CN114875430A - 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
- Publication number
- CN114875430A CN114875430A CN202210410264.9A CN202210410264A CN114875430A CN 114875430 A CN114875430 A CN 114875430A CN 202210410264 A CN202210410264 A CN 202210410264A CN 114875430 A CN114875430 A CN 114875430A
- Authority
- CN
- China
- Prior art keywords
- graphite
- catalytic material
- hydrogen peroxide
- electrosynthesis
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 43
- 239000010439 graphite Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 30
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000012467 final product Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 3
- 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
- 239000001257 hydrogen 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
- 239000000467 phytic acid Substances 0.000 claims description 3
- 229940068041 phytic acid Drugs 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000011300 coal pitch Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 abstract description 39
- 238000005868 electrolysis reaction Methods 0.000 abstract description 17
- 238000012986 modification Methods 0.000 abstract description 11
- 230000004048 modification Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 27
- 239000000725 suspension Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 238000003487 electrochemical reaction Methods 0.000 description 11
- 229910021607 Silver chloride Inorganic materials 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 10
- 235000015497 potassium bicarbonate Nutrition 0.000 description 10
- 239000011736 potassium bicarbonate Substances 0.000 description 10
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000004832 voltammetry Methods 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000000840 electrochemical analysis Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000011002 quantification Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 238000000746 purification 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- 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 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, and uniformly stirring the mixture to fully react for a certain time to obtain a mixed solution 2; (3) and washing and drying the mixed solution, and mixing the dried mixed solution with a surface modifier for pyrolysis to obtain a final product. The catalytic material for water electrolysis shows high electrochemical activity, selectivity and stability. The invention takes natural graphite as a raw material, obtains a high-efficiency bifunctional electrosynthesis hydrogen peroxide catalytic material through interface modification, realizes high-value utilization of natural spherical graphite, and has the advantages of green and simple process, low cost and wide scale preparation prospect.
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) 2 O 2 ) Is a high-value and green chemical oxidant, and has wide application in industry and daily life, including water purification, industrial pulp bleaching and chemical synthesis. In particular, the hydrogen peroxide is used as long-acting active oxygen, is a high-efficiency disinfection medium, and does not generate safety problems such as fire, secondary pollution and the like in the using process. At present, the industry mainly produces hydrogen peroxide by an anthraquinone method, and the method not only needs to consume higher energy, but also has complex operation conditions. Furthermore, H 2 O 2 And the method is relatively unstable, and brings safety challenges to long-distance transportation.
The electrochemical method can utilize solar energy, wind energy and the like as energy sources, green precursors (such as water, oxygen and the like) are used as raw materials, hydrogen peroxide is generated in situ, and H concentration is avoided 2 O 2 And (4) transporting. Electrosynthesis of H 2 O 2 There are two pathways for the generation of (2e-ORR) and (2e-WOR) for the two-electron oxygen reduction reaction. However, 2e-ORR is limited by oxygen solubility, and its kinetics are very slow. 2e-ORR, 2e-WOR is drawing attention because it uses only water as a raw material and does not rely on oxygen bubbling or gas diffusion electrodes. If the cathode 2e-ORR and the anode 2e-WOR can be coupled to prepare hydrogen peroxide at the same time, the electrosynthesis of H with low energy consumption and high efficiency can be realized 2 O 2 . However, both the cathode and the anode, there is a reaction with 4e, limiting H 2 O 2 And (4) synthesizing. Therefore, the development of an inexpensive and stable electrocatalyst material to simultaneously improve the selectivity and activity of the cathode-anode reaction has a very broad prospect. Carbon materials have received much attention because of their easily regulated structure and their acid and alkali resistance. The natural crystalline flake graphite is rich and cheap in resources, has a highly ordered carbon structure and a pi-pi stacking structure, and is beneficial to realizing higher electronic conductivity and improving the adsorption force on gas molecules, so that the graphite is an excellent carbon-based catalyst raw material.
