CN113555569B - Catalyst precursor, metal carbon-based catalyst, and preparation methods and applications thereof - Google Patents
Catalyst precursor, metal carbon-based catalyst, and preparation methods and applications thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 109
- 239000002184 metal Substances 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 87
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000012018 catalyst precursor Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000000197 pyrolysis Methods 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000446 fuel Substances 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 150000004696 coordination complex Chemical class 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 8
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- -1 zeolite imidazole ester Chemical class 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical group 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical group [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 238000001035 drying Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 208000021251 Methanol poisoning Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst precursor, a metal carbon-based catalyst, and a preparation method and application thereof. The catalyst precursor is a mixture comprising a metal-doped zeolitic imidazolate framework material and an inorganic salt, or a mixture comprising a metal-doped zeolitic imidazolate framework material and a surfactant. The metal carbon-based catalyst is prepared by grinding a catalyst precursor, placing a ground product in an inert atmosphere for pyrolysis, then cooling the pyrolysis product, and carrying out ammonia treatment in the cooling process. The invention also provides a catalyst precursor, a preparation method and application of the metal carbon-based catalyst. The metal carbon-based catalyst prepared by the method has a sheet structure, a higher specific surface area, rich nanopores and defect active centers, more active sites are exposed, and the mass diffusion property of the metal carbon-based catalyst is improved, so that the metal carbon-based catalyst has excellent catalytic activity and stability.
Description
Technical Field
The invention relates to the technical field of catalysts. More particularly, to a catalyst precursor, a metal carbon-based catalyst, and a preparation method and application thereof.
Background
Energy crisis and environmental pollution limit global economic development, however, the widespread use of fossil energy not only exacerbates energy crisis, but also causes environmental pollution worldwide and global climate warming. Among the renewable energy sources, hydrogen energy sources with high combustion heat value, cleanness, no pollution, wide sources and wide application range are attracting attention of various countries, and for the world, the development of hydrogen energy sources can reestablish a set of high-efficiency energy systems and effectively alleviate the energy crisis and climate problems commonly faced by the world.
The fuel cell for converting hydrogen energy into electric energy is a device for directly converting chemical energy into electric energy, can be used as various fuel without discharging pollutant gas, has small noise in operation, only generates water after reaction, and almost does not generate nitrogen and sulfur oxides polluting environment. The reaction step of converting chemical energy into electric energy does not involve combustion process, so the energy conversion efficiency (up to 60% -80%) is not limited by the carnot cycle. At present, fuel cells are put into practical use, and the available energy efficiency of the fuel cells is found to be 2-3 times that of a common internal combustion engine.
Proton exchange membrane fuel cells, which are energy conversion devices, are the most developed fuel cells at present, and have advantages that make them ideal renewable energy utilization modes. The oxygen reduction reaction, which plays a key role in proton exchange membrane fuel cells, is subject to slow kinetics, and thus high performance catalysts are required to reduce its reaction energy barrier. Therefore, there is an urgent need for an efficient and desirable oxygen reduction catalyst, and application to fuel cells, which exhibits excellent performance.
Noble metal catalysts are still currently the most widely used catalysts in renewable energy technology and other important industrial processes. However, noble metal catalysts have various disadvantages such as lack of resources, high cost, poor stability, impurity poisoning and fuel crossover effects, and adverse effects on the environment.
Transition metal doped carbon-based electrocatalysts are considered to be the most promising materials for replacing noble metal catalysts because of their better stability and resistance to methanol poisoning. Among them, the monoatomic catalyst has received the most widespread attention due to its high intrinsic activity and maximum atom utilization efficiency. The cost of preparing single-atom catalysts is limited by expensive laboratory equipment requirements and low production efficiency. Therefore, developing a method for preparing non-noble metal single-or double-atom catalyst in large quantity with high efficiency, reliability, environmental protection and low cost would be of great significance in further industrial application.
Therefore, the invention provides a catalyst precursor, a metal carbon-based catalyst, and a preparation method and application thereof.
