic treatment by adopting an ultrasonic bath to obtain a stable dispersion liquid, slowly adding 80mg (2 times) of potassium permanganate into the stirred dispersion liquid at 0 ℃, ensuring that the temperature does not exceed 10 ℃, raising the temperature to 40 ℃ after the addition is finished, reacting for 2 hours, slowly adding 5mL of deionized water into the system, raising the temperature to 95 ℃, continuing to react for 15 minutes, adding deionized water to increase the carboxyl content, and adding 1mL of hydrogen peroxide terminator (the mass concentration is 30%) to terminate the reaction. And (3) cooling, filtering to remove reaction liquid, cleaning for 1 time by using dilute hydrochloric acid (the mass concentration is 5%), cleaning by using deionized water repeatedly, filtering by using a water system membrane with the aperture of 0.45 mu m after cleaning each time, cleaning for more than 10 times repeatedly until acid and impurity ions are completely removed, and drying in a vacuum oven at 50 ℃ to obtain the carboxylated graphene oxide.
The modified graphene oxide prepared in the embodiment is subjected to fourier transform infrared spectroscopy test and X-ray photoelectron spectroscopy test, is used for an electron transport layer of an organic photovoltaic device and tests the device performance, and is compared with the graphene oxide before modification, and the results are shown in the attached drawings 1 to 3.
As can be seen from FIG. 1, in the IR spectrum of the modified graphene oxide according to the method of the present invention, 1720cm-1The expansion vibration peak of C ═ O at the carboxyl group is enhanced, which indicates that the carboxylation degree is improved; 1617cm-1The C ═ C stretching vibration peak of the unoxidized graphite area is relatively weakened, which indicates that some defect sites are formed in the reduction process, and the conjugation of the graphene oxide is reduced; 1050cm-1And 1224cm-1The characteristic peak of C-O-C is changed from a sharp peak before modification to a blunt peak after modification, and the strength is reduced, which shows that the content of epoxy group is reduced by reducing and oxidizing the graphene oxide according to the method of the invention; another 3158cm-1And 3373cm-1A stretching vibration peak at-OH, wherein 3158cm-1The peak probably is the shift of the hydroxyl group in the carboxylic acid to the low wavenumber direction due to hydrogen bonding, and the peak is slightly enhanced after modification, which further explains the increase in the degree of carboxylation.
As can be seen from FIG. 2, the characteristic peak of carboxyl group at 288.8eV corresponds to a content of 3.1% before modification, and the peak intensity after modification becomes large, increasing the content to 9.0%. In addition, the characteristic peak at 286.7eV is related to the hydroxyl and epoxy groups, the peak intensity is obviously reduced after modification, and the corresponding content is reduced from 17.8% before modification to 16.8% after modification. The result of the X-ray photoelectron spectroscopy shows that the carboxyl content of the modified graphene oxide is obviously improved, and the contents of hydroxyl and epoxy are reduced.
As can be seen from FIG. 3, when the modified graphene oxide is loaded with cesium atoms and then used as an electron transport layer of an organic photovoltaic device, the short-circuit current density is 0mA/cm2And when the open-circuit voltage reaches 0.81V, the open-circuit voltage is obviously higher than the open-circuit voltage of 0.56V before modification, which shows that the increased carboxyl content after modification increases the loading capacity of cesium atoms, further improves the energy level of an electron transport layer and obviously increases the open-circuit voltage. The practical application value of the graphene oxide carboxylation modification method is reflected.
Example 2:
the embodiment provides a method for modifying carboxyl functionalization of graphene oxide, which is carried out according to the following steps:
adding 100mg of graphene oxide and 100mL of deionized water into a round-bottom flask, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cell crusher under the power of 600W to obtain a uniform and stable graphene oxide aqueous dispersion. Slowly adding 1g of NaOH into the dispersion liquid under magnetic stirring, heating to 40 ℃, keeping the temperature, stirring and reacting for 1 hour, cooling to room temperature, centrifuging for 10 minutes at the rotating speed of 9000 r/min, pouring out supernatant alkali liquor, washing the solid with deionized water, filtering with a water system membrane with the pore diameter of 0.45 mu m, repeatedly washing and filtering for 5 times, and removing the residual NaOH.
Adding 40mg of the obtained reduced graphene oxide and 10mL of deionized water into a round-bottom flask, performing ultrasonic dispersion to obtain a stable dispersion liquid, slowly adding 3mL of perchloric acid (with the mass concentration of 50%) and 4mg (0.1 times of) of potassium permanganate into the dispersion liquid at about 0 ℃, fully stirring for 10 minutes, and adding 5mL of a citric acid aqueous solution terminator (0.2g/mL) to terminate the reaction. Filtering to remove reaction liquid, cleaning with deionized water, filtering with a water system membrane with the aperture of 0.45 mu m, repeatedly cleaning for more than 10 times until acid and impurity ions are completely removed, and drying in a vacuum oven at 50 ℃ to obtain the carboxylated graphene oxide.
The fourier transform infrared spectroscopy contrast plot, the X-ray photoelectron spectroscopy contrast plot, and the J-V curve for the electron transport layer of the organic photovoltaic device of the carboxylated graphene oxide of this example are substantially the same as those of example 1.
Example 3:
the embodiment provides a method for modifying carboxyl functionalization of graphene oxide, which is carried out according to the following steps:
adding 100mg of graphene oxide and 100mL of deionized water into a round-bottom flask, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cell crusher under the power of 600W to obtain a uniform and stable graphene oxide aqueous dispersion. Slowly adding 1g of CsOH into the dispersion liquid under magnetic stirring, heating to 40 ℃, keeping the temperature, stirring, reacting for 0.5 hour, cooling to room temperature, centrifuging at the rotating speed of 9000 r/min for 10 minutes, pouring off the supernatant alkali liquor, washing the solid with deionized water, filtering with an aqueous membrane with the pore diameter of 0.45 mu m, and repeatedly washing and filtering for 5 times to remove the residual CsOH.
