CN114875430B - Graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material and preparation method thereof - Google Patents
Graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material and preparation method thereof Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 39
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 32
- 239000010439 graphite Substances 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 229920000877 Melamine resin Polymers 0.000 claims description 3
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims description 3
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
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- 210000003918 fraction a Anatomy 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011294 coal tar pitch Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229910021382 natural graphite Inorganic materials 0.000 abstract description 39
- 238000005868 electrolysis reaction Methods 0.000 abstract description 18
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- 229910052760 oxygen Inorganic materials 0.000 description 5
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- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000004076 pulp bleaching Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a preparation method of a high-efficiency graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material, belonging to the field of secondary resource utilization. The method takes natural graphite as a raw material, and prepares the high-efficiency bifunctional catalytic material after interface modification, and the method comprises the following steps: (1) Taking a certain amount of A, using a solvent B to fix the volume of the A according to a specific proportion, and fully mixing to obtain a reactant 1; (2) Weighing a certain amount of purified graphite, uniformly mixing the purified graphite with the product 1 according to a certain mass ratio, uniformly stirring and fully reacting for a certain time to obtain a mixed solution 2; (3) And (3) washing and drying the mixed solution, and then mixing and pyrolyzing the mixed solution with a surface modifier to obtain a final product. The catalytic material for water electrolysis shows high electrochemical activity, selectivity and stability. According to the invention, natural graphite is used as a raw material, and the high-efficiency dual-function electro-synthesis hydrogen peroxide catalytic material is obtained through interface modification, so that the high-value utilization of the natural spherical graphite is realized, the process is green and simple, the cost is low, and the large-scale preparation prospect is wide.
Description
Technical Field
The invention belongs to the technical field of energy conversion, and discloses a graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material and a preparation method thereof.
Background
Hydrogen peroxide (H 2O2) is a high-value, green chemical oxidant and has wide application in industry and daily life, including water purification, industrial pulp bleaching and chemical synthesis. Particularly, the hydrogen peroxide is taken as a long-acting active oxygen, is an efficient disinfection medium, and can not generate safety problems such as fire disaster, secondary pollution and the like in the use process. At present, hydrogen peroxide is mainly produced by an anthraquinone method, and the method not only needs to consume higher energy, but also has complex operation conditions. In addition, H 2O2 is relatively unstable, which presents a safety challenge for long distance transportation.
The electrochemical method can utilize solar energy, wind energy and the like as energy sources, and green precursors (such as water, oxygen and the like) as raw materials to generate hydrogen peroxide in situ, so that transportation of concentrated H 2O2 is avoided. The production of electrosynthesis H 2O2 has two pathways, namely the two-electron oxygen reduction reaction (2 e-ORR) and the two-electron water oxidation reaction (2 e-WOR). However, 2e-ORR is limited by oxygen solubility, which is very slow in kinetics. With 2e-ORR,2e-WOR is only water as a raw material, and does not rely on oxygen bubbling or gas diffusion electrodes, and is therefore of great interest. If the cathode 2e-ORR and the anode 2e-WOR can be coupled to prepare hydrogen peroxide simultaneously, the electrosynthesis of H 2O2 with low energy consumption and high efficiency can be realized. However, both the cathode and anode are available to react with 4e, limiting the synthesis of H 2O2. Therefore, development of an inexpensive and stable electrocatalyst material to simultaneously improve the selectivity and activity of cathode and anode reactions has a very broad prospect. Carbon materials are widely concerned because of their structure which is easy to control and acid and alkali resistance. Among them, natural crystalline flake graphite is abundant and inexpensive in resources, has a highly ordered carbon structure and pi-pi stacking structure, contributes to realization of higher electron conductivity and improvement of adsorption force to gas molecules, and therefore, graphite is an excellent carbon-based catalyst raw material.
The invention provides a graphite-based bifunctional electrosynthesis H 2O2 catalytic material and a preparation method thereof, wherein the preparation method is simple and green, is easy for large-scale preparation, realizes high-value utilization of natural graphite, and can be widely applied to efficient electrosynthesis H 2O2 to promote rapid development of the energy conversion field.