Disclosure of Invention
A first object of the present invention is to provide a catalyst precursor.
A second object of the present invention is to provide a method for preparing a catalyst precursor.
A third object of the present invention is to provide the use of a catalyst precursor.
A fourth object of the present invention is to provide a metal carbon-based catalyst.
A fifth object of the present invention is to provide a method for preparing a metal carbon-based catalyst.
A sixth object of the present invention is to provide the use of a metal carbon-based catalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalyst precursor that is a mixture comprising a metal-doped zeolitic imidazolate framework material and an inorganic salt, or a mixture comprising a metal-doped zeolitic imidazolate framework material and a surfactant; wherein the mass ratio of the inorganic salt to the metal doped zeolite imidazole ester framework material is 2.70:0.67 to 5.40.
In the catalyst precursor provided by the invention, atoms of the zeolite imidazole ester framework material doped with metal are arranged periodically, so that in the process of preparing the metal carbon-based catalyst by using the catalyst precursor, the volatilization of zinc element prevents agglomeration of the metal element, the metal element and the nitrogen element are uniformly distributed in the material, the content is controllable, and the regulation and control of doping are beneficial to the generation of single-atom active sites or double-atom active sites.
In the catalyst precursor, the inorganic salt is used as a domain limiter and an etchant in the preparation process of the metal carbon-based catalyst, and the generated carbide is in a three-dimensional porous shape and has a rich lamellar structure at the edge by utilizing the intercalation and stripping actions of the inorganic salt in the pyrolysis process, so that more mesopores are generated.
In the catalyst precursor provided by the invention, the surfactant is used as a pore-forming agent in the process of preparing the metal carbon-based catalyst, and the metal doped zeolite imidazole ester framework material constructs more pore structures under the action of the surfactant, so that the specific surface area and the porosity of the material are increased, more single-atom active sites are exposed, the transmission of protons and electrons is promoted, and the electrocatalytic performance is effectively improved; different surfactants in the catalyst precursor can have different effects on the formation of the metal carbon-based catalyst, and are beneficial to analyzing the influence of the structure on the oxygen reduction performance.
Preferably, the metal in the metal-doped zeolitic imidazolate framework material is a transition metal; further, the transition metal is iron.
Preferably, the inorganic salt is a sodium salt; further, the sodium salt is sodium chloride.
Preferably, the surfactant is P123.
In a second aspect, the present invention provides a method for preparing a catalyst precursor, comprising the steps of:
firstly, performing ball milling on inorganic salt or surfactant, and then adding zinc oxide, dimethyl imidazole and metal-containing complex solution for ball milling to prepare the catalyst precursor.
Preferably, the mass ratio of the inorganic salt or the surfactant, the zinc oxide, the dimethyl imidazole and the metal-containing complex solution is 700-900:60-90:150-170:40-60, and more preferably 800:81.38:164.2:50.72.
preferably, the inorganic salt is ball-milled for 20 to 60 minutes.
Preferably, the time for ball milling by adding zinc oxide, dimethyl imidazole and metal complex-containing solution is 30-60 minutes.
Preferably, the metal-containing complex in the metal-containing complex solution is a single metal complex or a multi-metal complex.
Preferably, the monometal complex is formed by complexing iron salt A and phenanthroline in a molar ratio of 1-3:6.
Preferably, the iron salt a is ferrous acetate.
Preferably, the bimetallic complex is formed by complexing iron salt B and cobalt salt in a molar ratio of 3-5:1.
Preferably, the iron salt B is iron acetylacetonate.
Preferably, the cobalt salt is cobalt nitrate hexahydrate.
Preferably, the solvent in the metal complex-containing solution is absolute ethanol.
Preferably, the preparation method of the catalyst precursor further comprises the steps of washing and drying ball-milling products after ball milling by adding zinc oxide, dimethyl imidazole and metal complex-containing solution.
