CN112142040A - Preparation method of thermal reduction graphene oxide modified graphite cathode - Google Patents
Preparation method of thermal reduction graphene oxide modified graphite cathode Download PDFInfo
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- CN112142040A CN112142040A CN202010896143.0A CN202010896143A CN112142040A CN 112142040 A CN112142040 A CN 112142040A CN 202010896143 A CN202010896143 A CN 202010896143A CN 112142040 A CN112142040 A CN 112142040A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000005096 rolling process Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 4
- 230000029058 respiratory gaseous exchange Effects 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 abstract description 10
- 239000010439 graphite Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000011946 reduction process Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 23
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- DCKVOWTXVYRDSU-UHFFFAOYSA-N O=[Ti].O=[Ir] Chemical compound O=[Ti].O=[Ir] DCKVOWTXVYRDSU-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/33—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The invention discloses a preparation method of a thermal reduction graphene oxide modified graphite cathode, which comprises the steps of carrying out thermal reduction on graphene oxide powder for 10min at 1100 ℃ in an argon atmosphere, mixing the thermally reduced graphene oxide with graphite, and rolling the mixture on a roller press to form a circular electrode plate with the radius of 1.5 cm. The specific surface area of the prepared electrode is 28cm2Electrochemical active area of 17cm2The method is obviously higher than the reduced graphene oxide modified graphite cathode prepared by a chemical oxidation-reduction method. The obtained thermal reduction graphene oxide modified air breathing cathode is used for an electrochemical system, and has high speed and current efficiency in the aspect of hydrogen peroxide synthesis. In addition, the reduction process of graphene oxide in the cathodeThe degree can be regulated and controlled by the thermal reduction temperature, and the higher the thermal reduction temperature is, the higher the reduction degree of the graphene oxide is, so that the reduction degree of the graphene oxide in the cathode can be simply and conveniently regulated and controlled according to actual needs.
Description
Technical Field
The invention relates to the field of electrochemical synthesis, in particular to a preparation method of a thermal reduction graphene oxide modified graphite cathode and research on efficient electrocatalytic synthesis of hydrogen peroxide by the thermal reduction graphene oxide modified graphite cathode.
Background
Hydrogen peroxide is an important strong oxidant, and has great demand in the fields of paper making, paper pulp, textile, chemical oxidation, environmental remediation and the like. Hydrogen peroxide can be used to disinfect and degrade organic contaminants, particularly in the field of environmental remediation.
The development of hydrogen peroxide generated by the carbon-based material catalytic oxygen reduction (ORR) has attracted attention because of its advantages of low energy consumption, high cost-effectiveness, no environmental pollution, etc. Reduced graphene oxide, a novel two-dimensional carbon material, has a large specific surface area, good electrical conductivity, and high selectivity to hydrogen peroxide, and is therefore widely used as a catalyst for oxygen reduction reactions. The reduced graphene oxide can control the reduction conditions in the reduction process, so as to adjust the oxygen content and the conductivity of the surface of the reduced graphene oxide. Thus, graphene oxide with different degrees of reduction has greatly different selectivity and electrocatalytic activity for hydrogen peroxide. In preparing the shaped electrode, the graphene, which determines the optimum degree of reduction, can generate hydrogen peroxide with higher efficiency, thereby reducing costs.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a thermal reduction graphene oxide modified graphite cathode, which is low in cost and relatively simple in preparation process. The graphene oxide is reduced by a thermal reduction method, the reduction of the chemical composition of the graphene oxide and the porosity of a physical structure are skillfully realized, the conductivity, the specific surface area and the hydrophobicity of the air self-breathing cathode are improved by double reduction of the graphene oxide, hydrogen peroxide can be efficiently produced under high current density, and the problems of poor conductivity, small specific surface area and poor hydrophobicity of the graphite self-breathing cathode in the prior art are solved. Meanwhile, the defect of small aperture of the graphene oxide reduced by a chemical method is overcome. The technical scheme of the invention is as follows: a preparation method of a thermal reduction graphene oxide modified graphite cathode comprises the following steps:
1) and placing the graphene oxide powder in a quartz boat, and annealing the graphene oxide powder at high temperature in an argon atmosphere. Before annealing, the quartz tube is cleaned for 5min by argon gas, and graphene oxide is heated to 1100 ℃ under the condition of keeping the argon gas uniform flow rate. After heating at this temperature for 10 minutes, the furnace was cooled in an argon atmosphere. And when the furnace temperature is reduced to below 50 ℃, taking out the reduced graphene oxide from the quartz tube.