Disclosure of Invention
In order to solve the problem of poor catalytic performance of natural graphite, the invention provides a graphite-based bifunctional electrosynthesis H 2O2 catalytic material and a preparation method thereof, and the preparation method is characterized in that the natural graphite interface is modified to prepare the low-cost and high-efficiency bifunctional electrosynthesis hydrogen peroxide catalytic material, thereby providing a new path for high-valued utilization of natural graphite, and specifically comprising the following steps:
(1) Measuring a certain mass fraction A in a beaker, and using a solvent B to fix the volume of the mixture in the A according to a specific proportion, and fully mixing to obtain a reactant 1;
(2) Weighing spherical graphite tailing after purification with a certain mass, uniformly mixing the spherical graphite tailing with the product 1 according to a certain mass ratio, uniformly stirring and fully reacting for a certain time to obtain a mixed solution 2;
(3) And washing the mixed solution with water, suction filtering, drying, and then mixing and pyrolyzing with a surface modifier to obtain a final product.
Further, in the step (1), A can be one or a combination of more of the following reagents, namely concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, hydrofluoric acid, hypochlorous acid, oxalic acid, potassium permanganate, hydrogen peroxide, sodium hydroxide, potassium hydroxide and ammonium chloride, and the effective content of A accounts for 2-50% of the mass fraction of the reactant 1;
Further, in the step (1), the solvent B used for dilution is one or more of deionized water, methanol, absolute ethyl alcohol, ethylene glycol, glycerol, isopropanol, n-butanol and tert-butanol, and the mass ratio of the solute to the solvent is 1:1-1:200;
Further, in the step (2), the particle diameter D50 of the spherical graphite is 800 nm-30 mu m, and the fixed carbon content after purification is more than 99%;
Further, in the step (2), the reaction time is 2-120 h;
Further, the surface modifier in the step (3) may be one or more of citric acid, ammonium chloride, melamine, thiourea, phytic acid, polypyrrole, urea, thiophenol, dimethyl sulfide, trimethyl phosphite, coal pitch, phenolic resin, oligomeric acrylonitrile and polyvinylpyrrolidone, the carbonization temperature is 50-1100 ℃, the heating rate is 1-10 ℃/min, the heat preservation time is 30-900 min, and the carbonization atmosphere is argon, nitrogen, ammonia or hydrogen-argon mixed atmosphere (wherein the hydrogen accounts for 5%).
The invention aims to combine the characteristics of natural spherical graphite raw materials, and modify certain interfaces to improve the electrocatalytic activity and selectivity of the natural spherical graphite raw materials, so as to finally obtain the low-cost and high-efficiency difunctional electrocatalytic hydrogen peroxide material. The natural graphite has complete lattice structure and less carbon defect, and has lower catalytic activity. The structure of the defect structure of the graphite material can be realized through interface structure regulation, so that active sites exist on the surface of the material, which is favorable for the loss and loss of electrons in electrochemical reaction, and further the efficiency of simultaneously generating H 2O2 by the anode and cathode is improved.
The method has simple operation and short modification period, and the required modifier is a conventional cheap reagent, has strong operability and is an effective means for realizing the high value of the natural graphite. The modified natural graphite has excellent H 2O2 productivity, can improve the defects of poor catalytic activity of carbon-based materials and the like while reducing the cost, and has very wide application prospect.
Drawings
FIG. 1 is a flow chart of the experiment of the present invention.
Fig. 2 is an SEM image of modified natural graphite according to embodiment 1 of the present invention: a) SEM images of modified graphite at low magnification; b) SEM images of modified graphite at high magnification.
FIG. 3 is an electrochemical performance chart of modified natural graphite in examples 1-3 of the present invention: a) Cathode electrochemical activity profile; b) Anode electrochemical activity profile.
FIG. 4 is a graph showing the yield of modified natural graphite H 2O2 in example 4 of the present invention: a) Cathode H 2O2 yield plot; b) Anode H 2O2 yield plot.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1
Placing purified natural graphite with a certain mass and mixed acid (15% HNO 3+15％H2O2) with a mass fraction of 30% in a beaker according to a mass ratio of 1:5 to form a mixture, vigorously stirring the mixture by using a magnetic stirrer, reacting for 48 hours, filtering, washing and drying the reacted suspension to obtain a product 1.
A scanning electron microscope (JSM-7800) was used to observe the morphology of the modified natural graphite material under the above conditions, as shown in FIG. 2.