Preferably, the detergent used for the washing is an alcohol, more preferably ethanol; in the invention, the alcohol can wash out superfluous metal complex; the alcohol is methanol or ethanol, wherein the ethanol is less toxic than the methanol and is more suitable for preparing the synthetic catalyst precursor on a large scale.
Preferably, the drying condition is that the drying is carried out under the vacuum condition, the drying temperature is 70-90 ℃, and the drying time is 12-24 hours; further, the drying temperature was 80 ℃.
In a third aspect, the present invention provides the use of a catalyst precursor in the preparation of a metal carbon-based catalyst.
In a fourth aspect, the invention provides a metal carbon-based catalyst, which is prepared by grinding the precursor of the catalyst, placing the ground product in an inert atmosphere for pyrolysis, and then cooling the pyrolysis product and performing ammonia treatment in the cooling process.
Preferably, the metal carbon-based catalyst includes Fe element, N element, O element, and C element.
Preferably, in the metal carbon-based catalyst, the ratio of the Fe element is 1.12at%, the ratio of the N element is 8.7at%, the ratio of the O element is 4.53at%, and the ratio of the C element is 85.66at%.
Preferably, the metal carbon-based catalyst is in a three-dimensional porous structure, and the edge is in a nano sheet structure.
Preferably, the saidThe specific surface area of the metal carbon-based catalyst is 1200-1400 m 2 g -1 Further preferably 1376.8m 2 g -1 。
Preferably, the metal carbon-based catalyst has a structural mesopore of 25 to 40%, and more preferably 30.47%.
Preferably, the metal in the metal carbon-based catalyst is iron.
In a fifth aspect, the present invention provides a method for preparing a metal carbon-based catalyst, comprising the steps of:
grinding the catalyst precursor, placing the ground product in inert atmosphere for pyrolysis, then cooling the pyrolysis product, and treating with ammonia gas in the cooling process to obtain the metal carbon-based catalyst.
Preferably, the catalyst precursor is milled for 20-30 min.
Preferably, the inert gas used in the inert atmosphere is nitrogen or argon, and the purity of the inert gas is more than or equal to 99.999% (V/V).
Preferably, the equipment used for pyrolysis is a high temperature tube furnace.
Preferably, the pyrolysis process comprises: heating to 200-400 ℃ at a speed of 2-10 ℃/min, and preserving heat for 0.5-2 h; then heating to 800-1100 ℃ at the speed of 2-10 ℃/min, and preserving heat for 2-4 h.
Preferably, the cooling process includes: cooling to 700-900 ℃ at the speed of 2-10 ℃/min, preserving heat for 5-10 min, stopping introducing inert gas, simultaneously introducing ammonia at the speed of 60-80 ml/min, stopping introducing ammonia and simultaneously introducing inert gas at the speed of 60-150 ml/min after finishing preserving heat for 5-20 min, and automatically cooling to normal temperature.
Preferably, the pyrolysis product is cooled to obtain a product which also needs washing, filtering and drying steps; wherein, the washing is ultrasonic washing for 30-60 min by using deionized water, thereby removing redundant inorganic salt or other impurities; the filtering is suction filtration for 3 to 6 hours; the drying is carried out for 10 to 16 hours under vacuum condition.
In a sixth aspect, the present invention provides the use of a metal carbon-based catalyst in the preparation of a zinc-air cell or fuel cell.
Any range recited in the present invention includes any numerical value between the end values and any sub-range formed by any numerical value between the end values or any numerical value between the end values unless specifically stated otherwise.
The beneficial effects of the invention are as follows:
(1) The components in the catalyst precursor provided by the invention are matched with each other to generate a synergistic effect in the preparation process of the metal carbon-based catalyst, so that the prepared metal carbon-based catalyst has a sheet structure, a higher specific surface area, rich nanopores and defect active centers and more active sites are exposed.
(2) The preparation method of the catalyst precursor provided by the invention adopts a one-step ball milling method, can prepare in large quantity, has a simple process, is not easy to introduce other impurities, and is beneficial to regulating and controlling the distribution and the content of doped metal elements in the metal doped zeolite imidazole ester framework material.
