CN115036517B - Graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, preparation method thereof, air electrode and fuel cell - Google Patents
Graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, preparation method thereof, air electrode and fuel cell Download PDFInfo
- Publication number
- CN115036517B CN115036517B CN202210508480.7A CN202210508480A CN115036517B CN 115036517 B CN115036517 B CN 115036517B CN 202210508480 A CN202210508480 A CN 202210508480A CN 115036517 B CN115036517 B CN 115036517B
- Authority
- CN
- China
- Prior art keywords
- metalloporphyrin
- oxygen reduction
- graphene aerogel
- graphene
- reduction catalyst
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000001301 oxygen Substances 0.000 title claims abstract description 75
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 75
- 239000004964 aerogel Substances 0.000 title claims abstract description 74
- 230000009467 reduction Effects 0.000 title claims abstract description 70
- 239000000446 fuel Substances 0.000 title claims abstract description 38
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006722 reduction reaction Methods 0.000 claims abstract description 79
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 238000000197 pyrolysis Methods 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims abstract description 12
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 16
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 150000004032 porphyrins Chemical class 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000000243 solution Substances 0.000 description 30
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229920000557 Nafion® Polymers 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- GMKGPTICAQPUJH-UHFFFAOYSA-N c1cc2cc3ccc(cc4ccc(cc5ccc(cc1n2)[nH]5)n4)[nH]3.c1ccc(cc1)[Co](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound c1cc2cc3ccc(cc4ccc(cc5ccc(cc1n2)[nH]5)n4)[nH]3.c1ccc(cc1)[Co](c1ccccc1)(c1ccccc1)c1ccccc1 GMKGPTICAQPUJH-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 cobalt nitride Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000003993 interaction Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 229910020676 Co—N Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000037303 wrinkles Effects 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
- H01M4/88—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
-
- 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
- H01M4/9008—Organic or organo-metallic compounds
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, a preparation method thereof, an air electrode and a fuel cell. The preparation method provided by the invention comprises the following steps: a) Under the action of an N-containing reducing agent, heating the aqueous dispersion of graphene oxide to perform a reduction reaction, and then washing and drying to obtain graphene aerogel; b) Dissolving 5,10,15, 20-tetraphenyl cobalt porphyrin and 5,10,15, 20-tetraphenyl porphyrin in an organic solvent to obtain a metalloporphyrin solution; c) Immersing the graphene aerogel in the metalloporphyrin solution for adsorption, and then taking out and drying to obtain a composite precursor; d) Carrying out pyrolysis treatment on the composite precursor to obtain a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst; the steps a) and b) are not limited in order. The catalyst has high-efficiency oxygen reduction catalytic performance, and can improve half-wave potential of oxygen reduction reaction and output power of a battery.
Description
Technical Field
The invention relates to the field of energy materials, in particular to a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, a preparation method thereof, an air electrode and a fuel cell.
Background
Since the industrial revolution, fossil energy has become a development proposition of the current human society, plays an important role in the aspects of our lives, and the development of our clothing, eating, living, going and cities is based on fossil energy. Traditional fossil energy sources have the defects of high pollution, low efficiency, unsustainability and the like, do not meet the strategic targets of sustainable development of human society, such as global warming, which is one of side effects of social development, and the emission of greenhouse gases causing global warming mainly comes from the transportation industry and power generation devices. There is therefore an effort to find clean, environmentally friendly, efficient and sustainable energy sources and energy conversion devices. While high capacity energy systems, such as fuel cells, metal-air batteries, etc., are highly promising for meeting the stringent demands for electric vehicles and sustainable energy utilization.
The chemical energy is converted into electric energy through electrochemical oxidation and reduction, the process can efficiently utilize energy, and the oxygen reduction reaction is a step-by-step in the fuel cell, so that the oxygen reduction reaction catalyst becomes a critical material of the device. At present, two types of catalysts, namely platinum-series catalysts and non-platinum-series catalysts, are mainly used, and the platinum-series catalysts are rare in platinum reserve, high in price, poor in stability and easy to poison. Therefore, the replacement of platinum-based catalysts with non-platinum-based catalysts, which are low in research price and excellent in properties, is a currently popular research direction.
Disclosure of Invention
In view of the above, the present invention aims to provide a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, a preparation method thereof, an air electrode and a fuel cell. The oxygen reduction catalyst provided by the invention has high-efficiency oxygen reduction catalytic performance, and can improve half-wave potential and output power of the fuel cell.
The invention provides a preparation method of a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, which comprises the following steps:
a) Under the action of an N-containing reducing agent, heating the aqueous dispersion of graphene oxide to perform a reduction reaction, and then washing and drying to obtain graphene aerogel;
b) Dissolving 5,10,15, 20-tetraphenyl cobalt porphyrin and 5,10,15, 20-tetraphenyl porphyrin in an organic solvent to obtain a metalloporphyrin solution;
c) Immersing the graphene aerogel in the metalloporphyrin solution for adsorption, and then taking out and drying to obtain a composite precursor;
d) Carrying out pyrolysis treatment on the composite precursor to obtain a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst;
the steps a) and b) are not limited in order.