2) Placing 0.1g of reduced graphene oxide prepared in the step 1), 1g of graphite powder and 40mL of absolute ethyl alcohol in a beaker, shaking up, placing the beaker in an ultrasonic cleaner, placing a stirring paddle on the ultrasonic cleaner, and carrying out ultrasonic cleaning for 10 minutes under the condition of keeping uniform stirring. Then 0.46mL of Polytetrafluoroethylene (PTFE) was added to the beaker with stirring. Ultrasonic cleaning was continued for 10 minutes with uniform stirring, and the mixture was transferred to a water bath at 60 ℃ and heated until ethanol was completely evaporated. And taking out the remaining bulk solid in the beaker, repeatedly rolling the solid on one side of a roller press until the thickness of the solid is changed into a strip-shaped slice A with the uniform thickness of 0.5mm, spraying absolute ethyl alcohol in the rolling process to prevent the slice from being dried and cracked, and marking the slice A as a catalytic layer.
3) 4g of carbon black and 60mL of absolute ethanol are placed in a beaker, sonicated and stirred for 10 minutes before 6.2mL of PTFE is added. After stirring and washing for another 10 minutes, the mixture was transferred to a 80 ℃ water bath and heated until the ethanol was completely evaporated. The remaining bulk solid in the beaker was taken out, repeatedly rolled on the roll press side until the solid thickness became a 0.5mm pore-free strip-like sheet B, and then the sheet B was heated in a muffle furnace at 340 ℃ for 20 minutes, and the finally obtained sheet B was marked as a diffusion layer.
4) Respectively placing the sheets A and B prepared in the steps 2) and 3) on two sides of a stainless steel mesh, and embedding the catalyst layer and the diffusion layer into the steel mesh sheet through rolling to form a sheet with the thickness of 1.0mm, so as to prepare the reduced graphene oxide modified graphite cathode with a composite layer structure.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the thermal reduction graphene oxide modified graphite cathode prepared by the invention has higher conductivity and promotes electron transfer.
2. The increase of the reduction degree of the thermal reduction graphene oxide can not only improve the electron transfer rate on the surface of the electrode, but also increase the mesopores on the surface of the electrode, increase the specific surface area, improve and promote oxygen adsorption, and promote the synthesis of hydrogen peroxide
3. Reduced graphene oxide is used as a catalyst, and the hydrogen peroxide yield of the graphite cathode can be improved by 2.2 times by only 50mg of reduced graphene oxide on one electrode. At 40mA cm-2At a current density of (3), the hydrogen peroxide yield is 1206 +/-36 mg L-1h-1The current efficiency is (82 +/-2)%, the electrode stability is good, and the electrode can be repeatedly used for many times.
Drawings
FIG. 1 is a thermally reduced graphene oxide (a) prepared according to the present invention;
a scanning electron microscope (b) of thermally reduced graphene oxide modified graphite cathode;
FIG. 2 is H of samples 1 to 42O2Histogram of yield of (a);
FIG. 3 is H of samples 1 to 42O2A current efficiency graph;
figure 4 is a cycle chart of 10 cycles of hydrogen peroxide production tests on electrodes prepared in example 4 in an air diffusion cathode of the present invention.
Detailed Description
The technical solutions of the present invention are further described in detail with reference to the accompanying drawings and specific embodiments, which are only illustrative of the present invention and are not intended to limit the present invention.
Example 1: a preparation method of a graphite cathode modified by thermal reduction graphene oxide comprises the following steps:
mixing 1.1g of graphite powder with 40mL of absolute ethyl alcohol, ultrasonically stirring for 10min to uniformly disperse graphite in the absolute ethyl alcohol, slowly adding 0.46mL of polytetrafluoroethylene emulsion under the condition of ultrasonic stirring, and ultrasonically stirring for 10 min; then, the mixture is heated in water bath at 60 ℃ to form colloidal paste, and the colloidal paste is pressed into a 0.5mm slice by using a roller press, and absolute ethyl alcohol is sprayed during the rolling process to ensure the bonding. The catalytic layer obtained in this comparative example was designated as sample 1.