(3) The metal carbon-based catalyst provided by the invention has a three-dimensional porous structure, and the edge of the catalyst is of a nano sheet structure, so that the catalyst has a larger specific surface area.
(4) The preparation method of the metal carbon-based catalyst provided by the invention adopts the catalyst precursor provided by the invention for preparation, so that the mass diffusion property of the metal carbon-based catalyst is improved, and the metal carbon-based catalyst has excellent catalytic activity and stability.
(5) The preparation method of the metal carbon-based catalyst provided by the invention has the advantages of simple steps, readily available raw materials, low cost, environment friendliness and easiness in large-scale production.
(6) The metal carbon-based catalyst provided by the invention has outstanding oxygen reduction catalytic performance, methanol resistance and outstanding stability, and simultaneously has good performance in oxyhydrogen fuel cells and renewable fuel cell equipment, and has wide application prospects.
(7) The invention adopts a simple synthesis method to prepare the oxygen reduction carbon-based catalyst doped with single metal atoms, provides a new thought for preparing the single-atom oxygen reduction catalyst in a large quantity, also provides a new scheme for constructing the high-efficiency electrocatalyst, and can open up a new way for developing renewable energy conversion and storage equipment.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 shows the metal carbon based catalysts prepared in example 2, example 6 and example 8 at 0.1M HClO 4 Linear sweep voltammogram of the oxygen reduction reaction below.
FIG. 2 shows a scanning electron microscope image of the metal carbon-based catalyst prepared in example 2.
Fig. 3 shows a transmission electron microscopic image of the metal carbon-based catalyst prepared in example 2.
Fig. 4 shows a high angle annular dark field image of the metal carbon based catalyst prepared in example 2.
FIG. 5 shows a graph of 25000s current versus time stability for the metal carbon based catalyst prepared in example 2.
FIG. 6 shows the application of the metal-carbon-based catalyst prepared in example 2 to H 2 /O 2 Discharge polarization curve and power density curve of fuel cell.
Fig. 7 shows a product map of the catalyst precursor prepared in example 1.
FIG. 8 shows a product map of the metal carbon-based catalyst prepared in example 2.
FIG. 9 shows a scanning electron microscope image of the metal carbon-based catalyst prepared in example 6.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
In the invention, the preparation methods are all conventional methods unless specified; the starting materials used are available commercially from the public sources unless otherwise specified; the percentages are mass percentages unless otherwise specified.
The following is a further explanation of the present invention by way of examples.
Example 1
The embodiment provides a preparation method of a catalyst precursor, which comprises the following steps:
1) 800g of sodium chloride is added into a ball milling tank, and ball milling is carried out for 30 minutes at a rotating speed of 400 rpm;
2) 12.34g of ferrous acetate (Fe (Ac) 2 ) And 38.38g of phenanthroline (molar ratio 1: 3) Dissolving in 200ml ethanol, and performing ultrasonic treatment for 30 minutes to form a metal complex-containing solution;
3) 81.38g of zinc oxide, 164.2g of 2-methylimidazole and the metal-containing complex solution obtained in the step 2) were charged into a ball mill pot, and ball-milled in the ball mill for 60 minutes to obtain a product, which was transferred to a filtration apparatus, washed by filtration with 30L of ethanol until the supernatant became colorless, and then dried in a vacuum drying oven at 80℃for 24 hours to obtain a catalyst precursor, as shown in FIG. 7.