The invention provides graphite-based bifunctional electrosynthesis H 2 O 2 CatalysisThe material and the preparation method thereof have the advantages that the preparation method is simple and green, the large-scale preparation is easy, the high-valued utilization of the natural graphite is realized, and the prepared bifunctional carbon-based catalytic material can be widely applied to the high-efficiency electrosynthesis of H 2 O 2 And promote the 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 graphite-based bifunctional electrosynthesis H 2 O 2 The catalytic material and the preparation method thereof are characterized in that the bifunctional electrosynthesis hydrogen peroxide catalytic material with low cost and high efficiency is prepared by natural graphite interface modification, a new path is provided for high-value utilization of natural graphite, and the preparation method comprises the following specific steps:
(1) measuring a certain mass fraction A in a beaker, fixing the volume of the mixture in the A by using a solvent B according to a specific proportion, and fully mixing to obtain a reactant 1;
(2) weighing a certain mass of the purified spherical graphite tailings, uniformly mixing the spherical graphite tailings with the product 1 according to a certain mass ratio, and uniformly stirring the mixture to fully react for a certain time to obtain a mixed solution 2;
(3) and washing, filtering, drying, mixing with a surface modifier, and pyrolyzing to obtain the final product.
Further, in the step (1), A can be one or a combination of more of 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 size D50 of the spherical graphite is 800 nm-30 μm, and the content of the purified fixed carbon 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 ℃ to 1100 ℃, the heating rate is 1 ℃/min to 10 ℃/min, the holding time is 30min to 900min, and the carbonization atmosphere is argon, nitrogen, ammonia or hydrogen and argon mixed atmosphere (wherein the hydrogen proportion is 5%).
The invention aims to combine the characteristics of natural spherical graphite raw materials, modify a certain interface of the natural spherical graphite raw materials to improve the electrocatalytic activity and selectivity of the natural spherical graphite raw materials, and finally obtain the low-cost and high-efficiency bifunctional electrosynthesis hydrogen peroxide catalytic material. The natural graphite has complete structural lattice and less carbon defects, so that the catalytic activity is lower. The defect structure of the graphite material can be constructed by regulating and controlling the interface structure, so that active sites exist on the surface of the material, the gain and loss of electrons in electrochemical reaction are facilitated, and the generation of H by the cathode and the anode is improved 2 O 2 The efficiency of (c).
The method has the advantages of simple operation, short modification period, high operability and effective means for realizing high-valued natural graphite, and all required modifiers are conventional cheap reagents. The modified natural graphite shows excellent H 2 O 2 The productivity can be reduced, the defects of poor catalytic activity of the carbon-based material and the like can be improved while the cost is reduced, and the method has a very wide application prospect.
Drawings
FIG. 1 is a flow chart of an experiment according to the present invention.
Fig. 2 is an SEM image of modified natural graphite in embodiment 1 of the present invention: a) SEM image of modified graphite under low magnification; b) SEM image of modified graphite at high magnification.
FIG. 3 is an electrochemical performance diagram of modified natural graphite in embodiments 1 to 3 of the present invention: a) a cathodic electrochemical activity profile; b) anode electrochemical activity diagram.
FIG. 4 shows modified natural graphite H in example 4 of the present invention 2 O 2 Yield chart: a) cathode H 2 O 2 Yield diagram(ii) a b) Anode H 2 O 2 The yield chart.
Detailed Description
The present invention will be further described with reference to the following 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 are commercially available, unless otherwise specified.
Example 1
Mixing the purified natural graphite with 30 wt% of mixed acid (15 wt% HNO) 3 +15％H 2 O 2 ) Placing the mixture into a beaker according to the mass ratio of 1:5 to form a mixture, violently stirring the mixture by using a magnetic stirrer for 48 hours, carrying out suction filtration and cleaning treatment on the suspension after reaction, and drying the suspension to obtain a product 1.
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 the example 1 is directly used for water electrolysis reaction, carbon cloth is used as a load electrode, and the load is 0.3mg/cm 2 The counter electrode is a graphite rod, Ag/AgCl is used as a reference electrode, 2mol/L potassium bicarbonate is used as an electrolyte at the anode and 0.1mol/L potassium hydroxide is used as an electrolyte at the cathode in an H-shaped electrolytic cell, and the electrochemical performance test is carried out in a three-electrode system. The scanning potential of the linear scanning voltammetry curve is from-0.2 to 1.1V vs. RHE, the scanning speed is 10mV/s, and the test is the result after the catalytic material is activated for 20 circles after the electrochemical reaction device, as shown in figure 3. Compared with natural graphite, the initial potential of the modified graphite cathode in electrochemistry is slightly reduced, but the current density is obviously improved, and the current density of the anode is improved by about 5 times. The activity of the modified natural graphite is obviously improved.