Preferably, in the step a), the N-containing reducing agent is one or more selected from ethylenediamine, dopamine and urea.
Preferably, in the step a), the temperature is raised to 85-100 ℃, and the reaction is performed for 6-10 hours after the temperature is raised.
Preferably, in the step b), the organic solvent is selected from one or more of chloroform, dichloromethane and N, N-dimethylformamide.
Preferably, in the step d), the pyrolysis temperature is 800 to 1000 ℃.
Preferably, in the step a), the mass ratio of the N-containing reducing agent to the graphene oxide in the graphene oxide aqueous dispersion is (36-792) to 40;
the concentration of the graphene oxide aqueous dispersion liquid is 1-4 mg/mL.
Preferably, in the step b), the molar ratio of the 5,10,15, 20-tetraphenylcobalt porphyrin to the 5,10,15, 20-tetraphenylporphyrin is 1: (1-2.5).
The invention also provides a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst prepared by the preparation method.
The invention also provides an air electrode, which comprises a matrix and a catalyst supported on the matrix, wherein the catalyst is the graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst in the technical scheme.
The invention also provides a fuel cell, and the air electrode in the fuel cell is the air electrode in the technical scheme.
According to the preparation method, a certain amount of nitrogen-doped graphene aerogel is prepared, and the graphene aerogel is adopted to adsorb metalloporphyrin dissolved in chloroform for active site loading to prepare the oxygen reduction catalyst. The graphene aerogel is oleophilic, the contact angle of the graphene aerogel to chloroform is close to 0 degrees, and the graphene aerogel can adsorb impregnating solution with 130 times of the self weight, so that sufficient metalloporphyrin can be loaded. The graphene aerogel has the advantages of lipophilicity, strong adsorptivity and an internally porous structure, and can effectively load active sites. At the same time tetraphenyl cobalt porphyrin Co-N 4 The structure provides an active site. The pi-pi interaction of tetraphenylporphyrin and tetraphenylcobalt porphyrin plays a role in protecting and dispersing central metal, and the cobalt nitride is preferentially generated, so that the catalytic performance and the catalytic stability of the tetraphenylcobalt porphyrin are further improved.
The test result shows that the oxygen reduction catalyst of the invention has high-efficiency oxygen reduction electrochemical performance and stability, so that the half-wave potential of the oxygen reduction electrochemical reaction reaches more than 0.86V vs. RHE, and the oxygen reduction catalyst is superior to commercial platinum carbon Pt/C (0.84V) under the same condition; assembled into a zinc-air battery, the open-circuit voltage of which reaches more than 1.50V and is superior to commercial platinum carbon Pt/C (1.46V) under the same conditions; the maximum output power of the battery was 96mW/cm 2 Under equivalent conditions, better than 20wt% of commercial platinum carbon (maximum output power 78mW/cm 2 )。
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the graphene aerogel obtained in step S1 of example 1;
FIG. 2 is an SEM image of an oxygen reduction catalyst obtained in example 1;
FIG. 3 is a graph of linear voltammograms of the CoTPP/TPP-RGO oxygen reduction catalyst obtained in example 1;
FIG. 4 is a graph showing the linear voltammogram of the CoTPP/TPP-RGO oxygen reduction catalyst obtained in example 1 at various rotational speeds (400-2025 rpm);
FIG. 5 is a graph of open circuit voltage for a zinc-air fuel cell of example 3;
FIG. 6 is a polarization graph of a zinc-air fuel cell of example 3;
FIG. 7 is a graph of linear voltammograms of the CoTPP/TPP-RGO oxygen reduction catalyst obtained in example 4;
FIG. 8 is a graph of open circuit voltage for a zinc-air fuel cell of example 4;
FIG. 9 is a polarization graph of the zinc-air fuel cell of example 4;
FIG. 10 is a graph of linear voltammograms of the CoTPP/TPP-RGO oxygen reduction catalyst obtained in example 5;
FIG. 11 is a graph of open circuit voltage for a zinc-air fuel cell of example 5;
fig. 12 is a polarization graph of the zinc-air fuel cell of example 5.
Detailed Description
The invention provides a preparation method of a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, which comprises the following steps:
a) Under the action of an N-containing reducing agent, heating the aqueous dispersion of graphene oxide to perform a reduction reaction, and then washing and drying to obtain graphene aerogel;
b) Dissolving 5,10,15, 20-tetraphenyl cobalt porphyrin and 5,10,15, 20-tetraphenyl porphyrin in an organic solvent to obtain a metalloporphyrin solution;
c) Immersing the graphene aerogel in the metalloporphyrin solution for adsorption, and then taking out and drying to obtain a composite precursor;
d) Carrying out pyrolysis treatment on the composite precursor to obtain a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst;
the steps a) and b) are not limited in order.