Example 2
The embodiment provides a preparation method of a metal carbon-based catalyst, which comprises the following steps:
1) 1000g of the catalyst precursor prepared in example 1 was ground with a mortar for 30 minutes to form a powder, put into a porcelain boat, put into a quartz tube, and pyrolyzed in a high-temperature tube furnace; in the pyrolysis process, argon with the flow of 100mL/min is introduced to be more than or equal to 99.999% (V/V), a high-temperature tube furnace is heated to 250 ℃ at the speed of 3 ℃/min and is kept at the temperature for pyrolysis for 1 hour, then the temperature is further increased to 900 ℃ at the heating speed of 5 ℃/min, the temperature is kept at the pyrolysis temperature for 3 hours, and the whole pyrolysis process is carried out under the protection of argon atmosphere;
2) Cooling after the pyrolysis process is finished, closing argon when the temperature is reduced to 800 ℃, introducing ammonia with the flow of 70mL/min, keeping the temperature of a tube furnace at 800 ℃ for 8 minutes, naturally cooling to obtain a product, transferring the product into a flask, adding 1000mL of deionized water, carrying out ultrasonic treatment for 50 minutes, filtering and washing, and then drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain the metal carbon-based catalyst, as shown in figure 8.
FIG. 2 shows a scanning electron microscope image of the metal carbon-based catalyst prepared in example 2. As can be seen in a typical scanning electron microscope schematic diagram 2, the metal carbon-based catalyst prepared in the example 2 contains a significant sheet structure, a large-scale sheet structure in some areas is removed, and in a three-dimensional porous structure formed in other areas, the outer edges of the material are sheet-shaped, and some sheets have a curling phenomenon. These sheet-like structures are interconnected to form a continuous porous three-dimensional structure. The presence of a large number of macropores can also be clearly seen in large-scale continuous sheet structures.
Fig. 3 shows a transmission electron microscope image of the metal carbon-based catalyst prepared in example 2, and it can be seen that the edge of the metal carbon-based catalyst has an ultrathin sheet structure (the electron microscope image is very transparent), which accords with the characterization result of the scanning electron microscope.
Fig. 4 shows a high angle annular dark field image of the metal carbon based catalyst prepared in example 2. The bright spots coming out of the white circles correspond to highly dispersed single iron atoms, as iron atoms are heavier than carbon and nitrogen atoms. And has a particle size of about 0.2 nm.
Example 3
The embodiment provides an oxidation-to-oxidation reaction of a metal carbon-based catalyst, comprising the steps of:
electrochemical testing was performed at room temperature using an electrochemical workstation (Autolab) under a three-electrode system. Graphite rod and Ag/AgCl (KCl-saturated) electrode were used as counter electrode and reference electrode, respectively, and the working electrode was a glassy carbon rotary disk electrode (area of 0.196cm 2 ). The glassy carbon rotary disk electrode was polished with 0.05 μm alumina slurry and then rinsed with ultrapure water. In each test, 5mg of the metal carbon-based catalyst prepared in example 2, example 6 and example 8 was mixed with 10. Mu.L of Nafion solution (5 wt%), 495. Mu.L of isopropyl alcohol and 495. Mu.L of ultrapure water, respectively, and then ultrasonically dispersed for about 30 minutes to form a uniform ink, and 20. Mu.L of ink droplets were collected in separate portions on the surface of a rotating disk electrode and dried under ambient conditions. The mass load of the metal carbon-based catalyst is 0.5mg cm -2 . At oxygen saturation of 0.1MHClO 4 Linear Sweep Voltammetry (LSV) test was performed. In the test process, high-purity oxygen is continuously introduced into the electrolyte to keep the oxygen saturated state, and the scanning speed is highAt a rate of 5mV s -1 The oxygen reduction performance of the metal carbon based catalyst was tested at a spin rate of 1600 revolutions, from 1.0V scan to 0V (versus reversible hydrogen electrode).
