CN109678142B - Functionalized porous graphene and preparation method thereof - Google Patents
Functionalized porous graphene and preparation method thereof Download PDFInfo
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- CN109678142B CN109678142B CN201811581769.1A CN201811581769A CN109678142B CN 109678142 B CN109678142 B CN 109678142B CN 201811581769 A CN201811581769 A CN 201811581769A CN 109678142 B CN109678142 B CN 109678142B
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Abstract
The invention belongs to the field of graphene materials, and discloses functionalized porous graphene and a preparation method thereof. The method takes a mixed solution of phytic acid and ammonium sulfate as an electrolyte, graphite foil as an anode and a platinum sheet as a cathode to form a two-electrode electrolysis system; providing direct current bias voltage for the anode by adopting a direct current power supply, and expanding and stripping graphite foil of the anode under the action of the bias voltage to form graphene and releasing the graphene into the electrolyte; and (2) filtering the electrolyte after ultrasonic treatment to remove impurities, centrifuging the obtained filtrate, selecting supernatant to obtain a suspension of the functionalized porous graphene, and finally filtering the suspension to obtain the functionalized porous graphene. According to the method, phytic acid is selected as electrolyte, so that hole graphene with vacancy defects is formed, and oxygen-phosphorus functional groups can be introduced to form functionalized porous graphene; meanwhile, the ammonium sulfate can promote the stripping of the graphite foil, and the graphene with few layers is prepared.
Description
Technical Field
The invention belongs to the field of graphene materials, and particularly relates to functionalized porous graphene and a preparation method thereof.
Background
Graphene is a two-dimensional carbon material composed of a single layer of carbon atoms arranged in a honeycomb shape, and is used as an ideal electrode material for energy storage devices such as batteries and supercapacitors due to its high electrical conductivity, excellent mechanical stability and large theoretical specific surface area.
However, taking a thin film micro-supercapacitor as an example, the wide application of the simple graphene-based micro-supercapacitor is limited by its relatively low capacity and energy density. The reason is that strong van der waals force exists between graphene layers, so that graphene sheets are easy to stack and agglomerate, electrolyte is prevented from entering the internal space of an electrode, the ion transmission efficiency and the effective specific surface area of the electrode are reduced, and finally the performance of the graphene-based supercapacitor is poor.
The problem can be effectively solved by introducing a pore structure on a graphene basal plane, and the existing method for preparing porous graphene mainly comprises the following steps: the catalytic oxidation method is characterized in that a large number of catalyst particles are scattered on a graphene basal plane, and then a catalyst attachment area is directionally oxidized to obtain porous graphene, and the method needs multi-step operation and is easy to generate large cracks on the surface of a material; the nano-lithography method forms micropores on the surface of graphene through high-energy laser etching, can generate an array uniformly-distributed pore structure, but is high in cost and not beneficial to large-scale manufacturing; the method comprises heating graphene powder at a certain temperature in air atmosphere by direct heating in air, wherein an amorphous region on a graphene basal plane preferentially reacts with oxygen to generate CO2Escaping to form a hole structure, the method is simple and easy to implement, but a graphene finished product needs to be prepared in advance, and the graphene is inevitably oxidized in a large area.
Disclosure of Invention
In view of the above disadvantages and/or needs for improvement of the prior art, the present invention provides a functionalized porous graphene and a preparation method thereof, wherein the preparation method realizes the preparation of the functionalized porous graphene by an electrochemical exfoliation method using a mixed solution of phytic acid and ammonium sulfate as an electrolyte.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing functionalized porous graphene, comprising the steps of:
(a) taking a mixed solution of phytic acid and ammonium sulfate as an electrolyte, taking a graphite foil as an anode and a platinum sheet as a cathode to form a two-electrode electrolysis system;
(b) in the two-electrode electrolysis system in the step (a), a direct current power supply is adopted to provide direct current bias voltage for the anode, and under the action of the bias voltage, graphite foil of the anode expands and peels off to form graphene which is released into the electrolyte;
(c) and (c) carrying out ultrasonic treatment on the electrolyte containing the graphene obtained in the step (b), dispersing the graphene, filtering to remove impurities, centrifuging the obtained filtrate, selecting supernatant to obtain a suspension of the functionalized porous graphene, and finally filtering the suspension to obtain the functionalized porous graphene.