The modified natural graphite electrocatalytic material prepared in example 1 was directly used for a water electrolysis reaction, carbon cloth was used as a load electrode, the load amount was 0.3mg/cm 2, a counter electrode was a graphite rod, ag/AgCl was used as a reference electrode, in an H-type electrolytic cell, 2mol/L potassium bicarbonate was used as an electrolyte for an anode, and 0.1mol/L potassium hydroxide was used as an electrolyte for a cathode, and an electrochemical performance test was performed in a three-electrode system. The linear sweep voltammogram sweep potential was from-0.2 to 1.1v vs. rhe, the sweep rate was 10mV/s, and the test was the result of the catalytic material after 20 cycles of activation after the electrochemical reaction apparatus, as shown in fig. 3. Compared with natural graphite, the modified graphite cathode has slightly reduced electrochemical initial potential, but obviously raised current density and raised anode current density by about 5 times. The activity of the modified natural graphite is obviously improved.
Example 2
Placing purified natural graphite with a certain mass and mixed acid (20% HNO 3+20％H2O2) with a mass fraction of 40% in a beaker according to a mass ratio of 1:5 to form a mixture, vigorously stirring the mixture by using a magnetic stirrer, reacting for 48 hours, filtering, washing and drying the reacted suspension to obtain a product 2.
The modified natural graphite electrocatalytic material prepared in example 2 was directly used for a water electrolysis reaction, carbon cloth was used as a load electrode, the load amount was 0.3mg/cm 2, a counter electrode was a graphite rod, ag/AgCl was used as a reference electrode, in an H-type electrolytic cell, 2mol/L potassium bicarbonate was used as an electrolyte for an anode, and 0.1mol/L potassium hydroxide was used as an electrolyte for a cathode, and an electrochemical performance test was performed in a three-electrode system. The linear sweep voltammogram sweep potential was from-0.2 to 1.1v vs. rhe, the sweep rate was 10mV/s, and the test was the result of the catalytic material after 20 cycles of activation after the electrochemical reaction apparatus, as shown in fig. 3. Compared with natural graphite, the initial potential of the modified graphite cathode electrochemistry is almost unchanged, the cathode current density is improved, and the anode current density is improved by about 4 times. The activity of the modified natural graphite is obviously improved.
Example 3
Placing purified natural graphite with a certain mass and mixed acid (25% HNO 3+25％H2O2) with a mass fraction of 50% in a beaker according to a mass ratio of 1:5 to form a mixture, vigorously stirring the mixture by using a magnetic stirrer, reacting for 48 hours, filtering, washing and drying the reacted suspension to obtain a product 3.
The modified natural graphite electrocatalytic material prepared in example 3 was directly used for a water electrolysis reaction, carbon cloth was used as a load electrode, the load amount was 0.3mg/cm 2, a counter electrode was a graphite rod, ag/AgCl was used as a reference electrode, in an H-type electrolytic cell, 2mol/L potassium bicarbonate was used as an electrolyte for an anode, and 0.1mol/L potassium hydroxide was used as an electrolyte for a cathode, and an electrochemical performance test was performed in a three-electrode system. The linear sweep voltammogram sweep potential is from-0.2 to 1.1v vs. rhe, the sweep speed is 10mV/s, the test is the result of the catalytic material after 20 turns of activation after the electrochemical reaction device, as shown in fig. 3, compared with the natural graphite, the initial potential of the modified graphite cathode electrochemistry is almost unaffected, the current density is slightly reduced, and the anode current density is improved by about 7 times. The activity of the modified natural graphite is obviously improved.
Example 4
Placing purified natural graphite with a certain mass and mixed acid (15% HNO 3+15％H2O2) with a mass fraction of 30% in a beaker according to a mass ratio of 1:5 to form a mixture, vigorously stirring the mixture by using a magnetic stirrer, reacting for 72 hours, filtering, washing and drying the reacted suspension to obtain a product 4.