FIG. 1 shows the metal carbon based catalysts prepared in example 2, example 6 and example 8 at 0.1M HClO 4 Linear sweep voltammogram of the oxygen reduction reaction below. The test shows that the initial potential of the metal carbon-based catalyst prepared in the example 2 is 0.951V, the half-wave potential is 0.820V, and the limiting current density is 5.68mA/cm 2 . The metal carbon-based catalyst prepared in example 6 had an initial potential of 0.912V, a half-wave potential of 0.775V and a limiting current density of 5.67mA/cm 2 . The metal carbon-based catalyst prepared in example 8 had an initial potential of 0.932V, a half-wave potential of 0.801V and a limiting current density of 5.32mA/cm 2 。
FIG. 5 shows a graph of 25000s current versus time stability for the metal carbon based catalyst prepared in example 2. The performance loss rate of the 25000s current-time stability test is only 6%, and the prepared metal carbon-based catalyst has excellent stability.
Example 4
This example provides a metal carbon based catalyst in H 2 /O 2 An application in a fuel cell comprising the steps of:
H 2 /O 2 fuel cell testing was performed in single cell fuel cells with direct parallel flow channels. In each test, the metal carbon-based catalyst prepared in example 2 was dispersed in a solution of water and isopropyl alcohol (1:8 v/v), and an ultrasonic dispersion was performed to prepare a uniform catalyst ink, and then the catalyst ink was sprayed to one side of NC700 film with a spray gun, and the area of the fabricated film electrode was 5cm -2 Forming catalyst load of 2mg cm -2 And serves as a cathode. Catalyst coated membranes (-0.20 mg) prepared using the same process on the other side using 40% commercial platinum carbon catalyst Pt cm -2 ) As an anode. The membrane electrode assembly was assembled into a fuel cell and the membrane electrode assembly thus prepared was then evaluated at 80 ℃,100% Relative Humidity (RH) and a back pressure of 2.0 bar. 500mL min -1 Is 500m and pure hydrogen of (2)L min -1 Is continuously supplied to the anode and cathode, respectively, during the test. The polarization curve of the fuel cell was recorded in the voltage control mode.
FIG. 6 shows the application of the metal-carbon-based catalyst prepared in example 2 to H 2 /O 2 Discharge polarization curve and power density curve of fuel cell. The metal carbon-based catalyst prepared in example 2 was assembled into a membrane electrode to test the practical performance of the catalyst in proton membrane hydrogen-oxygen fuel cells, the anode HOR catalyst was 40% Pt/C, and the loading was 1mg/cm 2 The proton membrane is DuPont 212 membrane, the temperature is 80 ℃, the hydrogen flow is 0.2L/min, the oxygen flow is 0.2L/min, and the relative humidity is 100%. The fuel cell had an open circuit voltage of 1.0V and a maximum power of 610mW/cm at a back pressure of 2 atm 2 。
Example 5
The embodiment provides a preparation method of a catalyst precursor, which comprises the following steps:
1) 12.34g of ferrous acetate (Fe (Ac) 2 ) And 38.38g of phenanthroline (molar ratio 1: 3) Dissolving in 200ml ethanol, adding 74.0g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), and performing ultrasonic treatment for 30 minutes to form a metal complex-containing solution;
2) 81.38g of zinc oxide, 164.2g of 2-methylimidazole and the metal-containing complex solution obtained in step 1) were charged into a ball mill, and ball-milled in the ball mill for 60 minutes to obtain a product, which was transferred to a filtration apparatus, washed by filtration with 30L of ethanol until the supernatant became colorless, and then dried in a vacuum drying oven at 80℃for 24 hours to obtain a catalyst precursor.
Example 6
The embodiment provides a preparation method of a metal carbon-based catalyst, which comprises the following steps:
1) 1000g of the catalyst precursor prepared in example 5 was ground with a mortar for 30 minutes to form a powder, put into a porcelain boat, put into a quartz tube, and pyrolyzed in a high-temperature tube furnace; in the pyrolysis process, argon with the flow of 100mL/min is introduced to be more than or equal to 99.999% (V/V), a high-temperature tube furnace is heated to 250 ℃ at the speed of 3 ℃/min and is kept at the temperature for pyrolysis for 1 hour, then the temperature is further increased to 900 ℃ at the heating speed of 5 ℃/min, the temperature is kept at the pyrolysis temperature for 3 hours, and the whole pyrolysis process is carried out under the protection of argon atmosphere;
2) Cooling after the pyrolysis process is finished, closing argon when the temperature is reduced to 800 ℃, introducing ammonia with the flow of 70mL/min, keeping the temperature of a tube furnace at 800 ℃ for 8 minutes, naturally cooling to obtain a product, transferring the product into a flask, adding 1000mL of deionized water, carrying out ultrasonic treatment for 50 minutes, filtering and washing, and then drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain the metal carbon-based catalyst.