More preferably, the concentration of the phytic acid in the electrolyte is preferably 0.02mol/L to 0.04 mol/L.
More preferably, the concentration of ammonium sulfate in the electrolyte is preferably 0.08 to 0.12 mol/L.
More preferably, the dc bias voltage is +8V to + 12V.
More preferably, the time of the ultrasound is preferably 20min to 40 min.
More preferably, the rotation speed of the centrifugation is preferably 3000r/min to 6000 r/min.
More preferably, the time for the centrifugation is preferably 15min to 25 min.
According to another aspect of the present invention, there is provided a functionalized porous graphene prepared by the above method.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1. according to the method, phytic acid is selected as electrolyte, so that the oxidation of the graphite foil anode is facilitated, a large number of amorphous regions exist in the graphene obtained by stripping, the regions are further selectively oxidized under the bias action of the anode, and carbon oxide gas is generated to escape, so that hole graphene with vacancy defects is formed; the phytic acid is used as organic strong acid rich in oxygen and phosphorus elements, the hydrogen ion concentration in the electrolyte is increased after hydrolysis, the stripping process can be accelerated, and meanwhile, oxygen and phosphorus functional groups are introduced into the product, so that functionalized porous graphene can be formed; the oxygen-phosphorus functional group can provide pseudo capacitance, namely, the oxygen-phosphorus functional group is used as a functional group of Faraday redox reaction, the specific capacity of the material is increased, and then the graphene product can be uniformly dispersed in water, so that liquid phase processing is facilitated;
2. meanwhile, the ammonium sulfate is added into the electrolyte, so that the stripping of the graphite foil can be promoted, the graphene with fewer layers is prepared, and the problems of reduction of ion transmission efficiency and reduction of effective specific surface area of the electrode caused by stacking and agglomeration of the graphene are solved;
3. particularly, the high concentration of the phytic acid can cause the high oxygen content in the product to reduce the conductivity of the product, and the low concentration of the phytic acid is not easy to form a porous structure, so the concentration of the phytic acid in the electrolyte is preferably 0.02 mol/L-0.04 mol/L; meanwhile, the oxidation of the graphite foil can be inhibited by too high concentration of ammonium sulfate, and the insufficient stripping of the graphite foil can be caused by too low concentration of ammonium sulfate, so that the concentration of ammonium sulfate in the electrolyte is preferably 0.08-0.12 mol/L; in addition, too low voltage of the direct current power supply can lead to slower peeling speed or incapability of peeling, and too high voltage can lead to too high peeling speed and more product layers, and is easy to cause excessive oxidation, so that the oxygen content of the product is higher and the conductivity of the product is influenced, therefore, the direct current bias is preferably +8 to +12V, and the functionalized porous graphene prepared under the appropriate conditions has rich pore structures and higher conductivity;
4. the method for preparing the functionalized porous graphene is time-saving, efficient, low in cost and capable of realizing large-scale production, and the prepared product has the advantages of multiple holes, few layers and oxygen and phosphorus functional groups, is particularly suitable for serving as an electrode material of a super capacitor, and can effectively improve the capacity of the capacitor.