According to the preparation method, a certain amount of nitrogen-doped graphene aerogel is prepared, and the graphene aerogel is adopted to adsorb metalloporphyrin dissolved in chloroform for active site loading to prepare the oxygen reduction catalyst. The graphene aerogel is oleophilic, the contact angle of the graphene aerogel to chloroform is close to 0 degrees, and 50mg of graphene aerogel can adsorb impregnating solution with the weight 130 times of that of the graphene aerogel, so that sufficient metalloporphyrin can be loaded. The graphene aerogel has the advantages of lipophilicity, strong adsorptivity and an internally porous structure, and can effectively load active sites. At the same time tetraphenyl cobalt porphyrin Co-N 4 The structure provides an active site. The pi-pi interaction of tetraphenylporphyrin and tetraphenylcobalt porphyrin plays a role in protecting and dispersing central metal, and the cobalt nitride is preferentially generated, so that the catalytic performance and the catalytic stability of the tetraphenylcobalt porphyrin are further improved.
[ about step a ]:
a) And under the action of an N-containing reducing agent, heating the aqueous dispersion of graphene oxide to perform a reduction reaction, and then washing and drying to obtain the graphene aerogel.
In the present invention, the concentration of the aqueous dispersion of graphene oxide is preferably 1 to 4mg/mL, and specifically may be 1mg/mL, 2mg/mL, 3mg/mL, or 4mg/mL.
In the present invention, the N-containing reducing agent is a reducing agent containing nitrogen, preferably one or more of ethylenediamine, dopamine and urea, and more preferably ethylenediamine. By adopting the reducing agent, the oxygen-containing functional groups on the graphene oxide sheets can be reduced, so that the graphene oxide can recover the sp of the graphene 2 And (3) hybridizing the structure to generate a ring-opening reaction, and connecting the graphene sheets to form aerogel. The catalyst performance can be improved most when ethylenediamine is adopted, and the ethylenediamine can oxidize graphene sheetsThe oxygen-containing functional group of (2) is reduced, so that GO gradually recovers sp of graphene in the process of being reduced 2 A hybridization structure, which has the characteristics of oleophilic and hydrophobic; because the large pi bond restores the acting force generated between the adjacent graphene sheets and the van der Waals force existing between the functional groups, the graphene sheets are randomly piled under the action of the steric hindrance of other graphene sheets, so that a three-dimensional porous network structure of the aerogel is formed; on the other hand, the ethylenediamine can be doped with N during reduction, so that the catalytic performance is improved, ethylenediamine molecules contain two amino groups, nucleophilic ring-opening reaction can be carried out between the ethylenediamine molecules and epoxy groups on the surface of GO, and covalent bonds formed between graphene sheets are used for connecting the graphene sheets.
In the invention, the mass ratio of the N-containing reducing agent to the graphene oxide in the graphene oxide aqueous dispersion is preferably (36-792) to 40, and can be 36:40, 100:40, 200:40, 300:40, 400:40, 500:40, 600:40, 700:40 and 792:40. Wherein the ethylenediamine reducing agent is liquid, and the dosage ratio of graphene oxide in the aqueous dispersion of ethylenediamine and graphene oxide is (40-880) μL:40 mg, specifically 40 μL:40 mg, 100 μL:40 mg, 150 μL:40 mg, 200 μL:40 mg, 250 μL:40 mg, 300 μL:40 mg, 350 μL:40 mg, 400 μL:40 mg, 440 μL:40 mg, 450 μL:40 mg, 500 μL:40 mg, 550 μL:40 mg, 600 μL:40 mg, 650 μL:40 mg, 700 μL:40 mg, 750 μL:40 mg, 800 μL:40 mg, 880 μL:40 mg.
In the present invention, the temperature is preferably raised to 85 to 100 ℃, and more specifically, 85 ℃, 90 ℃, 95 ℃ and 100 ℃. In the invention, the heating rate of the heating is preferably 1-5 ℃/min, and can be specifically 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min and 5 ℃/min. The reaction time after the temperature reaches the target temperature is preferably 6 to 10 hours, and more specifically, 6 hours, 7 hours, 8 hours, 9 hours, and 10 hours. Through the reaction, the graphene aerogel doped with nitrogen is formed in the system.
In the present invention, it is preferable that the method further comprises, after the reduction reaction: washing and drying. Wherein the washing is preferably pure water washing. The drying is preferably freeze-drying. The temperature of the freeze-drying is preferably-40 to-50 ℃. And (3) performing post-treatment to obtain the nitrogen-doped graphene aerogel.
[ concerning step b ]:
b) Dissolving 5,10,15, 20-tetraphenyl cobalt porphyrin and 5,10,15, 20-tetraphenyl porphyrin in an organic solvent to obtain a metalloporphyrin solution.