Example 2: a preparation method of a graphite cathode modified by thermal reduction graphene oxide comprises the following steps: mixing 1.0g of graphite powder and 0.1g of reduced graphene oxide (reduced at 700 ℃) with 40mL of absolute ethyl alcohol, ultrasonically stirring for 10min to uniformly disperse graphite and reduced graphene oxide powder in the absolute ethyl alcohol, slowly adding 0.46mL of polytetrafluoroethylene emulsion under the condition of ultrasonic stirring, and ultrasonically stirring for 10 min; then heating in water bath at 60 deg.C for 20min to obtain colloidal paste, pressing into 0.5mm sheet with roller press, and spraying anhydrous ethanol during rolling to ensure bonding. The catalytic layer obtained in this comparative example was designated as sample 2.
Example 3: the steps of preparing a graphite cathode modified by thermal reduction graphene oxide are the same as those in example 2, except that the reduced graphene oxide in the catalyst layer is reduced at 900 ℃, which is denoted as sample 3 in this example.
Example 4: the steps of preparing a graphite cathode modified by thermal reduction graphene oxide are the same as those in example 2, except that the reduced graphene oxide in the catalyst layer is reduced at 1100 ℃, which is denoted as sample 4 in this example.
Example 5: 4g of carbon black and 60mL of absolute ethanol are placed in a beaker, sonicated and stirred for 10 minutes before 6.2mL of PTFE is added. After stirring and washing for another 10 minutes, the mixture was transferred to a 80 ℃ water bath and heated until the ethanol was completely evaporated. Taking out the residual bulk solid in the beaker, repeatedly rolling in a roller press until the solid thickness becomes 0.5mm of a strip-shaped flake B without pores, then heating the flake B in a muffle furnace at 340 ℃ for 20 minutes, and finally marking the obtained flake B as a diffusion layer
Example 6: the catalytic layers prepared in examples 1-4 and the diffusion layer prepared in example 5 were placed on both sides of a steel mesh and rolled into a sheet conforming to the structure in a roll press to obtain final samples 1-4. The final samples 1-4 were placed in a 120mL electrolytic cell as the cathode. The anode adopts a titanium iridium dioxide plate. Connecting the cathode and the anode to the cathode and the anode of a DC power supply respectively, and applying 10-40mA cm-2Constant current of 50mM Na2SO4In solutionAfter 20 minutes of electrolysis, the hydrogen peroxide concentration was measured and the yield and current efficiency of hydrogen peroxide were calculated. The hydrogen peroxide production rate for each sample is shown in fig. 2, and the current efficiency for each sample is shown in fig. 3. The performance of sample 4 was optimal at each current density.
Example 7: the electrochemical alternating-current impedance spectroscopy performs electron transfer impedance test on the reduced graphene oxide modified graphite cathode prepared at different thermal reduction temperatures. Table 1 compares the charge transfer resistances of the thermally reduced graphene oxide-modified graphite cathodes obtained at different heat treatment temperatures in examples 1 to 4 of the present invention. As shown in the table, it was revealed that the cathode resistance decreased as the degree of reduction increased. The resistance of the 1100 ℃ thermal reduction graphene oxide modified graphite cathode is the minimum and is only 3.45 omega.
TABLE 1
Comparative example 1: a chemical reagent-reduced graphene oxide-modified graphite cathode was prepared using the same experimental procedures and experimental conditions as in example 1, except that: the reduced graphene oxide is reduced by hydrazine hydrate, so that a reduced graphene oxide modified graphite cathode can be obtained, but the yield and the current efficiency of the prepared hydrogen peroxide are only 63% of those of example 1.
Comparative example 2: a chemical reagent-reduced graphene oxide-modified graphite cathode was prepared using the same experimental procedures and experimental conditions as in example 1, except that: the reduced graphene oxide is reduced by ammonia water, and a graphite cathode modified by the reduced graphene oxide can be obtained, but the yield and the current efficiency of the prepared hydrogen peroxide are only 55% of those of example 1.