The modified natural graphite electrocatalytic material prepared in example 4 was directly used for a water electrolysis reaction, carbon cloth was used as a load electrode, the load amount was 0.3mg/cm 2, a counter electrode was a graphite rod, ag/AgCl was used as a reference electrode, in an H-type electrolytic cell, 2mol/L potassium bicarbonate was used as an electrolyte for an anode, and 0.1mol/L potassium hydroxide was used as an electrolyte for a cathode, and an electrochemical performance test was performed in a three-electrode system. The linear sweep voltammogram sweep potential was from-0.2 to 1.1v vs. rhe, the sweep rate was 10mV/s, and the test was the result of the catalytic material after 20 cycles of activation after the electrochemical reaction apparatus. During the electrolysis, 1ml of electrolyte is extracted for quantification of H 2O2, as shown in FIG. 4, 180umol/L H 2O2 can be generated at the cathode and 65umol/L H 2O2 can be generated at the anode within 4000s, and the capability of generating H 2O2 of the modified graphite is remarkably improved.
Example 5
Placing purified natural graphite with a certain mass and mixed acid (20% HNO 3+20％H2O2) with a mass fraction of 40% in a beaker according to a mass ratio of 1:5 to form a mixture, vigorously stirring the mixture by using a magnetic stirrer, reacting for 72 hours, filtering, washing and drying the reacted suspension to obtain a product 5. Mixing the product 5 with melamine according to a mass ratio of 1:1, heating to 700 ℃ at a speed of 5 ℃/min under an argon atmosphere, naturally cooling, and grinding to obtain a final product.
The modified natural graphite electrocatalytic material prepared in example 5 was directly used for a water electrolysis reaction, carbon cloth was used as a load electrode, the load amount was 0.3mg/cm 2, a counter electrode was a graphite rod, ag/AgCl was used as a reference electrode, in an H-type electrolytic cell, 2mol/L potassium bicarbonate was used as an electrolyte for an anode, and 0.1mol/L potassium hydroxide was used as an electrolyte for a cathode, and an electrochemical performance test was performed in a three-electrode system. The linear sweep voltammogram sweep potential was from-0.2 to 1.1v vs. rhe, the sweep rate was 10mV/s, and the test was the result of the catalytic material after 20 cycles of activation after the electrochemical reaction apparatus. Electrochemical testing showed an increase in cathodic reduction potential of about 0.05V and an increase in anodic current density of about 5.5-fold. During the electrolysis process, 1ml of electrolyte is extracted for quantification of H 2O2, 320umol/L H 2O2 can be generated at the cathode, 90umol/L H 2O2 can be generated at the anode within 4000s, and the capability of generating H 2O2 of the modified graphite is remarkably improved.
Example 6
Placing purified natural graphite with a certain mass and mixed acid (25% HNO 3+25％H2O2) with a mass fraction of 50% in a beaker according to a mass ratio of 1:5 to form a mixture, vigorously stirring the mixture by using a magnetic stirrer, reacting for 48 hours, filtering, washing and drying the reacted suspension to obtain a product 5. Mixing the product 5 with thiourea according to a mass ratio of 1:1, heating to 900 ℃ at a speed of 5 ℃/min under an argon atmosphere, naturally cooling, and grinding to obtain a final product.
The modified natural graphite electrocatalytic material prepared in example 6 was directly used for a water electrolysis reaction, carbon cloth was used as a load electrode, the load amount was 0.3mg/cm 2, a counter electrode was a graphite rod, ag/AgCl was used as a reference electrode, in an H-type electrolytic cell, 2mol/L potassium bicarbonate was used as an electrolyte for an anode, and 0.1mol/L potassium hydroxide was used as an electrolyte for a cathode, and an electrochemical performance test was performed in a three-electrode system. The linear sweep voltammogram sweep potential was from-0.2 to 1.1v vs. rhe, the sweep rate was 10mV/s, and the test was the result of the catalytic material after 20 cycles of activation after the electrochemical reaction apparatus. Electrochemical testing showed an increase in cathodic reduction potential of about 0.15V and an increase in anodic current density of about 4.5 times. During the electrolysis, 1ml of electrolyte is extracted to quantitatively determine H2O2, 265umol/L H 2O2 can be generated at the cathode, 106umol/L H 2O2 can be generated at the anode within 4000s, and the capability of generating H 2O2 of the modified graphite is remarkably improved.