FIG. 9 shows a scanning electron microscope image of the metal carbon-based catalyst prepared in example 6, in the form of particles, containing a pronounced regular dodecahedral morphology of ZIF-8.
Example 7
The embodiment provides a preparation method of a catalyst precursor, which comprises the following steps:
1) 800g of sodium chloride is added into a ball milling tank, and ball milling is carried out for 30 minutes at a rotating speed of 400 rpm;
2) 24.08g of iron acetylacetonate and 4.96g of cobalt nitrate hexahydrate (molar ratio 4: 1) Dissolving in 100ml ethanol, and performing ultrasonic treatment for 30 minutes to form a metal complex-containing solution;
3) 20.80g of zinc oxide, 164.2g of 2-methylimidazole and the metal-containing complex solution obtained in the step 2) were charged into a ball mill pot, and ball-milled in the ball mill for 60 minutes to obtain a product, which was transferred to a filter unit, filtered and washed with 30L of ethanol until the supernatant became colorless, and then dried in a vacuum drying oven at 80℃for 24 hours to obtain a catalyst precursor.
Example 8
The embodiment provides a preparation method of a metal carbon-based catalyst, which comprises the following steps:
1) 1000g of the catalyst precursor prepared in example 7 was ground with a mortar for 30 minutes to form a powder, put into a porcelain boat, put into a quartz tube, and pyrolyzed in a high-temperature tube furnace; in the pyrolysis process, argon with the flow of 100mL/min is introduced to be more than or equal to 99.999% (V/V), the high-temperature tube furnace is heated to 950 ℃ at the speed of 5 ℃/min and is kept at the temperature for pyrolysis for 2 hours, then the temperature is further increased to 900 ℃ at the heating speed of 5 ℃/min, and the temperature is kept at the pyrolysis temperature for 3 hours, and the whole pyrolysis process is carried out under the protection of argon atmosphere;
2) Cooling after the pyrolysis process is finished, closing argon when the temperature is reduced to 800 ℃, introducing ammonia with the flow of 70mL/min, keeping the temperature of a tube furnace at 800 ℃ for 8 minutes, naturally cooling to obtain a product, transferring the product into a flask, adding 1000mL of deionized water, carrying out ultrasonic treatment for 50 minutes, filtering and washing, and then drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain the metal carbon-based catalyst.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (23)
1. A catalyst precursor, characterized in that the catalyst precursor is a mixture comprising a metal-doped zeolitic imidazolate framework material and an inorganic salt, or a mixture comprising a metal-doped zeolitic imidazolate framework material and a surfactant; wherein the mass ratio of the inorganic salt to the metal doped zeolite imidazole ester framework material is 2.70:0.67 to 5.40; the metal in the metal doped zeolite imidazole ester framework material is transition metal; the inorganic salt is sodium salt; the sodium salt is sodium chloride; the surfactant is P123.
2. The catalyst precursor of claim 1, wherein the transition metal is iron.
3. A method for preparing the catalyst precursor according to claim 1 or 2, comprising the steps of:
and (3) ball-milling inorganic salt or surfactant, and then adding zinc oxide, dimethyl imidazole and metal-containing complex solution for ball-milling to obtain the catalyst precursor.
4. The method for preparing a catalyst precursor according to claim 3, wherein the mass ratio of the inorganic salt or surfactant, zinc oxide, dimethyl imidazole and metal-containing complex solution is 700 to 900:60 to 90:150 to 170:40 to 60.