In the invention, the structures of the 5,10,15, 20-tetraphenyl cobalt porphyrin and the 5,10,15, 20-tetraphenyl porphyrin are respectively shown as follows:
in the invention, the molar ratio of the 5,10,15, 20-tetraphenylcobalt porphyrin to the 5,10,15, 20-tetraphenylcobalt porphyrin is 1: (1-2.5), and can be specifically 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, 1:2.1, 1:2.2, 1:2.3, 1:2.4 and 1:2.5.
In the present invention, the organic solvent is preferably one or more of chloroform, dichloromethane and N, N-dimethylformamide (i.e., DMF), more preferably chloroform. The organic solvent can be used for dissolving the porphyrin compound, and the effect is optimal when the chloroform is used for bonding the subsequent aerogel with the graphene, the chloroform is used for better balancing the graphene aerogel impregnation process and the solvent volatilization process, so that the graphene aerogel can be fully impregnated before the solvent is volatilized cleanly, and the solvent can be better volatilized and removed on the basis of full impregnation, thereby achieving better loading effect.
In the invention, the dosage ratio of the 5,10,15, 20-tetraphenylcobalt porphyrin to the organic solvent is preferably 14mg to (4-8) mL, and can be specifically 14mg to 4mL, 14mg to 5mL, 14mg to 6mL, 14mg to 7mL and 14mg to 8mL.
In the present invention, the two porphyrin compounds are preferably dissolved in an organic solvent by stirring. The stirring speed is preferably 600-1000 rpm, and can be 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm. The stirring time is preferably 6 to 10 hours, and more preferably 6 hours, 8 hours and 10 hours. Stirring and dissolving to obtain a metalloporphyrin solution which is uniformly mixed.
The present invention is not particularly limited to the order of the above steps a) and b).
[ about step c ]:
and immersing the graphene aerogel in the metalloporphyrin solution for adsorption, and then taking out and drying to obtain the composite precursor.
In the invention, the relation between the dosage of the graphene aerogel and the metalloporphyrin solution is not particularly limited, and the graphene aerogel can be completely immersed in the metalloporphyrin solution.
In the present invention, the extent of adsorption is preferably up to saturation of graphene aerogel adsorption. According to the invention, the graphene aerogel is immersed in the metalloporphyrin solution obtained in the step b) by utilizing the lipophilicity and strong adsorptivity, and can adsorb the impregnating solution with 130 times of the self weight, and the contact angle of the graphene aerogel to the solvent in the impregnating solution is close to 0 degrees. In the adsorption process, pi-pi interaction of aromatic macrocyclic compound is used between cobalt porphyrin and porphyrin to form Co-N for cobalt porphyrin macrocyclic center 4 And performing in-situ protection, wherein the macrocyclic conjugated structure of the porphyrin can be adsorbed on the graphene sheet through pi-pi interaction.
In the invention, after the adsorption is finished, taking out the graphene aerogel and drying. In the present invention, the drying temperature is preferably 55 to 65℃and may specifically be 55℃56℃57℃58℃59℃60℃61℃62℃63℃64℃65 ℃. After drying, a composite precursor is obtained.
[ regarding step d ]:
d) And carrying out pyrolysis treatment on the composite precursor to obtain the graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst.
In the present invention, the pyrolysis treatment is preferably performed under a protective atmosphere. The kind of the protective gas for providing the protective atmosphere is not particularly limited, and may be any protective gas known to those skilled in the art, such as nitrogen, argon or helium.
In the present invention, the pyrolysis treatment is preferably carried out at a temperature of 800 to 1000 ℃, specifically 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, 1000 ℃. The heating rate of the pyrolysis treatment is preferably 2 to 5 ℃ per minute, specifically may be 2 ℃ per minute, 3 ℃ per minute, 4 ℃ per minute, 5 ℃ per minute, and more preferably is 5 ℃ per minute. The thermal insulation time of the pyrolysis treatment is preferably 1 to 2 hours, specifically may be 1 hour, 1.5 hours, 2 hours, and more preferably 2 hours. Through the pyrolysis treatment, cobalt porphyrin and a porphyrin macrocyclic structure are decomposed, cobalt nitride is generated by central metal, and mesoporous is increased after pyrolysis of graphene aerogel after the decomposition of porphyrin, so that the specific surface area is increased. Through the treatment, the graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst is obtained.
In the invention, the temperature is also reduced after the pyrolysis treatment. In the present invention, the cooling rate is preferably 2 to 5 ℃/min, more preferably 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, and even more preferably 5 ℃/min. The temperature is preferably reduced to room temperature, which may be 20 to 30 ℃, specifically 20 ℃, 25 ℃ and 30 ℃.
The invention also provides a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst prepared by the preparation method.
The invention also provides an oxygen reduction working electrode, wherein the catalyst is the graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst in the technical scheme.
In the present invention, the oxygen reduction working electrode is preferably produced by the following method: mixing an alcohol organic solvent with a Nafion solution to obtain a mixed solution; then ultrasonically dispersing the graphene aerogel adsorbed metalloporphyrin-based oxygen reduction catalyst into the mixed solution to obtain a dispersion liquid; then, the dispersion liquid is dropped drop by drop on the surface of the rotating disk electrode, and dried, thus obtaining the oxygen reduction working electrode.