Drawings
Fig. 1 is a diagram of a device for preparing functionalized porous graphene provided by the present invention;
FIGS. 2(a) to (b) are transmission electron micrographs of functionalized porous graphene C-1 prepared in example 1 of the present invention;
FIG. 3 shows functionalized porous graphene C-1 prepared in example 1 of the present invention after water injection1H nuclear magnetic resonance spectrogram;
FIG. 4 is an X-ray photoelectron spectrum of functionalized porous graphene C-1 prepared in example 1 of the present invention;
FIG. 5 is an X-ray photoelectron spectrum of high-resolution phosphorus element of functionalized porous graphene C-1 prepared in example 1 of the present invention;
fig. 6 is a raman spectrum of the functionalized porous graphene C-1 prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, the present invention provides a method for preparing functionalized porous graphene, which is characterized by comprising the following steps:
(a) the method comprises the following steps of assembling a mixed solution of phytic acid and ammonium sulfate as an electrolyte, a graphite foil with the size of 1cm multiplied by 2 cm-1 cm multiplied by 4cm as an anode and a platinum sheet as a cathode to form a two-electrode electrolysis system, wherein the concentration of the phytic acid in the electrolyte is preferably 0.02 mol/L-0.04 mol/L, and the concentration of the ammonium sulfate in the electrolyte is 0.08 mol/L-0.12 mol/L;
(b) in the two-motor electrolysis system in the step (a), a direct current power supply is adopted to provide a direct current bias voltage of +8V to +12V for an anode, the graphite foil gradually expands and peels to form graphene under the action of the bias voltage, and the graphene is released into the electrolyte;
(c) and (c) carrying out ultrasonic treatment on the electrolyte containing the graphene obtained in the step (b) for 20-40 min to disperse the graphene, then filtering to remove impurities, centrifuging the obtained filtrate for 15-25 min at the rotating speed of 3000-6000 r/min, selecting supernatant to obtain a suspension of the functionalized porous graphene, and finally filtering the suspension to obtain the functionalized porous graphene.
According to another aspect of the present invention, there is provided a functionalized porous graphene prepared by the above method.
Example 1
(a) A mixed solution with the phytic acid concentration of 0.03mol/L and the ammonium sulfate concentration of 0.1mol/L is used as an electrolyte, a graphite foil with the size of 1cm multiplied by 3cm is used as an anode, and a platinum sheet is used as a cathode, so that a two-electrode electrolysis system is formed by assembling;
(b) a direct current power supply is adopted to provide a direct current bias voltage of +10V for the anode, the graphite foil gradually expands and peels to form graphene under the action of the bias voltage, and the graphene is released into the electrolyte;
(c) and (C) performing ultrasonic treatment on the electrolyte containing the graphene obtained in the step (b) for 30min to disperse graphite foils in the electrolyte, then repeatedly filtering and cleaning the electrolyte by using a mixed cellulose membrane to remove residual impurities, centrifuging the obtained filtrate for 20min at the rotating speed of 4500r/min, selecting supernatant to obtain a suspension of the functionalized porous graphene, and finally filtering the suspension to obtain the functionalized porous graphene which is marked as C-1.
The transmission electron microscope test is carried out on the prepared functionalized porous graphene C-1, and the obtained result is shown in figures 2(a) to (b), wherein the surface of the C-1 is provided with micropores which have the diameters of a plurality of nanometers and are not uniform in size; FIG. 3 shows the C-1 after water injection1An H nuclear magnetic resonance spectrogram, wherein a peak A shows that water exists in a block form, a peak B shows that water exists between graphene layers, a peak C shows that water exists in micropores on a graphene basal plane, the chemical shift of the peak C relative to the peak A reflects the size of pores, the larger the chemical shift is, the smaller the pore diameter is, the spectrogram shows that the diameter of the micropores on the obtained C-1 is between 1 nm and 10nm, and the existence of the micropores is proved by matching with the transmission electron microscope result shown in figure 2;
FIG. 4 is an X-ray photoelectron spectrum of said C-1, showing that in addition to the C1s peak, there is a distinct O1s peak and a smaller P2P peak, indicating that the prepared graphene has oxygen-containing functional groups and phosphorus-containing functional groups introduced therein; the result of the X-ray photoelectron test of the high-resolution phosphorus element on C-1 is shown in fig. 5, wherein the phosphorus element exists in the graphene crystal lattice in the forms of P ═ O and P — O;
fig. 6 is a raman spectrum of the C-1, and the result shows that it has D, G and 2D main peaks, and the ratio of the D peak to the G peak is about 1.12, indicating that a large number of defects such as vacancy defects, boundary defects, etc. exist in the graphene lattice, thereby verifying the existence of holes and functional groups in the C-1.