5. The method for preparing a catalyst precursor according to claim 3, wherein the inorganic salt or the surfactant is ball-milled for 20 to 60 minutes.
6. The method for preparing a catalyst precursor according to claim 3, wherein the time for ball milling by adding zinc oxide, dimethyl imidazole and metal-containing complex solution is 30 to 60 minutes.
7. The method for producing a catalyst precursor according to claim 3, wherein the metal-containing complex in the metal-containing complex solution is a single metal complex or a multi-metal complex.
8. The method for preparing a catalyst precursor according to claim 7, wherein the monometal complex is formed by complexing iron salt a and phenanthroline in a molar ratio of 1-3:6.
9. The method for preparing a catalyst precursor according to claim 8, wherein the iron salt a is ferrous acetate.
10. The method for preparing a catalyst precursor according to claim 7, wherein the multi-metal complex is formed by complexing an iron salt B and a cobalt salt in a molar ratio of 3-5:1.
11. The method for preparing a catalyst precursor according to claim 10, wherein said iron salt B is iron acetylacetonate.
12. The method of preparing a catalyst precursor according to claim 10, wherein the cobalt salt is cobalt nitrate hexahydrate.
13. The method for producing a catalyst precursor according to claim 3, wherein the solvent in the metal-containing complex solution is absolute ethanol.
14. Use of the catalyst precursor according to claim 1 or 2 or the catalyst precursor prepared by the method of preparing the catalyst precursor according to any one of claims 3 to 13, for preparing a metal carbon-based catalyst.
15. A metal carbon-based catalyst, characterized in that the metal carbon-based catalyst is produced by grinding the catalyst precursor according to claim 1 or 2 or the catalyst precursor produced by the method for producing a catalyst precursor according to any one of claims 3 to 13, placing the ground product in an inert atmosphere for pyrolysis, then cooling the pyrolysis product, and treating ammonia gas during the cooling.
16. The metal carbon-based catalyst of claim 15, wherein the metal in the metal carbon-based catalyst is iron.
17. A method for preparing the metal carbon-based catalyst according to claim 15 or 16, comprising the steps of:
grinding the catalyst precursor according to claim 1 or 2 or the catalyst precursor prepared by the preparation method of the catalyst precursor according to any one of claims 3 to 13, placing the ground product in an inert atmosphere for pyrolysis, and then cooling the pyrolysis product, wherein ammonia is used for treatment in the cooling process to prepare the metal carbon-based catalyst.
18. The method for preparing a metal carbon-based catalyst according to claim 17, wherein the catalyst precursor is ground for 20 to 30 minutes.
19. The method for preparing a metal carbon-based catalyst according to claim 17, wherein the inert gas used in the inert atmosphere is nitrogen or argon, and the purity of the inert gas is not less than 99.999% (V/V).
20. The method for preparing a metal carbon-based catalyst according to claim 17, wherein the equipment used for pyrolysis is a high-temperature tube furnace.
21. The method of preparing a metal carbon-based catalyst according to claim 17, wherein the pyrolysis process comprises: heating to 200-400 ℃ at a speed of 2-10 ℃/min, and preserving heat for 0.5-2 h; then heating to 800-1100 ℃ at the speed of 2-10 ℃/min, and preserving heat for 2-4 h.
22. The method for preparing a metal carbon-based catalyst according to claim 17, wherein the cooling process comprises: cooling to 700-900 ℃ at the speed of 2-10 ℃/min, preserving heat for 5-10 min, stopping introducing inert gas, simultaneously introducing ammonia at the speed of 60-80 ml/min, stopping introducing ammonia and simultaneously introducing inert gas at the speed of 60-150 ml/min after finishing preserving heat for 5-20 min, and automatically cooling to normal temperature.
23. Use of a metal carbon-based catalyst according to claim 15 or 16 or a metal carbon-based catalyst prepared by a method according to any one of claims 17 to 22 for the preparation of a zinc-air cell or fuel cell.
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