Example 2
Mixing the purified natural graphite with 40 wt% of mixed acid (20% HNO) 3 +20％H 2 O 2 ) Placing the mixture into a beaker according to the mass ratio of 1:5 to form a mixture, and violently stirring the mixture by using a magnetic stirrer for reaction for a reaction time ofAnd (5) performing suction filtration, washing and drying on the reacted suspension liquid to obtain a product 2.
The modified natural graphite electrocatalytic material prepared in the example 2 is directly used for water electrolysis reaction, carbon cloth is used as a load electrode, and the load is 0.3mg/cm 2 The counter electrode is a graphite rod, Ag/AgCl is used as a reference electrode, 2mol/L potassium bicarbonate is used as an electrolyte at the anode and 0.1mol/L potassium hydroxide is used as an electrolyte at the cathode in an H-shaped electrolytic cell, and the electrochemical performance test is carried out in a three-electrode system. The scanning potential of the linear scanning voltammetry curve is from-0.2 to 1.1V vs. RHE, the scanning speed is 10mV/s, and the test is the result after the catalytic material is activated for 20 circles after the electrochemical reaction device, as shown in figure 3. Compared with natural graphite, the initial potential of the modified graphite cathode is almost kept 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
Mixing purified natural graphite with 50 wt% of mixed acid (25% HNO) 3 +25％H 2 O 2 ) Placing the mixture into a beaker according to the mass ratio of 1:5 to form a mixture, violently stirring the mixture by using a magnetic stirrer for 48 hours, carrying out suction filtration and cleaning treatment on the suspension after reaction, and drying the suspension to obtain a product 3.
The modified natural graphite electrocatalytic material prepared in the example 3 is directly used for water electrolysis reaction, carbon cloth is used as a load electrode, and the load is 0.3mg/cm 2 The counter electrode is a graphite rod, Ag/AgCl is used as a reference electrode, 2mol/L potassium bicarbonate is used as an electrolyte at the anode and 0.1mol/L potassium hydroxide is used as an electrolyte at the cathode in an H-shaped electrolytic cell, and the electrochemical performance test is carried out in a three-electrode system. The scanning potential of the linear scanning voltammetry curve is from-0.2 to 1.1V vs. RHE, the scanning speed is 10mV/s, the test is the result after the catalytic material is activated for 20 circles after the electrochemical reaction device, as shown in figure 3, compared with natural graphite, the initial potential of the modified graphite cathode electrochemistry is hardly influenced, 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
Mixing purified natural graphite with 30 wt% mixed acid (15% HNO) 3 +15％H 2 O 2 ) Placing the mixture into a beaker according to the mass ratio of 1:5 to form a mixture, violently stirring the mixture by using a magnetic stirrer for 72 hours, carrying out suction filtration and cleaning treatment on the suspension after reaction, and drying the suspension to obtain a product 4.
The modified natural graphite electrocatalytic material prepared in the example 4 is directly used for water electrolysis reaction, carbon cloth is used as a load electrode, and the load is 0.3mg/cm 2 The counter electrode is a graphite rod, Ag/AgCl is used as a reference electrode, 2mol/L potassium bicarbonate is used as an electrolyte at the anode and 0.1mol/L potassium hydroxide is used as an electrolyte at the cathode in an H-shaped electrolytic cell, and the electrochemical performance test is carried out in a three-electrode system. The scanning potential of the linear scanning voltammetry curve is from-0.2 to 1.1V vs. RHE, the scanning speed is 10mV/s, and the test is the result after the catalytic material is activated for 20 circles after the electrochemical reaction device. 1ml of electrolyte was withdrawn during the electrolysis for quantification of H 2 O 2 As shown in FIG. 4, the cathode can generate 180umol/L H in 4000s 2 O 2 The anode can generate 65umol/L H 2 O 2 Modification of graphite to produce H 2 O 2 The ability of (a) is significantly improved.
Example 5
Mixing the purified natural graphite with 40 wt% of mixed acid (20% HNO) 3 +20％H 2 O 2 ) Placing the mixture into a beaker according to the mass ratio of 1:5 to form a mixture, violently stirring the mixture by using a magnetic stirrer for 72 hours, carrying out suction filtration and cleaning treatment on the suspension after reaction, and drying the suspension to obtain a product 5. And mixing the product 5 with melamine according to the mass ratio of 1:1, heating to 700 ℃ at the speed of 5 ℃/min under the argon atmosphere, naturally cooling, and grinding to obtain the final product.