Adding 40mg of the obtained reduced graphene oxide and 6mL of concentrated sulfuric acid (the mass concentration is 98%) into a round-bottom flask, carrying out ultrasonic treatment by adopting an ultrasonic bath to obtain a stable dispersion liquid, slowly adding 20mg (0.5 times of) of potassium permanganate into the stirred dispersion liquid at 0 ℃, ensuring that the temperature does not exceed 10 ℃ in the process, raising the temperature to 40 ℃ after the addition is finished, reacting for 2 hours, and adding 1mL of hydrogen peroxide terminator (the mass concentration is 30%) to terminate the reaction. And (3) cooling, filtering to remove reaction liquid, cleaning for 1 time by using dilute hydrochloric acid (the mass concentration is 5%), cleaning by using deionized water repeatedly, filtering by using a water system membrane with the aperture of 0.45 mu m after cleaning each time, cleaning for more than 10 times repeatedly until acid and impurity ions are completely removed, and drying in a vacuum oven at 50 ℃ to obtain the carboxylated graphene oxide.
The fourier transform infrared spectroscopy contrast plot, the X-ray photoelectron spectroscopy contrast plot, and the J-V curve for the electron transport layer of the organic photovoltaic device of the carboxylated graphene oxide of this example are substantially the same as those of example 1.
Example 4:
the embodiment provides a method for modifying carboxyl functionalization of graphene oxide, which is carried out according to the following steps:
adding 100mg of graphene oxide and 100mL of deionized water into a round-bottom flask, and carrying out ultrasonic treatment for 30 minutes by using an ultrasonic cell crusher under the power of 600W to obtain a uniform and stable graphene oxide aqueous dispersion. Slowly adding 6mL of hydrazine hydrate (the mass concentration is 85%) into the dispersion liquid under magnetic stirring, heating to 90 ℃, keeping the temperature and stirring for reaction for 6 hours, cooling to room temperature, centrifuging at the rotating speed of 9000 r/min for 10 minutes, pouring out the supernatant alkali liquor, washing the solid with deionized water, filtering with a water system membrane with the pore diameter of 0.45 mu m, and repeatedly washing and filtering for 5 times to remove the residual hydrazine hydrate.
Adding 40mg of the obtained reduced graphene oxide and 10mL of deionized water into a round-bottom flask, performing ultrasonic dispersion to obtain a stable dispersion liquid, slowly adding 3mL of perchloric acid (with the mass concentration of 50%) and 8mg (0.2 times of) of potassium permanganate into the dispersion liquid at about 0 ℃, fully stirring for 10 minutes, and adding 5mL of a citric acid aqueous solution terminator (0.2g/mL) to terminate the reaction. Filtering to remove reaction liquid, cleaning with deionized water, filtering with a water system membrane with the aperture of 0.45 mu m, repeatedly cleaning for more than 10 times until acid and impurity ions are completely removed, and drying in a vacuum oven at 50 ℃ to obtain the carboxylated graphene oxide.
The fourier transform infrared spectroscopy contrast plot, the X-ray photoelectron spectroscopy contrast plot, and the J-V curve for the electron transport layer of the organic photovoltaic device of the carboxylated graphene oxide of this example are substantially the same as those of example 1.
Claims (10)
1. A method for modifying carboxyl functionalization of graphene oxide is characterized in that graphene oxide is used as a raw material, alkali is used for reducing the graphene oxide to generate a defect site in a basal plane of the graphene oxide, an oxidant is used for oxidizing the graphene oxide generating the defect site, and carboxyl is obtained at the defect site of the graphene oxide;
the oxidant is potassium permanganate and concentrated sulfuric acid, or potassium permanganate and perchloric acid.
2. The method for carboxyl functional modification of graphene oxide according to claim 1, wherein the amount of potassium permanganate in the oxidant is 0.1 to 3 times the mass of graphene oxide.
3. The method for carboxyl functional modification of graphene oxide according to claim 1, wherein concentrated sulfuric acid or perchloric acid is added to the reaction system, and then potassium permanganate is added.
4. The method for carboxyl functional modification of graphene oxide according to claim 1, wherein the amount of concentrated sulfuric acid used in the oxidizing agent is 6mL per 40mg of graphene oxide; or in the oxidant, the dosage of perchloric acid is 3mL of perchloric acid added for every 40mg of graphene oxide.
5. The method for carboxyl functional modification of graphene oxide according to claim 1, wherein the temperature of the reaction system is 0-10 ℃ in the addition process of the oxidant.
6. The method for carboxyl functional modification of graphene oxide according to claim 1, wherein the reaction time of the oxidation is 10 minutes to 2 hours, and the reaction temperature is 0 to 40 ℃.
7. The method for carboxyl functional modification of graphene oxide according to claim 1, wherein after the oxidation, water is added into the reaction system, the temperature is raised for reaction, and then a terminator is added to terminate the reaction.
8. The method for carboxyl functional modification of graphene oxide according to claim 1, wherein 6mL of water is added for every 40mg of graphene oxide, and the temperature is raised to 95 ℃ for reaction for 15 minutes.
9. The method for carboxyl functional modification of graphene oxide according to claim 1, wherein the base is LiOH, NaOH, KOH, RbOH, CsOH or hydrazine hydrate.
10. The method for carboxyl functional modification of graphene oxide according to claim 1, wherein the reaction time of the reduction is 0.5 to 6 hours, and the reaction temperature is 40 to 90 ℃.
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