Wherein:
the alcohol organic solvent is preferably absolute ethanol. The Nafion solution is preferably a 5% Nafion solution. The volume ratio of the alcohol organic solvent to the Nafion solution is preferably 800:30-40, and can be specifically 800:30, 800:35 or 800:40.
The ratio of the graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst to the mixed solution is preferably 5mg to (0.8-1.0) mL, and can be specifically 5mg to 0.8mL, 5mg to 0.9mL and 5mg to 1.0mL. The diameter of the disk electrode is preferably 5mm. The drying is preferably natural drying. After the above treatment, an oxygen reduction working electrode was obtained. The preparation of the oxygen reduction working electrode can be used for testing electrochemical catalytic performance so as to show the effect of the catalyst.
The invention also provides an air electrode, which comprises a matrix and a catalyst supported on the matrix, wherein the catalyst is the graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst in the technical scheme.
In the present invention, the substrate is preferably carbon paper or carbon cloth.
In the present invention, the air electrode is preferably produced by the following method: mixing an alcohol organic solvent with a Nafion solution to obtain a mixed solution; then ultrasonically dispersing the graphene aerogel adsorbed metalloporphyrin-based oxygen reduction catalyst into the mixed solution to obtain a dispersion liquid; then, the dispersion was applied dropwise to a substrate, and dried to obtain an air electrode.
Wherein:
the alcohol organic solvent is preferably absolute ethanol. The Nafion solution is preferably a 5% Nafion solution. The volume ratio of the alcohol organic solvent to the Nafion solution is preferably 800:30-40, and can be specifically 800:30, 800:35 or 800:40.
The dosage ratio of the graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst to the mixed solution is preferably 4mg to (0.8-1.2) mL, and can be specifically 4mg to 0.8mL, 4mg to 0.9mL, 4mg to 1.0mL, 4mg to 1.1mL and 4mg to 1.2mL. After the ultrasonic dispersion is dripped on a substrate and dried, a catalyst is loaded on the surface of the substrate, thereby obtaining the air electrode. In the invention, the catalyst loading of the air electrode is preferably 0.5-2 mg/cm 2 Specifically, it may be 0.5mg/cm 2 、1mg/cm 2 、1.5mg/cm 2 、2mg/cm 2 。
The invention also provides a fuel cell, wherein the air electrode is the air electrode in the technical scheme. In the present invention, the fuel cell is of the type of an oxyhydrogen fuel cell, a zinc-air fuel cell, a magnesium-air fuel cell or an aluminum-air fuel cell, preferably a zinc-air fuel cell. In the present invention, the fuel cell includes: a cathode, an anode and an electrolyte; wherein the cathode is the air electrode in the technical scheme. The types of the anode and the electrolyte are not particularly limited, and are conventional types of fuel cells in the prior art, such as zinc-air fuel cells, and zinc sheets are used as the anode.
The technical scheme provided by the invention has the following beneficial effects:
according to the preparation method, a certain amount of nitrogen-doped graphene aerogel is prepared, and the graphene aerogel is adopted to adsorb metalloporphyrin dissolved in chloroform for active site loading to prepare the oxygen reduction catalyst. The graphene aerogel is oleophilic, the contact angle of the graphene aerogel to chloroform is close to 0 degrees, and the graphene aerogel can adsorb impregnating solution with 130 times of the self weight, so that sufficient metalloporphyrin can be loaded. The graphene aerogel has the advantages of lipophilicity, strong adsorptivity and an internally porous structure, and can effectively load active sites. At the same time tetraphenyl cobalt porphyrin Co-N 4 The structure provides an active site. The pi-pi interaction of tetraphenylporphyrin and tetraphenylcobalt porphyrin plays a role in protecting and dispersing central metal, and the cobalt nitride is preferentially generated, so that the catalytic performance and the catalytic stability of the tetraphenylcobalt porphyrin are further improved.
The test result shows that the oxygen reduction catalyst of the invention has high-efficiency oxygen reduction electrochemical performance and stability, so that the half-wave potential of the oxygen reduction electrochemical reaction reaches more than 0.86V vs. RHE, and the oxygen reduction catalyst is superior to commercial platinum carbon Pt/C (0.84V) under the same condition; assembled into a zinc-air battery, the open-circuit voltage of which reaches more than 1.50V and is superior to commercial platinum carbon Pt/C (1.46V) under the same conditions; the maximum output power of the battery was 96mW/cm 2 Under equivalent conditions, better than 20wt% of commercial platinum carbon (maximum output power 78mW/cm 2 )。
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
Example 1
S1, placing 10mL of graphene oxide aqueous dispersion (4 mg/mL) in a reaction kettle, adding 440 mu L of ethylenediamine, heating to 95 ℃ at 5 ℃/min, preserving heat, reacting for 8 hours, taking out, washing with pure water twice to obtain graphene hydrogel, and freeze-drying the graphene hydrogel to obtain the graphene aerogel.