The modified natural graphite electrocatalytic material prepared in the example 5 is directly used for water electrolysis reaction, carbon cloth is used as a load electrode, and the load is 0.3mg/cm 2 The counter electrode is a graphite rod, Ag/AgCl is used as a reference electrode, and 2mol/L potassium bicarbonate is used as electrolyte in an H-shaped electrolytic tankAnd the cathode takes 0.1mol/L potassium hydroxide as electrolyte and carries out electrochemical performance test in a three-electrode system. The scanning potential of the linear scanning voltammetry curve is from-0.2 to 1.1V vs. RHE, the scanning speed is 10mV/s, and the test is the result after the catalytic material is activated for 20 circles after the electrochemical reaction device. Electrochemical tests showed that the cathodic reduction potential increased by about 0.05V and the anodic current density increased by about 5.5 times. 1ml of electrolyte was withdrawn during the electrolysis for quantification H 2 O 2 The cathode can generate 320umol/L H in 4000s 2 O 2 The anode can generate 90umol/L H 2 O 2 Modification of graphite to produce H 2 O 2 The ability of (a) is significantly improved.
Example 6
Mixing purified natural graphite with 50 wt% of mixed acid (25% HNO) 3 +25％H 2 O 2 ) Placing the mixture into a beaker according to the mass ratio of 1:5 to form a mixture, stirring the mixture vigorously by using a magnetic stirrer for 48 hours, carrying out suction filtration and cleaning treatment on the suspension after reaction, and drying the suspension to obtain a product 5. And mixing the product 5 with thiourea according to the mass ratio of 1:1, heating to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere, naturally cooling, and grinding to obtain the final product.
The modified natural graphite electrocatalytic material prepared in the example 6 is directly used for water electrolysis reaction, carbon cloth is used as a load electrode, and the load is 0.3mg/cm 2 The counter electrode is a graphite rod, Ag/AgCl is used as a reference electrode, 2mol/L potassium bicarbonate is used as an electrolyte at the anode and 0.1mol/L potassium hydroxide is used as an electrolyte at the cathode in an H-shaped electrolytic cell, and the electrochemical performance test is carried out in a three-electrode system. The scanning potential of the linear scanning voltammetry curve is from-0.2 to 1.1V vs. RHE, the scanning speed is 10mV/s, and the test is the result after the catalytic material is activated for 20 circles after the electrochemical reaction device. Electrochemical tests showed that the cathodic reduction potential increased by about 0.15V and the anodic current density increased by about 4.5 times. 1ml of electrolyte is extracted for quantitative H2O2 in the electrolytic process, and 265umol/L H can be generated at the cathode within 4000s 2 O 2 The anode can generate 106umol/L H 2 O 2 Modification of graphite to produce H 2 O 2 The capacity of (2) is remarkably improved.
Example 7
Mixing purified natural graphite with 50 wt% of mixed acid (25% HNO) 3 +25％H 2 O 2 ) Placing the mixture into a beaker according to the mass ratio of 1:5 to form a mixture, violently stirring the mixture by using a magnetic stirrer for 72 hours, carrying out suction filtration and cleaning treatment on the suspension after reaction, and drying the suspension to obtain a product 5. And mixing the product 5 with urea according to a mass ratio of 1:1, heating to 600 ℃ at a speed of 2 ℃/min under a nitrogen atmosphere, naturally cooling, and grinding to obtain a final product.
The modified natural graphite electrocatalytic material prepared in the example 7 is directly used for water electrolysis reaction, carbon cloth is used as a load electrode, and the load is 0.3mg/cm 2 The counter electrode is a graphite rod, Ag/AgCl is used as a reference electrode, 2mol/L potassium bicarbonate is used as an electrolyte at the anode and 0.1mol/L potassium hydroxide is used as an electrolyte at the cathode in an H-shaped electrolytic cell, and the electrochemical performance test is carried out in a three-electrode system. The scanning potential of the linear scanning voltammetry curve is from-0.2 to 1.1V vs. RHE, the scanning speed is 10mV/s, and the test is the result after the catalytic material is activated for 20 circles after the electrochemical reaction device. Electrochemical tests showed that the cathodic reduction potential increased by about 0.13V and the anodic current density increased by about 4.9 times. 1ml of electrolyte was withdrawn during the electrolysis for quantification H 2 O 2 The cathode can generate 215umol/L H in 4000s 2 O 2 The anode can generate 116umol/L H 2 O 2 Modification of graphite to produce H 2 O 2 The ability of (a) is significantly improved.