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A preparation method of a thermal reduction graphene oxide modified graphite cathode is characterized by comprising the following steps:
1) placing graphene oxide powder in a quartz boat, and annealing the graphene oxide powder at high temperature in the atmosphere of argon; heating the graphene oxide to 700-1100 ℃ under the condition of keeping the uniform flow rate of argon; cooling in an argon atmosphere; when the furnace temperature is reduced to below 50 ℃, taking out the reduced graphene oxide from the quartz tube;
2) placing the reduced graphene oxide prepared in the step 1), graphite powder and absolute ethyl alcohol in a beaker, uniformly shaking, placing the beaker in an ultrasonic cleaner, placing a stirring paddle on the ultrasonic cleaner, and ultrasonically cleaning under the condition of keeping uniform stirring;
then adding the polytetrafluoroethylene into the beaker uniformly while stirring;
continuing ultrasonic cleaning under the condition of uniform stirring, transferring the mixture into a water bath, and heating until the ethanol is completely evaporated;
taking out the remaining bulk solid in the beaker, repeatedly rolling the solid on one side of a roller press until the thickness of the solid becomes uniform strip-shaped thin slices A, spraying absolute ethyl alcohol in the rolling process to prevent the thin slices from being dried and cracked, and marking the thin slices A as a catalyst layer;
3) putting carbon black and absolute ethyl alcohol into a beaker, performing ultrasonic treatment and stirring, and adding PTFE; after stirring and washing evenly, transferring the mixture into a water bath and heating until the ethanol is completely evaporated; taking out the residual bulk solid in the beaker, repeatedly rolling on one side of a roller press until the thickness of the solid becomes a strip-shaped sheet B without pores, and then heating the sheet B in a muffle furnace to finally obtain a sheet B marked as a diffusion layer;
4) respectively placing the sheets A and B prepared in the steps 2) and 3) on two sides of a stainless steel mesh, and embedding the catalyst layer and the diffusion layer into the steel mesh sheet through rolling to form sheets, so as to prepare the air breathing cathode with a composite layer structure.
2. The method for preparing the thermally reduced graphene oxide modified graphite cathode according to claim 1, wherein in the step 2), 0.1g of reduced graphene oxide, 1g of graphite powder and 40mL of anhydrous ethanol are used.
3. The method for preparing a graphene oxide modified graphite cathode by thermal reduction according to claim 1, wherein the reduced graphene oxide in the step 2) has a carbon content of 97.14%, an oxygen content of 2.44% and a carbon-oxygen ratio of 39.81.
4. The method for preparing the thermally reduced graphene oxide modified graphite cathode according to claim 1, wherein 4g of carbon black and 60mL of absolute ethyl alcohol are used in the step 3).
5. The preparation method of the thermal reduction graphene oxide modified graphite cathode as claimed in claim 1, wherein the current density is 20mA cm/cm in an electrochemical system-2The yield of the hydrogen peroxide reaches 687mg L after 1 hour under the condition-1The current efficiency reaches 93%.
6. The method for preparing the thermal reduction graphene oxide modified graphite cathode according to claim 1, wherein hydrogen peroxide generated by the cathode has strong stability, and the yield and current efficiency of hydrogen peroxide do not change obviously after 10 cycles.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011147A (en) * | 2012-12-27 | 2013-04-03 | 中南大学 | Method for preparing graphene through thermal reduction |
| CN104129778A (en) * | 2014-06-25 | 2014-11-05 | 天津师范大学 | Preparation method of functionalized graphene used for positive electrode material of lithium ion battery |
| US20190169033A1 (en) * | 2016-08-16 | 2019-06-06 | King Abdullah University Of Science And Technology | Graphene materials and improved methods of making, drying, and applications |
| CN110565112A (en) * | 2019-08-19 | 2019-12-13 | 天津大学 | method for changing cathode oxygen reduction activity by regulating hydrophilicity and hydrophobicity |
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- 2020-08-31 CN CN202010896143.0A patent/CN112142040A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011147A (en) * | 2012-12-27 | 2013-04-03 | 中南大学 | Method for preparing graphene through thermal reduction |
| CN104129778A (en) * | 2014-06-25 | 2014-11-05 | 天津师范大学 | Preparation method of functionalized graphene used for positive electrode material of lithium ion battery |
| US20190169033A1 (en) * | 2016-08-16 | 2019-06-06 | King Abdullah University Of Science And Technology | Graphene materials and improved methods of making, drying, and applications |
| CN110565112A (en) * | 2019-08-19 | 2019-12-13 | 天津大学 | method for changing cathode oxygen reduction activity by regulating hydrophilicity and hydrophobicity |
Non-Patent Citations (1)
| Title |
|---|
| HANNES C. SCHNIEPP ET AL: "Functionalized Single Graphene Sheets Derived from Splitting Graphite Oxide", 《J. PHYS. CHEM. B》 * |
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