Example 7
Placing purified natural graphite with a certain mass and mixed acid (25% HNO 3+25％H2O2) with a mass fraction of 50% in a beaker according to a mass ratio of 1:5 to form a mixture, vigorously stirring the mixture by using a magnetic stirrer, reacting for 72 hours, filtering, washing and drying the reacted suspension to obtain a product 5. Mixing the product 5 with urea according to the mass ratio of 1:1, heating to 600 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, naturally cooling and grinding to obtain the final product.
The modified natural graphite electrocatalytic material prepared in example 7 was directly used for a water electrolysis reaction, carbon cloth was used as a load electrode, the load amount was 0.3mg/cm 2, a counter electrode was a graphite rod, ag/AgCl was used as a reference electrode, in an H-type electrolytic cell, 2mol/L potassium bicarbonate was used as an electrolyte for an anode, and 0.1mol/L potassium hydroxide was used as an electrolyte for a cathode, and an electrochemical performance test was performed in a three-electrode system. The linear sweep voltammogram sweep potential was from-0.2 to 1.1v vs. rhe, the sweep rate was 10mV/s, and the test was the result of the catalytic material after 20 cycles of activation after the electrochemical reaction apparatus. Electrochemical testing showed an increase in cathodic reduction potential of about 0.13V and an increase in anodic current density of about 4.9 times. During the electrolysis, 1ml of electrolyte is extracted for quantification of H 2O2, within 4000 seconds, 215umol/L H 2O2 can be produced at the cathode, 116umol/L H 2O2 can be produced at the anode, and the capacity of producing H 2O2 of the modified graphite is remarkably improved.
Example 8
Placing purified natural graphite with a certain mass and mixed acid with a mass fraction of 30% (25% HNO 3+25％H2O2) in a beaker according to a mass ratio of 1:5 to form a mixture, vigorously stirring the mixture by using a magnetic stirrer for 96 hours, filtering, washing and drying the suspension after the reaction to obtain a product 5. Mixing the product 5 with phytic acid according to the mass ratio of 1:1, heating to 800 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, naturally cooling and grinding to obtain the final product.
The modified natural graphite electrocatalytic material prepared in example 8 was directly used for a water electrolysis reaction, carbon cloth was used as a load electrode, the load amount was 0.3mg/cm 2, a counter electrode was a graphite rod, ag/AgCl was used as a reference electrode, in an H-type electrolytic cell, 2mol/L potassium bicarbonate was used as an electrolyte for an anode, and 0.1mol/L potassium hydroxide was used as an electrolyte for a cathode, and an electrochemical performance test was performed in a three-electrode system. The linear sweep voltammogram sweep potential was from-0.2 to 1.1v vs. rhe, the sweep rate was 10mV/s, and the test was the result of the catalytic material after 20 cycles of activation after the electrochemical reaction apparatus. Electrochemical testing showed an increase in cathodic reduction potential of about 0.21V and an increase in anodic current density of about 5.3 times. During the electrolysis, 1ml of electrolyte is extracted for quantification of H 2O2, within 4000 seconds, 335umol/L H 2O2 can be produced at the cathode, 156umol/L H 2O2 can be produced at the anode, and the capacity of producing H 2O2 of the modified graphite is remarkably improved.
Example 9
Placing purified natural graphite with a certain mass and mixed acid with a mass fraction of 30% (25% HNO 3+25％H2O2) in a beaker according to a mass ratio of 1:5 to form a mixture, vigorously stirring the mixture by using a magnetic stirrer for 96 hours, filtering, washing and drying the suspension after the reaction to obtain a product 5. Mixing the product 5 with polypyrrole according to a mass ratio of 1:1, heating to 700 ℃ at a speed of 2 ℃/min under an argon atmosphere, naturally cooling, and grinding to obtain a final product.
The modified natural graphite electrocatalytic material prepared in example 9 was directly used for a water electrolysis reaction, carbon cloth was used as a load electrode, the load amount was 0.3mg/cm 2, a counter electrode was a graphite rod, ag/AgCl was used as a reference electrode, in an H-type electrolytic cell, 2mol/L potassium bicarbonate was used as an electrolyte for an anode, and 0.1mol/L potassium hydroxide was used as an electrolyte for a cathode, and an electrochemical performance test was performed in a three-electrode system. The linear sweep voltammogram sweep potential was from-0.2 to 1.1v vs. rhe, the sweep rate was 10mV/s, and the test was the result of the catalytic material after 20 cycles of activation after the electrochemical reaction apparatus. Electrochemical testing showed an increase in cathodic reduction potential of about 0.03V and an increase in anodic current density of about 2.3 times. During the electrolysis, 1ml of electrolyte is extracted for quantification of H 2O2, 120umol/L H 2O2 can be generated at the cathode and 48umol/L H 2O2 can be generated at the anode within 4000s, and the capability of generating H 2O2 of the modified graphite is remarkably improved.