Example 8
Mixing the purified natural graphite with 30% mixed acid (25% HNO) 3 +25％H 2 O 2 ) Placing the mixture into a beaker according to the mass ratio of 1:5 to form a mixture, violently stirring the mixture by using a magnetic stirrer for 96 hours, carrying out suction filtration and cleaning treatment on the suspension after reaction, and drying the suspension 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.
Mixing all the materialsThe modified natural graphite electrocatalytic material prepared in example 8 was directly used for water electrolysis reaction, and carbon cloth was used as a load electrode with a load of 0.3mg/cm 2 The counter electrode is a graphite rod, Ag/AgCl is used as a reference electrode, 2mol/L potassium bicarbonate is used as an electrolyte at the anode and 0.1mol/L potassium hydroxide is used as an electrolyte at the cathode in an H-shaped electrolytic cell, and the electrochemical performance test is carried out in a three-electrode system. The scanning potential of the linear scanning voltammetry curve is from-0.2 to 1.1V vs. RHE, the scanning speed is 10mV/s, and the test is the result after the catalytic material is activated for 20 circles after the electrochemical reaction device. Electrochemical tests showed that the cathodic reduction potential increased by about 0.21V and the anodic current density increased by about 5.3 times. 1ml of electrolyte was withdrawn during the electrolysis for quantification H 2 O 2 The cathode can produce 335umol/L H in 4000s 2 O 2 The anode can generate 156umol/L H 2 O 2 Modification of graphite to produce H 2 O 2 The ability of (a) is significantly improved.
Example 9
Mixing the purified natural graphite with 30% mixed acid (25% HNO) 3 +25％H 2 O 2 ) Placing the mixture into a beaker according to the mass ratio of 1:5 to form a mixture, violently stirring the mixture by using a magnetic stirrer for 96 hours, carrying out suction filtration and cleaning treatment on the suspension after reaction, and drying the suspension to obtain a product 5. And 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 the example 9 is directly used for water electrolysis reaction, carbon cloth is used as a load electrode, and the load is 0.3mg/cm 2 The counter electrode is a graphite rod, Ag/AgCl is used as a reference electrode, 2mol/L potassium bicarbonate is used as an electrolyte at the anode and 0.1mol/L potassium hydroxide is used as an electrolyte at the cathode in an H-shaped electrolytic cell, and the electrochemical performance test is carried out in a three-electrode system. The scanning potential of the linear scanning voltammetry curve is from-0.2 to 1.1V vs. RHE, the scanning speed is 10mV/s, and the test is the result after the catalytic material is activated for 20 circles after the electrochemical reaction device. Electrochemical tests show that the reduction potential of the cathode is improved by about0.03V, the anode current density increased by about 2.3 times. 1ml of electrolyte was withdrawn during the electrolysis for quantification of H 2 O 2 The cathode can generate 120umol/L H in 4000s 2 O 2 The anode can generate 48umol/L H 2 O 2 Modification of graphite to produce H 2 O 2 The ability of (a) is significantly improved.
Example 10
Mixing the purified natural graphite with 40 wt% of mixed acid (20% HNO) 3 +20％H 2 O 2 ) Placing the mixture into a beaker according to the mass ratio of 1:5 to form a mixture, violently stirring the mixture by using a magnetic stirrer for 96 hours, carrying out suction filtration and cleaning treatment on the suspension after reaction, and drying the suspension to obtain a product 5. Mixing the product 5 with the oligomeric acrylonitrile according to the mass ratio of 1:1, heating to 900 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, naturally cooling, and grinding to obtain the final product.
The modified natural graphite electrocatalytic material prepared in the example 10 is directly used for water electrolysis reaction, carbon cloth is used as a load electrode, and the load is 0.3mg/cm 2 The counter electrode is a graphite rod, Ag/AgCl is used as a reference electrode, 2mol/L potassium bicarbonate is used as an electrolyte at the anode and 0.1mol/L potassium hydroxide is used as an electrolyte at the cathode in an H-shaped electrolytic cell, and the electrochemical performance test is carried out in a three-electrode system. The scanning potential of the linear scanning voltammetry curve is from-0.2 to 1.1V vs. RHE, the scanning speed is 10mV/s, and the test is the result after the catalytic material is activated for 20 circles after the electrochemical reaction device. Electrochemical tests show that the reduction potential of the cathode is improved by about 0.15V, and the current density of the anode is improved by about 3.3 times. 1ml of electrolyte was withdrawn during the electrolysis for quantification H 2 O 2 The cathode can generate 249umol/L H in 4000s 2 O 2 The anode can generate 168umol/L H 2 O 2 Modification of graphite to produce H 2 O 2 The ability of (a) is significantly improved.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like, 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 invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. 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 more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. It will be apparent to those skilled in the art that a number of simple derivations or substitutions can be made without departing from the inventive concept.