S2, dissolving 14mg of 5,10,15, 20-tetraphenyl cobalt porphyrin and 25mg of 5,10,15, 20-tetraphenyl porphyrin in 5mL of chloroform, and stirring for 8 hours to obtain a metalloporphyrin solution which is uniformly mixed.
S3, soaking 50mg of graphene aerogel into metalloporphyrin solution, taking out after adsorption saturation, and drying at 60 ℃ to obtain a composite precursor.
S4, placing the obtained composite precursor into a tube furnace, heating to 900 ℃ at a speed of 5 ℃/min in a nitrogen environment, maintaining for 2 hours, and then cooling to 25 ℃ at a speed of 5 ℃/min to obtain an oxygen reduction catalyst named CoTPP/TPP-RGO.
Characterization of the graphene aerogel obtained in step S1 is performed, and as a result, as shown in fig. 1, fig. 1 is an SEM image of the graphene aerogel obtained in step S1 in example 1, it can be seen that a large number of wrinkles are formed on the graphene sheet, and the graphene sheet is crosslinked with each other to form a porous structure.
Characterization of the catalyst product obtained in step S4 is shown in fig. 2, and fig. 2 is an SEM image of the oxygen reduction catalyst obtained in example 1, which shows that a large number of decomposers released by porphyrin pyrolysis form more holes on the carbon substrate in the graphene aerogel after pyrolysis.
Example 2
Preparation of oxygen reduction working electrode:
uniformly mixing 800 mu L of ethanol and 30 mu L of Nafion solution (concentration 5%) and performing ultrasonic dispersion to obtain a mixed solution; 5mg of the oxygen reduction catalyst obtained in example 1 was dispersed in the above mixed solution, and the dispersion was carried out by ultrasonic dispersion for 1 hour to obtain a catalyst ink uniformly dispersed. And (3) dripping 10 mu L of catalyst ink onto the rotating disk electrode, and drying to obtain the oxygen reduction working electrode.
Reducing oxygen to working electrode at O 2 Electrochemical tests were carried out in 0.1mol/L KOH solution at saturation, and the results are shown in FIGS. 3 to 4.
FIG. 3 is a graph of linear voltammetric scans of the CoTPP/TPP-RGO oxygen reduction catalyst obtained in example 1, and the results of the tests under the same conditions are also shown in FIG. 3, while using a commercial platinum carbon catalyst as a control, it can be seen that the half-wave potential of the CoTPP/TPP-RGO oxygen reduction catalyst obtained in example 1 reaches 0.88V, which is 0.84V higher than the half-wave potential of the commercial platinum carbon, and the catalyst obtained in the invention has better catalytic activity than the commercial platinum carbon.
FIG. 4 is a graph of linear voltammetric scans of the CoTPP/TPP-RGO oxygen reduction catalyst obtained in example 1 at different rotational speeds (400-2025 rpm), and the electron transfer number of the CoTPP/TPP-RGO oxygen reduction catalyst after k-l line fitting is 4, which shows that the oxygen reduction reaction is mainly four-electron reaction under the action of the CoTPP/TPP-RGO oxygen reduction catalyst obtained in example 1, and the CoTPP/TPP-RGO oxygen reduction catalyst has high-efficiency oxygen reduction catalytic activity.
Example 3
Preparation of an air electrode:
uniformly mixing 800 mu L of ethanol and 30 mu L of Nafion solution (concentration 5%) and performing ultrasonic dispersion to obtain a mixed solution; 4mg of the oxygen reduction catalyst obtained in example 1 was dispersed in the above mixed solution, and the dispersion was subjected to ultrasonic dispersion for 1 hour to obtain a catalyst dispersion liquid having a uniform dispersion. 830. Mu.L of the catalyst dispersion was coated on a carbon paper and dried to obtain an air electrode. In addition, air electrodes were made as a comparison according to the procedure described above, using commercial 20wt% platinum carbon as a control catalyst.
The prepared air electrode is taken as a cathode, a zinc sheet is taken as an anode, KOH solution (concentration is 6M) is taken as electrolyte, a zinc-air fuel cell is formed, and the open-circuit voltage and polarization curve of the cell are obtained through testing at normal temperature and normal pressure, and the results are shown in figures 5-6.
Fig. 5 is a graph showing the open circuit voltage of the zinc-air fuel cell in example 3, and it can be seen that the oxygen reduction catalyst of the present invention, which is obtained in example 1, has an open circuit voltage of 1.52V for the fuel cell, and a commercial platinum carbon catalyst of 20wt% has an open circuit voltage of 1.46V for the fuel cell, and the oxygen reduction catalyst of the present invention increases the open circuit voltage of the fuel cell under the same conditions.
FIG. 6 is a polarization graph of a zinc-air fuel cell of example 3, from which a corresponding maximum power density was calculated to obtain a maximum power density of 110mW/cm for the CoTPP/TPP-RGO oxygen reduction catalyst of example 1 2 Whereas 20wt% of commercial platinum carbon catalyst corresponds to a maximum power density of 78mW/cm for the fuel cell 2 The oxygen reduction catalyst obtained by the invention improves the maximum power density of the fuel cell under the same conditions.
Example 4
1. Preparation of the catalyst
The procedure is as in example 1, except that the temperature is increased to 85℃in step S1 and 800℃in step S4.
2. And (3) testing:
the electrochemical performance test was conducted in accordance with examples 2 to 3, and the results are shown in FIGS. 7 to 9, and the results show that the half-wave potential of the oxygen reduction catalyst obtained in example 4 was 0.87V, the open circuit voltage of the corresponding fuel cell was 1.51V, and the maximum power density was 99mW/cm 2 Under equivalent conditions, better than 20wt% of commercial platinum carbon catalyst (0.84V, 1.46V, 78 mW/cm) 2 )。
Example 5
1. Preparation of the catalyst
The procedure is as in example 1, except that the temperature is raised to 100℃in step S1 and to 1000℃in step S4.
2. And (3) testing:
the electrochemical performance test was conducted in accordance with examples 2 to 3, and the results are shown in FIGS. 10 to 12, and the results show that the half-wave potential of the oxygen reduction catalyst obtained in example 4 was 0.86V, the open circuit voltage of the corresponding fuel cell was 1.50V, and the maximum power density was 96mW/cm 2 Under equivalent conditions, better than 20wt% of commercial platinum carbon catalyst (0.84V, 1.46V, 78 mW/cm) 2 )。
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (9)
1. The preparation method of the graphene aerogel adsorbed metalloporphyrin-based oxygen reduction catalyst is characterized by comprising the following steps of:
a) Under the action of an N-containing reducing agent, heating the aqueous dispersion of graphene oxide to perform a reduction reaction, and then washing and drying to obtain graphene aerogel;
b) Dissolving 5,10,15, 20-tetraphenyl cobalt porphyrin and 5,10,15, 20-tetraphenyl porphyrin in an organic solvent to obtain a metalloporphyrin solution;
the organic solvent is selected from one or more of chloroform, dichloromethane and N, N-dimethylformamide;
c) Immersing the graphene aerogel in the metalloporphyrin solution for adsorption, and then taking out and drying to obtain a composite precursor;
d) Carrying out pyrolysis treatment on the composite precursor to obtain a graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst;
the steps a) and b) are not limited in order.
2. The method according to claim 1, wherein in the step a), the N-containing reducing agent is one or more selected from ethylenediamine, dopamine and urea.
3. The preparation method according to claim 1, wherein in the step a), the temperature is raised to 85-100 ℃, and the reaction is performed for 6-10 hours after the temperature is raised.
4. The method according to claim 1, wherein in the step d), the pyrolysis temperature is 800-1000 ℃.
5. The preparation method according to claim 1 or 2, wherein in the step a), the mass ratio of graphene oxide in the aqueous dispersion of the N-containing reducing agent to graphene oxide is (36-792) to 40;
the concentration of the graphene oxide aqueous dispersion liquid is 1-4 mg/mL.
6. The method according to claim 1, wherein in the step b), the molar ratio of 5,10,15, 20-tetraphenylcobalt porphyrin to 5,10,15, 20-tetraphenylporphyrin is 1:1-2.5.
7. A graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst prepared by the preparation method of any one of claims 1 to 6.
8. An air electrode comprising a substrate and a catalyst supported on the substrate, wherein the catalyst is the graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst of claim 7.
9. A fuel cell, wherein the air electrode in the fuel cell is the air electrode of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210508480.7A CN115036517B (en) | 2022-05-11 | 2022-05-11 | Graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, preparation method thereof, air electrode and fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210508480.7A CN115036517B (en) | 2022-05-11 | 2022-05-11 | Graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, preparation method thereof, air electrode and fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115036517A CN115036517A (en) | 2022-09-09 |
| CN115036517B true CN115036517B (en) | 2023-12-01 |
Family
ID=83120405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210508480.7A Active CN115036517B (en) | 2022-05-11 | 2022-05-11 | Graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, preparation method thereof, air electrode and fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115036517B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688995A (en) * | 2016-01-21 | 2016-06-22 | 湖南科技大学 | Method for preparing metalloporphyrin-graphene nano composite material under condition of room temperature |
| CN109046460A (en) * | 2018-08-03 | 2018-12-21 | 湖南大学 | A kind of composite electrocatalyst for electro-catalysis reduction nitrobenzene |
| CN110176607A (en) * | 2019-05-14 | 2019-08-27 | 清华大学 | A kind of fuel battery cathod catalyst and preparation method thereof |
| CN111342057A (en) * | 2020-02-18 | 2020-06-26 | 江苏理工学院 | Preparation method and application of metalloporphyrin-modified sulfur-doped reduced graphene oxide electrocatalyst |
| CN111952605A (en) * | 2020-07-29 | 2020-11-17 | 天津大学 | Preparation method of integrated oxygen reduction catalytic electrode |
| CN113363514A (en) * | 2021-06-29 | 2021-09-07 | 中北大学 | Carbon aerogel supported cobalt monoatomic catalyst for metal air battery, preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8975326B2 (en) * | 2010-03-15 | 2015-03-10 | Lei Zhai | Carbon nanotube or graphene-based aerogels |
-
2022
- 2022-05-11 CN CN202210508480.7A patent/CN115036517B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688995A (en) * | 2016-01-21 | 2016-06-22 | 湖南科技大学 | Method for preparing metalloporphyrin-graphene nano composite material under condition of room temperature |
| CN109046460A (en) * | 2018-08-03 | 2018-12-21 | 湖南大学 | A kind of composite electrocatalyst for electro-catalysis reduction nitrobenzene |
| CN110176607A (en) * | 2019-05-14 | 2019-08-27 | 清华大学 | A kind of fuel battery cathod catalyst and preparation method thereof |
| CN111342057A (en) * | 2020-02-18 | 2020-06-26 | 江苏理工学院 | Preparation method and application of metalloporphyrin-modified sulfur-doped reduced graphene oxide electrocatalyst |
| CN111952605A (en) * | 2020-07-29 | 2020-11-17 | 天津大学 | Preparation method of integrated oxygen reduction catalytic electrode |
| CN113363514A (en) * | 2021-06-29 | 2021-09-07 | 中北大学 | Carbon aerogel supported cobalt monoatomic catalyst for metal air battery, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115036517A (en) | 2022-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lv et al. | In-situ embedding zeolitic imidazolate framework derived Co–N–C bifunctional catalysts in carbon nanotube networks for flexible Zn–air batteries | |
| CN1292507C (en) | High concentration carbon supported catalyst, method of preparing the same, catalyst electrode utilizing the catalyst, and fuel cell utilizing the same | |
| Sanetuntikul et al. | Cobalt and nitrogen co-doped hierarchically porous carbon nanostructure: a bifunctional electrocatalyst for oxygen reduction and evolution reactions | |
| Guo et al. | Ruthenium oxide coated ordered mesoporous carbon nanofiber arrays: A highly bifunctional oxygen electrocatalyst for rechargeable Zn–air batteries | |
| CN106602092B (en) | Preparation method and application of single-walled carbon nanotube hollow sphere oxygen reduction catalyst | |
| CN102637882B (en) | Metal-free nitrogen- functionalized carbon catalyst as well as preparation method and application thereof | |
| JP2007250274A (en) | Electrode catalyst for fuel cell with enhanced noble metal utilization efficiency, its manufacturing method, and solid polymer fuel cell equipped with this | |
| JP2007519165A (en) | Nanostructured metal-carbon composite for electrode catalyst of fuel cell and production method thereof | |
| Lefèvre et al. | Recent advances in non-precious metal electrocatalysts for oxygen reduction in PEM fuel cells | |
| JP7368853B2 (en) | Multifunctional electrode additive | |
| Xu et al. | Embellished hollow spherical catalyst boosting activity and durability for oxygen reduction reaction | |
| CN113659158B (en) | Carbon-based Fe/S/N co-doped oxygen reduction catalyst and preparation method and application thereof | |
| CN111725524B (en) | Fuel cell cathode catalyst, preparation method thereof, membrane electrode and fuel cell | |
| CN111146459B (en) | Fuel cell cathode catalyst, preparation method thereof and application thereof in fuel cell | |
| CN110707337B (en) | Preparation method and application of carbon-based non-noble metal oxygen reduction catalyst | |
| JPWO2006003950A1 (en) | Composite, catalyst structure, electrode for polymer electrolyte fuel cell, method for producing the same, and polymer electrolyte fuel cell | |
| CN103401000B (en) | Used in proton exchange membrane fuel cell catalyst, its preparation method and Proton Exchange Membrane Fuel Cells | |
| CN109873174B (en) | Preparation method of three-dimensional carrier supported platinum-palladium-cobalt alloy structure catalyst for low-temperature fuel cell | |
| JP4311070B2 (en) | Cathode for fuel cell and polymer electrolyte fuel cell having the same | |
| CN115036517B (en) | Graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, preparation method thereof, air electrode and fuel cell | |
| JP2004342337A (en) | Electrode catalyst and its manufacturing method | |
| Huang et al. | Calcined cobalt-chelated, N-containing poly (methylenediphenyl urea) as an ORR cathode catalyst | |
| JP4433518B2 (en) | Solid polymer electrolyte fuel cell | |
| CN114759199A (en) | Method for preparing Fe/N co-doped carbon nanotube under assistance of ZIF-8 derived carboxylate and application of method | |
| EP1994590A1 (en) | Solid polymer fuel cell and method for producing mea used for solid polymer fuel cell |
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 |