Example 10
Placing purified natural graphite with a certain mass and mixed acid (20% HNO 3+20％H2O2) with a mass fraction of 40% in a beaker according to a mass ratio of 1:5 to form a mixture, vigorously stirring the mixture by using a magnetic stirrer for 96 hours, filtering, washing and drying the suspension after the reaction to obtain a product 5. Mixing the product 5 with oligomeric acrylonitrile according to the mass ratio of 1:1, heating to 900 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, naturally cooling and grinding to obtain the final product.
The modified natural graphite electrocatalytic material prepared in example 10 was directly used for a water electrolysis reaction, carbon cloth was used as a load electrode, the load amount was 0.3mg/cm 2, a counter electrode was a graphite rod, ag/AgCl was used as a reference electrode, in an H-type electrolytic cell, 2mol/L potassium bicarbonate was used as an electrolyte for an anode, and 0.1mol/L potassium hydroxide was used as an electrolyte for a cathode, and an electrochemical performance test was performed in a three-electrode system. The linear sweep voltammogram sweep potential was from-0.2 to 1.1v vs. rhe, the sweep rate was 10mV/s, and the test was the result of the catalytic material after 20 cycles of activation after the electrochemical reaction apparatus. Electrochemical testing showed an increase in cathodic reduction potential of about 0.15V and an increase in anodic current density of about 3.3-fold. During the electrolysis, 1ml of electrolyte is extracted for quantification of H 2O2, in 4000s, 249umol/L H 2O2 can be produced at the cathode, 168umol/L H 2O2 can be produced at the anode, and the capacity of producing H 2O2 of the modified graphite is remarkably improved.
In the description of the present specification, the descriptions of the terms "one implementation," "some implementations," "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is a further detailed description of the invention in connection with specific embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several simple deductions or substitutions can be made without departing from the spirit of the invention.
Claims (3)
1. The preparation method of the graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material is characterized by comprising the following steps of:
(1) Measuring a certain mass fraction A in a beaker, and using a solvent B to fix the volume of the mixture in the A according to a specific proportion, and fully mixing to obtain a reactant 1; wherein A is one or a combination of more of the following reagents, namely concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, hydrofluoric acid, hypochlorous acid, oxalic acid, potassium permanganate, hydrogen peroxide, sodium hydroxide, potassium hydroxide and ammonium chloride, and the effective content of A accounts for 2-50% of the mass fraction of the reactant 1; the solvent B used for dilution is one or more of deionized water, methanol, absolute ethyl alcohol, glycol, glycerol, isopropanol, n-butanol and tert-butanol, and the mass ratio of the solute to the solvent is 1:1-1:200;
(2) Weighing spherical graphite tailing after purification with a certain mass, uniformly mixing the spherical graphite tailing with the product 1 according to a certain mass ratio, uniformly stirring and fully reacting for a certain time to obtain a mixed solution 2;
(3) Washing the mixed solution with water, suction filtering, drying, and then mixing and pyrolyzing with a surface modifier to obtain a final product; wherein the surface modifier is one or more of citric acid, ammonium chloride, melamine, thiourea, phytic acid, polypyrrole, urea, thiophenol, dimethyl sulfide, trimethyl phosphite, coal tar pitch, phenolic resin, oligomeric acrylonitrile and polyvinylpyrrolidone, the carbonization temperature is 50-1100 ℃, the heating rate is 1-10 ℃/min, the heat preservation time is 30-900 min, and the carbonization atmosphere is argon, nitrogen, ammonia or hydrogen-argon mixed atmosphere.
2. The method for preparing the graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material of claim 1, wherein the particle diameter D50 of the spherical graphite in the step (2) is 800 nm-30 μm, and the fixed carbon content after purification is more than 99%.
3. The method for preparing the graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material of claim 1, wherein in step (2), the reaction time is 2-120 h.
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