Claims (6)
1. A graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material and a preparation method thereof are characterized by comprising the following steps:
(1) measuring a certain mass fraction A in a beaker, 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 a certain mass of purified spherical graphite tailings, uniformly mixing the spherical graphite tailings with the product 1 according to a certain mass ratio, and uniformly stirring the mixture to fully react for a certain time to obtain a mixed solution 2;
(3) and washing, filtering, drying, mixing with a surface modifier, and pyrolyzing to obtain the final product.
2. The graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material as defined in claim 1 and the preparation method thereof, wherein A in step (1) can be a combination of one or more of 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 reactant 1.
3. The graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material and the preparation method thereof as claimed in claim 1 are characterized in that in the step (1), the solvent B used for dilution is one or a mixture 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.
4. The graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material as defined in claim 1 and the preparation method thereof are characterized in that in the step (2), the particle size D50 of the spherical graphite is 800 nm-30 μm, and the content of the purified fixed carbon is more than 99%.
5. The graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material and the preparation method thereof as claimed in claim 1, wherein in the step (2), the reaction time is 2-120 h.
6. The graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material as defined in claim 1 and preparation method thereof, characterized in that in step (3), the surface modifier can be one or more of citric acid, ammonium chloride, melamine, thiourea, phytic acid, polypyrrole, urea, thiophenol, dimethyl sulfide, trimethyl phosphite, coal pitch, phenol-formaldehyde resin, oligomeric acrylonitrile, and polyvinylpyrrolidone, the carbonization temperature is 50-1100 ℃, the heating rate is 1-10 ℃/min, the holding time is 30-900 min, and the carbonization atmosphere is argon, nitrogen, ammonia or hydrogen-argon mixed atmosphere (wherein the hydrogen content is 5%).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210410264.9A CN114875430B (en) | 2022-04-19 | 2022-04-19 | Graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210410264.9A CN114875430B (en) | 2022-04-19 | 2022-04-19 | Graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114875430A true CN114875430A (en) | 2022-08-09 |
| CN114875430B CN114875430B (en) | 2024-05-03 |
Family
ID=82671018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210410264.9A Active CN114875430B (en) | 2022-04-19 | 2022-04-19 | Graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114875430B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104599863A (en) * | 2015-01-15 | 2015-05-06 | 华东理工大学 | Method for preparation of composite material, composite material and application thereof |
| CN105271170A (en) * | 2015-11-03 | 2016-01-27 | 山西中兴环能科技有限公司 | Preparation method of nano carbon and composite material of nano carbon |
| US20180190996A1 (en) * | 2017-01-05 | 2018-07-05 | City University Of Hong Kong | Method for preparing hierarchically porous doped carbon material and its use |
| KR20210069301A (en) * | 2019-12-03 | 2021-06-11 | 경희대학교 산학협력단 | Highly Efficient and Durable Electrochemical Catalysts and Use Thereof |
| WO2021189836A1 (en) * | 2020-03-25 | 2021-09-30 | 江西正拓新能源科技股份有限公司 | Graphite negative electrode material for high-performance lithium ion battery and preparation method therefor |
| CN113652699A (en) * | 2021-07-05 | 2021-11-16 | 南昌大学 | Method for improving activity of hydrogen production by electrocatalysis of graphene |
-
2022
- 2022-04-19 CN CN202210410264.9A patent/CN114875430B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104599863A (en) * | 2015-01-15 | 2015-05-06 | 华东理工大学 | Method for preparation of composite material, composite material and application thereof |
| CN105271170A (en) * | 2015-11-03 | 2016-01-27 | 山西中兴环能科技有限公司 | Preparation method of nano carbon and composite material of nano carbon |
| US20180190996A1 (en) * | 2017-01-05 | 2018-07-05 | City University Of Hong Kong | Method for preparing hierarchically porous doped carbon material and its use |