Example 2
(a) A mixed solution with the phytic acid concentration of 0.02mol/L and the ammonium sulfate concentration of 0.12mol/L is used as an electrolyte, a graphite foil with the size of 1cm multiplied by 2cm is used as an anode, and a platinum sheet is used as a cathode, so that a two-electrode electrolysis system is formed by assembling;
(b) a direct current power supply is adopted to provide +8V direct current bias voltage for the anode, the graphite foil gradually expands and peels to form graphene under the action of the bias voltage, and the graphene is released into the electrolyte;
(c) and (C) performing ultrasonic treatment on the electrolyte containing the graphene obtained in the step (b) for 20min to disperse graphite foils in the electrolyte, then repeatedly filtering and cleaning the electrolyte by using a mixed cellulose membrane to remove residual impurities, centrifuging the obtained filtrate for 15min at the rotating speed of 6000r/min, selecting supernatant to obtain a suspension of the functionalized porous graphene, and finally filtering the suspension to obtain the functionalized porous graphene which is marked as C-2.
The C-2 is found to have nanometer micropores and oxygen phosphorus functional groups through transmission electron microscope tests and X-ray photoelectron spectroscopy tests.
Example 3
(a) A mixed solution with the phytic acid concentration of 0.04mol/L and the ammonium sulfate concentration of 0.08mol/L is used as an electrolyte, a graphite foil with the size of 1cm multiplied by 4cm is used as an anode, and a platinum sheet is used as a cathode, so that a two-electrode electrolysis system is formed by assembling;
(b) a direct current power supply is adopted to provide a direct current bias voltage of +12V for the anode, the graphite foil gradually expands and peels to form graphene under the action of the bias voltage, and the graphene is released into the electrolyte;
(c) and (C) carrying out ultrasonic treatment on the electrolyte containing the graphene obtained in the step (b) for 40min to disperse graphite foils in the electrolyte, then repeatedly filtering and cleaning the electrolyte by using a mixed cellulose membrane to remove residual impurities, centrifuging the obtained filtrate for 25min at the rotating speed of 3000r/min, selecting supernatant to obtain a suspension of the functionalized porous graphene, and finally filtering the suspension to obtain the functionalized porous graphene, wherein the label of the functionalized porous graphene is C-3.
The C-3 is found to have nanometer micropores and oxygen phosphorus functional groups through transmission electron microscope tests and X-ray photoelectron spectroscopy tests.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A preparation method of functionalized porous graphene is characterized by comprising the following steps:
(a) taking a mixed solution of phytic acid and ammonium sulfate as an electrolyte, taking a graphite foil as an anode and a platinum sheet as a cathode to form a two-electrode electrolysis system;
(b) in the two-electrode electrolysis system in the step (a), a direct current power supply is adopted to provide direct current bias voltage for the anode, the graphite foil of the anode expands and peels to form graphene under the action of the bias voltage and releases the graphene into the electrolyte, and meanwhile, the amorphous region of the graphene is further selectively oxidized under the action of the bias voltage of the anode and generates carbon oxide gas to escape, so that the porous graphene with vacancy defects is formed;
(c) and (c) carrying out ultrasonic treatment on the electrolyte containing the graphene obtained in the step (b), dispersing the graphene, filtering to remove impurities, centrifuging the obtained filtrate, selecting supernatant to obtain a suspension of the functionalized porous graphene, and finally filtering the suspension to obtain the functionalized porous graphene.
2. The method according to claim 1, wherein the concentration of phytic acid in the electrolyte is 0.02mol/L to 0.04 mol/L.
3. The method according to claim 1, wherein the concentration of ammonium sulfate in the electrolyte is 0.08mol/L to 0.12 mol/L.
4. The method according to claim 1, wherein the dc bias is +8V to + 12V.
5. The method of claim 1, wherein the sonication time is 20-40 min.
6. The method according to claim 1, wherein the rotation speed of the centrifugation is 3000r/min to 6000 r/min.
7. The method for preparing functionalized porous graphene according to any one of claims 1 to 6, wherein the centrifugation time is 15min to 25 min.
8. A functionalized porous graphene prepared by the method according to any one of claims 1 to 7.
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