| KR20210069301A (en) * | 2019-12-03 | 2021-06-11 | 경희대학교 산학협력단 | Highly Efficient and Durable Electrochemical Catalysts and Use Thereof |
| WO2021189836A1 (en) * | 2020-03-25 | 2021-09-30 | 江西正拓新能源科技股份有限公司 | Graphite negative electrode material for high-performance lithium ion battery and preparation method therefor |
| CN113652699A (en) * | 2021-07-05 | 2021-11-16 | 南昌大学 | Method for improving activity of hydrogen production by electrocatalysis of graphene |
Non-Patent Citations (4)
| Title |
|---|
| BABAEI-SATI, RASOUL等: ""Electrogeneration of H2O2 using graphite cathode modified with electrochemically synthesized polypyrrole/MWCNT nanocomposite for electro-Fenton process"", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》, vol. 52, pages 270 - 276, XP085009569, DOI: 10.1016/j.jiec.2017.03.056 * |
| ZHANG, TONG等: ""Carbon charge population and oxygen molecular transport regulated by program-doping for highly efficient 4e-ORR"", 《CARBON CHARGE POPULATION AND OXYGEN MOLECULAR TRANSPORT REGULATED BY PROGRAM-DOPING FOR HIGHLY EFFICIENT 4E-ORR》, vol. 444, pages 136560 * |
| 徐夫元 等: ""氧还原合成过氧化氢电极的研究进展"", 《材料导报》, pages 32 - 35 * |
| 王以恒 等: ""杂原子掺杂碳材料用于电合成过氧化氢的研究进展"", 《环境化学》, pages 1 - 15 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114875430B (en) | 2024-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111604048B (en) | Method for synthesizing ammonia by electrocatalytic reduction of nitrogen and catalyst used in same | |
| CN113371693A (en) | Cobalt-nitrogen co-doped three-dimensional structure carbon material and preparation method and application thereof | |
| CN112501662B (en) | Preparation method of copper nanosheet applied to efficient carbon dioxide reduction reaction for generating methane | |
| CN110846678A (en) | Dual-function catalyst electrode for urea electrolysis-assisted hydrogen production by foam nickel load | |
| CN113136597B (en) | Copper-tin composite material and preparation method and application thereof | |
| CN108441885A (en) | A kind of composite material and its application in urea aoxidizes assistance Acid-Base electrolytic cell device for preparing hydrogen | |
| Liu et al. | A high-performance continuous-flow MEA reactor for electroreduction CO 2 to formate | |
| CN113026031A (en) | Electrode material, preparation method and application thereof, and assembled water electrolysis device | |
| CN110592616A (en) | Method for preparing platinum/titanium dioxide nanotube composite electrode by electroplating method | |
| CN111939914B (en) | Method for preparing high-activity ternary metal oxygen evolution catalyst by using waste copper foil | |
| CN110965075A (en) | Preparation and application of carbon dioxide electrochemical reduction electrode | |
| CN115537865B (en) | Application and preparation method of nanocrystallized foam silver electrode | |
| CN114875430B (en) | Graphite-based bifunctional electrosynthesis hydrogen peroxide catalytic material and preparation method thereof | |
| CN114959772B (en) | Long-life noble metal oxide oxygen evolution reaction electrocatalyst, preparation method and application | |
| CN113684499B (en) | Preparation method and application of nickel-nitrogen co-doped carbon-based catalyst with high metal loading efficiency | |
| CN114604850B (en) | Preparation method and application of porous microsphere carbon anode material | |
| CN112717980B (en) | Composite catalyst and preparation method and application thereof | |
| CN111593371B (en) | Municipal sludge multistage carbon material and application thereof in carbon dioxide electrochemical reduction | |
| CN113644284A (en) | Carbon material loaded fluorine-doped niobium carbide nano composite material and preparation method and application thereof | |
| CN112281185A (en) | Preparation method and application of hierarchical pore covalent organic framework compound and metal composite hydrogen evolution catalyst | |
| CN115020723B (en) | Ultrathin vanadium/nitrogen-doped carbon composite material and preparation method thereof | |
| CN114481160B (en) | Preparation method of CNT-Zn monoatomic catalytic material | |
| CN114990618B (en) | Preparation method and application of biomass carbon aerogel electrocatalytic deuterium separation material | |
| CN112191239B (en) | In-situ grown self-supporting nickel-oxygen co-doped carbon nanotube catalyst and preparation and application thereof | |
| CN117926307A (en) | Multifunctional seawater heterostructure catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |