CN115064705A - Catalyst of dissimilar metal atom pair, preparation method and application thereof - Google Patents
Catalyst of dissimilar metal atom pair, preparation method and application thereof Download PDFInfo
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- 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
Abstract
The invention relates to a dissimilar metal atom pair catalyst and a preparation method and application thereof. The dissimilar metal atom pair catalyst comprises a carrier and an active component, wherein the active component is loaded on the carrier, the active component comprises a first metal atom and a second metal atom, the first metal atom is Mn, Fe or Co, the second metal atom is Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and the first metal atom and the second metal atom are different. The catalyst comprises a carrier and an active component, wherein the active component comprises different first metal atoms and second metal atoms, and the adsorption energy of an oxidation reaction intermediate can be adjusted through the selection and the matching of the different first metal atoms and second metal atoms, so that the damage of a Fenton-like process to an active center is relieved, and the good activity and the durability are both considered.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a dissimilar metal atom pair catalyst and a preparation method and application thereof.
Background
Fuel cells use fuel and oxygen as raw materials and can convert chemical energy of the fuel into electrical energy. From the viewpoint of energy saving and ecological environment protection, the fuel cell has a wide development prospect. For example, a proton exchange membrane fuel cell is an important means for efficiently utilizing hydrogen energy, and has the advantages of high energy conversion efficiency and environmental friendliness, but the catalyst used in the proton exchange membrane fuel cell is often a platinum-containing noble metal catalyst, so that the cost of the proton exchange membrane fuel cell is greatly increased, and the large-scale application of the proton exchange membrane fuel cell is restricted. In order to reduce the manufacturing cost of the proton exchange membrane fuel cell, it is an effective way to reduce the amount of precious metals or to use non-precious metals to prepare corresponding catalysts, but it is difficult for these improved catalysts to effectively combine good activity and durability.
Disclosure of Invention
In view of the above, it is necessary to provide a dissimilar metal atom pair catalyst which can effectively achieve both good activity and durability, and a method for producing the same and use thereof.
In order to solve the above technical problems, an embodiment of the present invention has a technical solution:
a dissimilar metal atom pair catalyst, comprising a support and an active component, said active component being supported on said support, said active component comprising a first metal atom and a second metal atom, said first metal atom being Mn, Fe or Co, said second metal atom being Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and said first metal atom and said second metal atom being different.
In one embodiment, the active component comprises a plurality of atom pairs, each of the atom pairs comprising one of the first metal atoms and one of the second metal atoms.
In one embodiment, the distance between the first metal atom and the second metal atom in each of the atom pairs is 2 to 4 angstroms.
In one embodiment, the mass percentage of the sum of the first metal atom and the second metal atom is 0.3 to 4% in terms of mass percentage of the dissimilar metal atom to the catalyst.
In one embodiment, the support comprises at least one of carbon black, activated carbon, carbon nanotubes, graphene, mesoporous carbon, carbon nitride, nitrogen doped carbon material, and an organic framework.
A method for preparing a dissimilar metal atom pair catalyst comprises the following steps:
mixing a metal precursor and a carrier in a solvent to prepare a mixture; the metal precursor comprises a first metal atom and a second metal atom, the first metal atom is Mn, Fe or Co, the second metal atom is Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and the first metal atom and the second metal atom are different;
carrying out solid-liquid separation treatment on the mixture to obtain a solid phase serving as a catalyst preform;
and carrying out pyrolysis treatment on the catalyst preform under the protective gas atmosphere.
In one embodiment, the metal precursor comprises a metal-carbonyl compound comprising the first metal atom and the second metal atom therein; alternatively, the first and second electrodes may be,
the metal precursor comprises at least one of compounds shown in formulas I-III;
wherein, M 1 And M 2 One of Mn, Fe or Co, the other of Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and M 1 And M 2 Different;
n is an integer of 0 to 4; x is a non-metallic group;
R 1 selected from substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 An aryl group; r 4 、R 5 、R 6 、R 11 、R 12 、R 13 、R 14 And R 16 Each independently selected from-H, -D, substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 An aryl group; r 2 And R 3 Each independently selected from-H, -D, substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or notSubstituted C 6 ～C 20 Aryl, or R 2 、R 3 And M 2 Connecting to form a ring; r 7 、R 8 、R 9 And R 10 Each independently selected from-H, -D, substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 Aryl, or R 7 And M 1 Linked to form a ring, R 8 And M 1 Linked to form a ring, R 9 And M 2 Linked to form a ring, R 10 And M 2 Connecting to form a ring; r 15 Selected from O or S, or R 15 、M 1 、M 2 Are connected.
In one embodiment, formula I is selected from the structures of formula I-1, formula II is selected from the structures of formula II-1, and formula III is selected from the structures of formula III-1:
wherein R is 17 Selected from substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 And (4) an aryl group.
In one embodiment, the pyrolysis treatment temperature is 300 ℃ to 1000 ℃.
In one embodiment, the pyrolysis treatment time is 0.5h to 4 h.
In one embodiment, the solvent comprises at least one of water, an alcohol, an amide, and a nitrile.
A fuel cell electrode comprising the dissimilar metal atom pair catalyst described in any one of the above embodiments or the dissimilar metal atom pair catalyst prepared by the preparation method described in any one of the above embodiments.
A fuel cell comprising an anode, a cathode, and an electrolyte, the anode and/or the cathode comprising a dissimilar metal atom pair catalyst as described in any of the embodiments above; alternatively, the first and second liquid crystal display panels may be,
the anode and/or the cathode comprise the dissimilar metal atom pair catalyst prepared by the preparation method described in any one of the above embodiments.
The catalyst comprises a carrier and an active component, wherein the active component comprises different first metal atoms and second metal atoms, and the adsorption energy of an oxidation reaction intermediate can be adjusted through the selection and the matching of the different first metal atoms and second metal atoms, so that the damage of a Fenton-like process to an active center is relieved, and good activity and durability are both considered.
The preparation method can prepare the dissimilar metal atom pair catalyst which can effectively give consideration to good activity and durability on one hand, and has good directionality and universality on the other hand, wherein the directionality shows that the active site of the catalyst can be regulated and controlled through the selection of the metal precursor, and the universality shows that various dissimilar metal atom pair catalysts can be prepared through the selection of the metal precursor, so that different requirements of the fuel cell are met.
Drawings
FIG. 1 is a high-angle annular dark-field scanning transmission electron micrograph of FeCu-N/C dissimilar metal atoms on a catalyst in example 1 of the present invention;
FIG. 2 is a synchrotron radiation X-ray absorption spectrum of FeCu-N/C metalloid atoms on the catalyst and the comparative sample in example 1 of the present invention;
FIG. 3 shows the results of time-of-flight secondary ion mass spectrometry of FeCu-N/C metalloid atom pair catalyst and FeCu-SA catalyst of comparative sample in example 1 of the present invention;
FIG. 4 is a schematic diagram showing the mechanism of the preparation process of the catalyst by FeCu-N/C metalloid atoms in example 1 of the present invention;
FIG. 5 is a graph showing the results of a rotating disk electrode test of FeCu-N/C metalloid atoms on a catalyst in example 1 of the invention;
FIG. 6 is a graph showing the results of the rotating disk electrode test of MnNi-N/C metalloid atoms to catalyst in example 2 of the invention;
FIG. 7 is a graph showing the results of a rotating disk electrode test of CoZn-N/C dissimilar metal atoms on a catalyst in example 3 of the present invention;
FIG. 8 is a graph showing the results of a rotating disk electrode test of FeCo-N/C metalloid atoms on a catalyst in example 4 of the invention;
FIG. 9 is a graph showing the results of the rotating disk electrode test of FeZn-N/C metalloid atoms on the catalyst in example 5 of the invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
In the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
One embodiment of the present invention provides a dissimilar metal atom pair catalyst. The catalyst comprises a carrier and an active component, wherein the active component is loaded on the carrier and comprises a first metal atom and a second metal atom, the first metal atom is Mn, Fe or Co, the second metal atom is Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and the first metal atom and the second metal atom are different.
In the catalyst of the embodiment, the active component includes different first metal atoms and second metal atoms, and by selection and coordination of the different first metal atoms and second metal atoms, the adsorption energy of the oxidation reaction intermediate can be adjusted, the damage of the fenton-like process to the active center is slowed down, and good activity and durability are both considered.
In one particular example, the active component includes a plurality of atom pairs, each atom pair including one first metal atom and one second metal atom. Further, in each atom pair, the distance between the first metal atom and the second metal atom is 2 to 4 angstroms. For example, the distance between the first metal atom and the second metal atom can be, but is not limited to, 2 angstroms, 2.5 angstroms, 3 angstroms, 3.5 angstroms, 4 angstroms, or the like. It is understood that 1 angstrom-0.1 nm.
In another specific example, regarding the mass percentage of the first metal atom and the second metal atom, the mass percentage of the sum of the first metal atom and the second metal atom is 0.3% to 4% in terms of mass percentage of the dissimilar metal atom to the catalyst. It is understood that the mass percentage of the sum of the first metal atom and the second metal atom means the mass percentage of the total mass of the first metal atom and the second metal atom to the catalyst of the dissimilar metal atom. Alternatively, the mass percentage of the sum of the first metal atom and the second metal atom may be, but is not limited to, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, or 4%. Further optionally, the mass percentage of the sum of the first metal atom and the second metal atom is 1% to 2%. Of course, the mass percentage of the sum of the first metal atom and the second metal atom may be selected from 0.3% to 4%.
As an alternative to the support in some examples of the invention, the support comprises carbon black, activated carbon, carbon nanotubes, graphene, mesoporous carbon, carbon nitride (g-C) 3 N 4 ) At least one of a nitrogen doped carbon material and an organic framework. Wherein the organic framework comprises a metal-organic framework and/or a covalent organic framework. Can be used forIt is understood that the mesoporous carbon includes carbon materials having a mesoporous structure prepared by a template method, such as FDU-15, CMK-3, CMK-8, and the like. Nitrogen-doped carbon material refers to carbon materials containing nitrogen elements with a separate nitrogen source or a source of nitrogen and carbon from the same species. Alternatively, the carbon black includes ketjen black or acetylene black or the like. Specifically, activated carbon is from Norit corporation and ketjen black is from Cabot corporation.
In one particular example, the support is a nitrogen-doped carbon material support. The dissimilar metal atom pair catalyst in this example may now be represented as M 1 M 2 N/C, i.e. the N is doped with a C catalyst by a dissimilar metal atom. Wherein M is 1 And M 2 Respectively represent a first metal atom and a second metal atom. Specifically, M 1 And M 2 One of Mn, Fe or Co, the other of Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and M 1 And M 2 Different.
In selecting the first metal atom and the second metal atom in the active component, the first metal atom and the second metal atom are partially enumerated in some examples of the invention. For example, the first metal atom is Fe and the second metal atom is Cu. For another example, the first metal atom is Mn and the second metal atom is Ni. For another example, the first metal atom is Co and the second metal atom is Zn. For another example, the first metal atom is Fe and the second metal atom is Co. For another example, the first metal atom is Fe and the second metal atom is Zn.
In yet another embodiment of the present invention, a method for preparing a catalyst comprising a pair of dissimilar metal atoms is provided. The preparation method comprises the following steps: mixing a metal precursor and a carrier in a solvent to prepare a mixture; the metal precursor comprises a first metal atom and a second metal atom, the first metal atom is Mn, Fe or Co, the second metal atom is Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and the first metal atom and the second metal atom are different; carrying out solid-liquid separation treatment on the mixture to obtain a solid phase serving as a catalyst preform; and carrying out pyrolysis treatment on the catalyst preform under the protective gas atmosphere. The preparation method in the embodiment can prepare the dissimilar metal atom pair catalyst which can effectively give consideration to good activity and durability on one hand, and has good directionality and universality on the other hand, wherein the directionality shows that the active sites of the catalyst can be regulated and controlled through the selection of the metal precursor, and the universality shows that various dissimilar metal atom pair catalysts can be prepared through the selection of the metal precursor, so that different requirements of the fuel cell are met.
In one particular example, the metal precursor includes a metal carbonyl compound including a first metal atom and a second metal atom.
In another specific example, the metal precursor comprises at least one of compounds of formulae i to iii;
wherein M is 1 And M 2 One of Mn, Fe or Co, the other of Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and M 1 And M 2 Different;
n is an integer of 0 to 4; x is a non-metallic group;
R 1 selected from substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 An aryl group; r 4 、R 5 、R 6 、R 11 、R 12 、R 13 、R 14 And R 16 Each independently selected from-H, -D, substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 An aryl group; r 2 And R 3 Each independently selected from-H, -D, substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 An aryl group which is a radical of an aromatic group,or R 2 、R 3 And M 2 Connecting to form a ring; r 7 、R 8 、R 9 And R 10 Each independently selected from-H, -D, substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 Aryl, or R 7 And M 1 Linked to form a ring, R 8 And M 1 Linked to form a ring, R 9 And M 2 Linked to form a ring, R 10 And M 2 Connecting to form a ring; r 15 Selected from O or S, or R 15 、M 1 、M 2 Are connected.
In some specific examples, R 2 、R 3 And M 2 Linked to form a ring, R 7 And M 1 Linked to form a ring, R 8 And M 1 Linked to form a ring, R 9 And M 2 Linked to form a ring, R 10 And M 2 When the bond forms a ring, an alkane ring, an aromatic ring, a heteroaromatic ring, or the like may be formed. The heteroatoms may be Si, N, P, O, S and/or Ge, preferably Si, N, P, O and/or S.
It is understood that n is 0,1, 2, 3 or 4. n represents the valence of X. When n-0, X is absent.
In a specific example, formula I is selected from the structures of formula I-1, formula II is selected from the structures of formula II-1, and formula III is selected from the structures of formula III-1:
wherein R is 17 Selected from substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 And (4) an aryl group.
In one specific example, X n- Selected from NO 3 - 、OAc - 、SO 4 2- 、ClO 4 - 、BF 4 - 、PF 6 - 、F - 、Cl - Or Br - 。
In the present invention, "substituted" means substitutedThe hydrogen atom is substituted by a substituent. With respect to substituted C 1 ～C 6 Alkyl, substituted C 6 ～C 20 And the substituent groups are respectively and independently selected from-H, -D, halogen group, sulfur-containing group, nitrogen-containing group, oxygen-containing group and phosphorus-containing group. Further, with respect to substituted C 1 ～C 6 Alkyl, substituted C 6 ～C 20 Aryl, wherein the substituents are independently selected from-H, -D, -OH and-NH 2 、-NO 2 、-CF 3 CN, -halogen radical, methyl, ethyl. It is understood that halo groups include-F, -Cl, -Br, -I, and the like.
In one specific example of the invention, the temperature of the pyrolysis process is 300 ℃ to 1000 ℃. Optionally, the temperature of the pyrolysis treatment is 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 1000 ℃. Preferably, the temperature of the pyrolysis treatment is 600 ℃ to 800 ℃. Furthermore, during the pyrolysis treatment, the temperature is increased to the pyrolysis treatment temperature at the heating rate of 3-8 ℃/min. For example, the temperature rise rate can be 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, or 8 ℃/min, etc.
In another specific example of the present invention, the pyrolysis treatment time is 0.5h to 4 h. The pyrolysis treatment is, for example, carried out for a time of 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h or 4 h. Preferably, the time of the pyrolysis treatment is 1h to 2 h.
In another specific example of the present invention, the protective gas used in the protective gas atmosphere includes at least one of nitrogen and an inert gas. It is understood that the inert gas includes at least one of helium, neon, argon, krypton, and xenon. Preferably, the protective gas used for the protective gas atmosphere includes at least one of nitrogen and argon. Further, the protective gas used in the protective gas atmosphere is nitrogen and/or argon.
In another specific example of the present invention, the solvent includes at least one of water, alcohol, amide, and nitrile. Optionally, the alcohol comprises methanol and/or ethanol. The amide includes at least one of N, N ' -dimethylformamide, N ' -dimethylacetamide, and N, N ' -diethylformamide. Nitriles include acetonitrile and/or propionitrile.
In the preparation method of the dissimilar metal atom pair catalyst, the step of mixing the metal precursor and the carrier in the solvent comprises the following steps: respectively mixing a metal precursor and a carrier with a solvent to obtain a precursor dispersion liquid and a carrier dispersion liquid; the precursor dispersion and the carrier dispersion are mixed. Firstly, respectively mixing the metal precursor and the carrier with a solvent, and fully dispersing the metal precursor and the carrier respectively to obtain a precursor dispersion liquid and a carrier dispersion liquid. Then, the precursor dispersion liquid and the carrier dispersion liquid are mixed to load the metal precursor on the carrier.
It is understood that when the mixture is subjected to solid-liquid separation treatment, the solid-liquid separation treatment may be performed by filtration, centrifugation, rotary evaporation, or the like.
Yet another embodiment of the present invention provides a fuel cell electrode. The fuel cell electrode comprises the dissimilar metal atom pair catalyst or the dissimilar metal atom pair catalyst prepared by the preparation method. Specifically, the fuel cell electrode includes an anode and/or a cathode.
Yet another embodiment of the present invention provides a fuel cell. The fuel cell comprises an anode, a cathode and an electrolyte, wherein the anode and/or the cathode comprises the dissimilar metal atom pair catalyst; alternatively, the anode and/or the cathode comprise the dissimilar metal atom pair catalyst prepared by the preparation method.
Alternatively, the fuel cell comprises an anode, a cathode and an electrolyte, wherein the cathode comprises the above-mentioned dissimilar metal atom pair catalyst, or the cathode comprises the dissimilar metal atom pair catalyst prepared by the above-mentioned preparation method.
The following are specific examples.
Example 1
(1) The chemical formula of the metal precursor in this example is FeCu (C) 24 H 26 N 4 O 2 )Cl 2 Abbreviated FeCuLCl 2 The structural formula is as follows:
the preparation method of the metal precursor comprises the following steps: 10mL of a methanol solution of 0.493g of 2-hydroxy-5-methyl-m-phthalaldehyde was mixed with 1mL of a methanol solution of 0.125mL of propylenediamine, followed by addition of 0.3g of solid Cu (OAc) 2 ·H 2 O, stirring for 30min at 40 ℃, and filtering and drying the obtained solid. 4mL of a methanol solution containing 0.44g of the above solid and 0.2g of FeCl 2 ·4H 2 Mixing 3mL of methanol solution of O, adding 1mL of methanol solution of 0.084mL of propane diamine, stirring at room temperature for 2 hours, filtering and drying the obtained precipitate to obtain a metal precursor FeCu (C) 24 H 26 N 4 O 2 )Cl 2 。
(2) The preparation method of the FeCu-N/C dissimilar metal atom pair catalyst in the embodiment comprises the following steps:
s101: 1.6g of Zn (NO) are weighed out 3 ) 2 ·6H 2 O, dissolved in 80mL of methanol, and 3.7g of 2-methylimidazole were weighed out and dissolved in 80mL of methanol. Mixing the two solutions, stirring at room temperature for 24 hours, centrifugally separating, washing with methanol, and drying to obtain powder. And (3) placing 400mg of the powder into a porcelain boat, heating to 900 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere, keeping for 3 hours, and naturally cooling to obtain the nitrogen-doped carbon material carrier derived from the metal-organic framework ZIF-8.
S102: 100mg of the nitrogen-doped carbon material carrier was weighed, dispersed in 20mL of methanol, and 10mg of FeCu (C) was weighed 24 H 26 N 4 O 2 )Cl 2 The complex is dissolved in 20mL of mixed solvent with the volume ratio of water to methanol being 1: 1. Mixing the two dispersions, stirring overnight at room temperature, filtering, and drying to obtain catalyst preform powder.
S103: putting the catalyst preformed product powder into a porcelain boat, heating to 800 ℃ at 5 ℃/min under the nitrogen atmosphere, and keeping for 2 h. Then naturally cooling to obtain the FeCu-N/C dissimilar metal atom pair catalyst in the embodiment. Wherein the mass sum of Fe and Cu accounts for 2 percent of the mass of FeCu-N/C dissimilar metal atoms to the catalyst. In the FeCu-N/C dissimilar metal atom pair catalyst in this example, the distance between Fe and Cu in the atom pair was 3.1 angstroms.
The morphology of FeCu-N/C metalloid atoms versus catalyst in this example is shown in FIG. 1. The circles in FIG. 1 indicate the Fe-Cu bimetallic atoms. As can be seen from FIG. 1, many metal atoms present in pairs are uniformly distributed in the FeCu-N/C metalloid atom pair catalyst.
(3) The catalyst was tested for FeCu-N/C metalloid atoms in this example.
The synchrotron radiation X-ray absorption spectrum of the FeCu-N/C metalloid atom pair catalyst and the comparative sample in the example is shown in FIG. 2. FIG. 2 a and FIG. 2 b show that FeCu-N/C hetero-metal atom has valence between bivalent FePc (ferrous phthalocyanine) and trivalent Fe 2 O 3 Is close to Fe 2 O 3 Cu having a valence between one and two 2 Between O and divalent CuO, close to Cu 2 And O. In the FeCu-N/C dissimilar metal atom pair catalyst, the valence state of Fe is lower than that of a monoatomic iron comparison sample Fe-SA, and the valence state of Cu is higher than that of a monoatomic copper comparison sample Cu-SA, which shows that certain electron transfer exists between Cu and Fe atoms in the FeCu-N/C dissimilar metal atom pair catalyst, so that the valence states of Fe and Cu are respectively shifted to the lower direction and the higher direction relative to the monoatomic comparison sample. In C of FIG. 2, FeCu-N/C metalloid atom pair catalyst
The peaks at the left and right correspond to Fe-N/O coordination, and no Fe-N/O coordination was observed
The peak corresponding to Fe-Fe in Fe foil indicates that Fe in FeCu diatomic catalyst exists in Fe-N/O atomic dispersion form and no Fe cluster or nano particle in aggregation state is generated. In d in FIG. 2, FeCu-N/C hetero metal atom is mainly responsible for Cu in the catalyst
The Cu-N/O coordination of (A) is dominant, and no observation is made
The peak at (b) corresponds to the Cu-Cu bond in Cu foil, which indicates FeCu-N/C isoThe metal atoms exist in the form of atomic dispersion mainly in Cu-N/O coordination in the catalyst, and Cu clusters or nanoparticles in an aggregation state do not exist.
The test results of the FeCu-N/C metalloid atom pair catalyst and the FeCu-SA catalyst of the comparative sample by the time-of-flight secondary ion mass spectrometry are shown in FIG. 3. Wherein, FeCu-SA catalyst represents FeCu double-monatomic catalyst, which means that Fe and Cu in the catalyst do not exist in the form of atom pairs, but are catalyst comparative samples randomly distributed in a carrier. A in FIG. 3, b in FIG. 3, and c in FIG. 3 correspond to [ FeCuN ], respectively 4 O 2 ]、[FeN 4 ]And [ CuN 4 ]Molecular ion peak intensities of the three fragments. For the expected FeCu-N/C metalloid atom pair active site of the catalyst [ FeCuN 4 O 2 ]The molecular ion peak intensity of the catalyst in FeCu-N/C dissimilar metal atom pair is obviously higher than that of FeCu-SA double monoatomic catalyst, indicating that [ FeCuN 4 O 2 ]The different metal diatomic sites mainly exist in FeCu-N/C different metal atom pair catalysts; on the other hand, [ FeN 4 ]And [ CuN 4 ]The molecular ion peak intensity of the two monoatomic sites is that the FeCu-SA double monoatomic catalyst is obviously higher than that of the FeCu-N/C dissimilar metal atom pair catalyst, and the two monoatomic sites are less existed in the FeCu-N/C dissimilar metal atom pair catalyst.
A schematic diagram of the mechanism study of the preparation process of the catalyst by FeCu-N/C metalloid atoms in this example is shown in FIG. 4. The study was performed using a thermogravimetric-infrared-mass spectrometry (TG-FTIR-MS) coupled method. In FIG. 4 b, in FIG. 4 c free FeCuLCl is given 2 Complex and carbon-supported FeCuLCl 2 Infrared spectrum contour map of the escaping gas during thermal decomposition of the complex. It can be seen that the free complex produced a significant amount of outgas at around 410 ℃ (b in fig. 4) and the supported complex produced a significant amount of outgas at around 210 ℃ (c in fig. 4), the evolution of outgas indicating significant decomposition of the complex, indicating a significant change in the decomposition temperature of the complex before and after nitrogen-doped carbon loading. Meanwhile, the difference between the two decomposition process temperatures is also shown in the thermogravimetric curves (a in fig. 4) of the two. Before and after nitrogen-doped carbon loadingThe difference of the decomposition temperature of the complex reflects the difference of the dispersion degree of the complex in a free state and a loaded state, the complex in the free state is in a highly crystalline state, molecules of the complex are closely stacked together through pi-pi interaction and electrostatic interaction, and the complex has strong intermolecular interaction, so that the decomposition temperature is high; on the surface of the carrier, the complex and the carrier are anchored through pi-pi interaction and coordination between metal centers and heteroatoms on the surface of the carrier, and the molecules of the complex which are not anchored are washed away, so that the complex exists on the surface of the carrier in a higher dispersion degree, the interaction between the molecules of the complex is reduced, and the decomposition temperature of the complex is reduced. The component of the evolved gas generated by the thermal decomposition of the complex before and after loading was measured using infrared spectroscopy and mass spectrometry, and several molecular ion peaks with specific mass-to-charge ratios (m/z) were used as comparison targets. For the molecular ion peak of m/z 17, it is in FeCuLCl 2 The signal occurring before 200 ℃ during the decomposition of the complex can be identified as a water molecule, while the molecular ion peak with m/z of 17, which occurs after 300 ℃, corresponds to NH 3 In FeCuLCl 2 Only the Schiff base group of the complex contains N element, so NH is generated after 300 DEG C 3 Necessarily accompanied by decomposition of the coordination structure of the complex, consistent with thermogravimetric results analysis of free-state complexes. In the decomposition process of the supported complex, the signal intensity of the molecular ion peak with m/z of 17 is very low after 200 ℃, which indicates that NH generated by the decomposition of the supported complex 3 Very little means that the M-N bond (i.e.the metal-nitrogen bond) in its coordination structure is well preserved (d in FIG. 4). Furthermore, the molecular ion peak of m/z ═ 65 corresponds to C generated by decomposition of propylenediamine group in the complex 3 N 2 The H group and the molecular ion peak signal only appear in the decomposition process of the free complex above 400 ℃, while the molecular ion peak signal is not observed in the nitrogen-doped carbon-supported complex, which also shows that the structure of the N-containing element of the complex species can be well preserved after the nitrogen-doped carbon is supported (e in figure 4). Similarly, the phenol structure C of the corresponding complex contains oxygen coordinating groups 7 H 7 O (m/z: 107) is also present only inDuring the decomposition of the free complex, and the temperature interval in which the signal appears also corresponds to the decomposition temperature of the complex, the signal of the molecular ion peak is not observed during the decomposition of the carbon-supported complex (f in fig. 4). The above results illustrate FeCuLCl 2 The thermal decomposition behaviors of the complex before and after nitrogen-doped carbon loading are greatly different, and the interaction between the complex and the surface of the carrier improves the stability of the coordination environment near the metal center of the carrier, so that the coordination structure of the complex is well reserved after the thermal decomposition process.
The oxygen reduction performance of the FeCu-N/C dissimilar metal atom pair catalyst in this example was tested using a rotating disk electrode. The test method comprises the following steps: the electrolyte used was 0.1M HClO saturated with oxygen at a temperature of 25 deg.C 4 In the water solution, a working electrode is a glassy carbon material rotating disc electrode with the diameter of 5mm, and the rotating speed is 1600 rpm; the counter electrode is a platinum wire, and the reference electrode is a saturated Ag/AgCl electrode. The reference electrode potential was corrected by a reversible hydrogen electrode. Weighing 5mg FeCu-N/C dissimilar metal atom pair catalyst, adding 990 muL isopropanol and 10 muL 5% nafion solution, performing ultrasonic dispersion to prepare catalyst ink, dripping 30 muL of catalyst ink on a rotating disc electrode, and naturally drying. The scan rate for the oxygen reduction test was 10 mV/s. Stability test at 0.1MHClO saturated with oxygen 4 And (3) testing in an aqueous solution by adopting a cyclic voltammetry method, wherein the scanning range is 0.6-1V vs RHE, the scanning speed is 50mV/s, and the number of scanning circles is 5000 circles and 10000 circles. The results of the rotating disk electrode test of FeCu-N/C metalloid atoms on the catalyst are shown in FIG. 5 and Table 1. As can be seen from FIG. 5 and Table 1, FeCu-N/C metalloid atoms in this example have good durability to the catalyst, and the oxygen reduction half-wave potential drop of the catalyst after 10000 cyclic voltammetry scans was 5mV (below 10 mV). The stability of Fe monatomic catalyst (Fe-SA) and FeCu dimono catalyst (FeCu-SA) is obviously different from that of FeCu-N/C catalyst, and the half-wave potential drop values of the Fe monatomic catalyst (Fe-SA) and the FeCu dimono catalyst (FeCu-SA) are respectively 28mV and 30mV under the same test conditions.
TABLE 1
Example 2
(1) The chemical formula of the metal precursor in this example is MnNi (C) 27 H 24 N 4 O 2 )Cl 2 The structural formula is as follows:
the preparation method of the metal precursor comprises the following steps: 10mL of a methanol solution of 0.493g of 2-hydroxy-5-methyl-m-phthalaldehyde and 1mL of a methanol solution of 0.162g of o-phenylenediamine were mixed, followed by addition of 0.3g of solid Ni (OAc) 2 ·H 2 O, stirring for 30min at 40 ℃, and filtering and drying the obtained solid. 4mL of a methanol solution containing 0.48g of the above solid and 0.2g of MnCl 2 ·4H 2 3mL of methanol solution of O, adding 1mL of methanol solution of 0.084mL of propane diamine, stirring for 48 hours at room temperature, filtering and drying the obtained precipitate to obtain a complex precursor MnNi (C) 27 H 24 N 4 O 2 )Cl 2 。
(2) The preparation method of the MnNi-N/C dissimilar metal atom pair catalyst in the embodiment comprises the following steps:
s101: 1.6g of Zn (NO) are weighed 3 ) 2 ·6H 2 O, dissolved in 80mL of methanol, and 3.7g of 2-methylimidazole were weighed out and dissolved in 80mL of methanol. Mixing the two solutions, stirring at room temperature for 24 hours, centrifugally separating, washing with methanol, and drying to obtain powder. And (3) placing 400mg of the powder into a porcelain boat, heating to 900 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere, keeping for 3 hours, and naturally cooling to obtain the nitrogen-doped carbon material carrier derived from the metal-organic framework ZIF-8.
S102: weighing 100mg of the nitrogen-doped carbon material carrier, dispersing in 20mL of methanol, and weighing 25mg of MnNi (C) 27 H 24 N 4 O 2 )Cl 2 The complex is dissolved in 20mL of mixed solvent with the volume ratio of water to methanol being 1: 1. Mixing the two dispersions, stirring overnight at room temperature, filtering, and drying to obtain catalyst preform powder.
S103: putting the catalyst preformed product powder into a porcelain boat, heating to 900 ℃ at 5 ℃/min under the nitrogen atmosphere, and keeping the temperature for 3 h. Then naturally cooling to obtain the MnNi-N/C dissimilar metal atom pair catalyst in the embodiment. Wherein the mass sum of Mn and Ni accounts for 1.5 percent of the mass of MnNi-N/C dissimilar metal atoms to the catalyst. In the MnNi-N/C dissimilar metal atom pair catalyst in this example, the distance between Mn and Ni in the atom pair was 3.1 angstroms.
(3) The MnNi-N/C metalloid atoms in this example were tested on the catalyst.
The MnNi-N/C dissimilar metal atom pair catalyst in this example was subjected to an oxygen reduction performance test using a rotating disk electrode. The test method comprises the following steps: at 25 deg.C, the electrolyte used is 0.5M H saturated with oxygen 2 SO 4 In the water solution, a working electrode is a glassy carbon material rotating disc electrode with the diameter of 5mm, and the rotating speed is 1600 rpm; the counter electrode is a platinum wire, and the reference electrode is a saturated Ag/AgCl electrode. The reference electrode potential was corrected by a reversible hydrogen electrode. Weighing 5mg MnNi-N/C dissimilar metal atom pair catalyst, adding 990 muL isopropanol and 10 muL 5% nafion solution, performing ultrasonic dispersion to prepare catalyst ink, dripping 25 muL of catalyst ink on a rotating disc electrode, and naturally drying. The scan rate for the oxygen reduction test was 10 mV/s. Stability test at 0.5M H saturated with oxygen 2 SO 4 And (3) testing in an aqueous solution by adopting a cyclic voltammetry method, wherein the scanning range is 0.6-1V vs RHE, the scanning speed is 50mV/s, and the number of scanning circles is 5000 circles and 10000 circles. The results of the rotating disk electrode tests of MnNi-N/C metalloid atoms on the catalyst are shown in FIG. 6 and Table 2. As can be seen from FIG. 6 and Table 2, the MnNi-N/C metalloid atom pair catalyst in this example is at 0.5M H 2 SO 4 The half-wave potential under the condition is 0.630V vs RHE, and the half-wave potential is reduced by only 8mV after 10000 cycles.
TABLE 2
Example 3
(1) The chemical formula of the metal precursor in this example is CoZn (C) 35 H 37 N 6 O 3 ) The structural formula is as follows:
the preparation method of the metal precursor comprises the following steps: 2-bis { [ (2-pyridylmethyl) -aminomethyl]-6- [ (2-hydroxybenzyl) (2-picolyl)]Adding 0.11g of zinc acetate, 0.15g of cobalt nitrate and 0.08g of sodium acetate into 0.265g of methanol solution of-aminomethyl } -4-methylphenol, stirring at 40 ℃ for 30 minutes, standing for 3 days, and filtering to obtain a complex precursor CoZn (C) 35 H 37 N 6 O 3 )。
(2) The preparation method of the CoZn-N/C dissimilar metal atom pair catalyst in the embodiment comprises the following steps:
s101: 500mg of Ketjenblack (Ketjenblack EC-300J) and 30mg of CoZn (C) were weighed out 35 H 37 N 6 O 3 ) And dispersing the complex in 80mL of methanol, performing ultrasonic treatment for 30min, stirring for 12h, and performing rotary evaporation to obtain black catalyst preformed product powder.
S102: 100mg of the catalyst preform powder is placed in a porcelain boat, heated to 600 ℃ at 5 ℃/min under the argon atmosphere, and kept for 2 h. And then naturally cooling to obtain the CoZn-N/C dissimilar metal atom pair catalyst in the embodiment. Wherein the mass sum of Co and Zn accounts for 1 percent of the mass of CoZn-N/C dissimilar metal atoms to the catalyst. In the CoZn-N/C dissimilar metal atom pair catalyst in this example, the distance between Co and Zn in the atom pair was 3.5 angstroms.
(3) The CoZn-N/C dissimilar metal atoms in this example were tested against the catalyst.
The CoZn-N/C dissimilar metal atom pair catalyst in this example was subjected to an oxygen reduction performance test using a rotating disk electrode. The test method was the same as in example 1. The results of the rotating disk electrode tests of CoZn-N/C dissimilar metal atom pair catalysts are shown in FIG. 7 and Table 3. As can be seen from FIG. 7 and Table 3, the CoZn-N/C dissimilar metal atom pair catalyst in this example was in 0.1M HClO 4 The half-wave potential under the condition is 0.725V vs RHE, and the half-wave potential is reduced by only 9mV after 10000 cycles.
TABLE 3
Example 4
(1) The chemical formula of the metal precursor in this example is FeCo (C) 11 H 5 O 6 ) The structural formula is as follows:
the preparation method of the metal precursor comprises the following steps: 0.7g of [ CpFe (CO) 2 ] 2 And 0.68g Co 2 (CO) 8 Dispersing in 120mL of freshly distilled toluene, illuminating for 16 hours by a 250W xenon lamp, filtering and drying a product, and separating by column chromatography to obtain a complex precursor FeCo (C) 11 H 5 O 6 )。
(2) The preparation method of the FeCo-N/C dissimilar metal atom pair catalyst in the embodiment comprises the following steps:
s101: 1.6g of Zn (NO) are weighed 3 ) 2 ·6H 2 O, dissolved in 80mL of methanol, and 3.7g of 2-methylimidazole were weighed out and dissolved in 80mL of methanol. Mixing the two solutions, stirring at room temperature for 24 hours, centrifugally separating, washing with methanol, and drying to obtain powder. And (3) placing 400mg of the powder into a porcelain boat, heating to 900 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere, keeping for 3 hours, and naturally cooling to obtain the nitrogen-doped carbon material carrier derived from the metal-organic framework ZIF-8.
S102: the above nitrogen-doped carbon material support and 0.15g of FeCo (C) 11 H 5 O 6 ) And dispersing the complex in 80mL of methanol, stirring at room temperature for 24h, centrifuging, washing with methanol, and drying to obtain catalyst preform powder.
S103: putting the catalyst preformed product powder into a porcelain boat, heating to 900 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, and keeping for 2 h. Then naturally cooling to obtain the FeCo-N/C dissimilar metal atom pair catalyst in the embodiment. Wherein the mass sum of Fe and Co accounts for 2 percent of the mass of FeCo-N/C dissimilar metal atoms to the catalyst. In the FeCo-N/C dissimilar metal atom pair catalyst in this example, the distance between Fe and Co in the atom pair was 2.5 angstroms.
(3) The catalyst was tested for FeCo-N/C metalloid atoms in this example.
The oxygen reduction performance of the FeCo-N/C dissimilar metal atom pair catalyst in this example was tested using a rotating disk electrode. The test method was the same as in example 1. The results of the rotating disk electrode test of FeCo-N/C dissimilar metal atoms versus catalyst are shown in FIG. 8 and Table 4. As can be seen from FIG. 8 and Table 4, the FeCo-N/C metalloid atom pair catalyst in this example was at 0.1M HClO 4 The half-wave potential under the condition is 0.775V vs RHE, and the half-wave potential is reduced by only 5mV after 10000 cycles.
TABLE 4
Example 5
(1) The chemical formula of the metal precursor in this example is FeZn (C) 54 H 13 F 20 N 6 O) Cl, having the formula:
the preparation method of the metal precursor comprises the following steps: under the protection of nitrogen, 5,10,15, 20-tetra (pentafluorophenyl) - [26 ]]Hexaporphyrin 150mg was dissolved in 150mL of dichloromethane and 15mL of methanol. 110mg of sodium acetate and 180mg of zinc chloride were added and stirred for 5 hours. The solution was poured into a large volume of water, extracted with dichloromethane, the solvent was dried by spinning to give a solid powder, and the solid powder was separated by column chromatography and recrystallized to give compound 1. 50mg of Compound 1 was dissolved in 50mL of chloroform, and 3mL of trifluoroacetic acid was added. The solution is poured into water, extracted by dichloromethane, the solvent is dried by spinning to obtain solid powder, and the solid powder is separated by column chromatography and recrystallized to obtain the compound 2. 38mg of Compound 2 was dissolved in 30mL of dichloromethane, and 5mg of sodium acetate and 3.5mg of anhydrous ferrous chloride were added thereto, followed by stirring for 48 hours. The solution is poured into water toExtracting with dichloromethane, spin-drying solvent to obtain solid powder, separating with column chromatography, and recrystallizing to obtain FeZn (C) as complex precursor 54 H 13 F 20 N 6 O)Cl。
(2) The preparation method of the FeZn-N/C dissimilar metal atom pair catalyst in the embodiment comprises the following steps:
s101: 1.6g of Zn (NO) are weighed out 3 ) 2 ·6H 2 O, dissolved in 80mL of methanol, and 3.7g of 2-methylimidazole were weighed out and dissolved in 80mL of methanol. Mixing the two solutions, stirring at room temperature for 24 hours, centrifugally separating, washing with methanol, and drying to obtain powder. And (3) placing 400mg of the powder into a porcelain boat, heating to 900 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere, keeping for 3 hours, and naturally cooling to obtain the nitrogen-doped carbon material carrier derived from the metal-organic framework ZIF-8.
S102: 100mg of the nitrogen-doped carbon material carrier was weighed, dispersed in 20mL of methanol, and 10mg of FeZn (C) was weighed 54 H 13 F 20 N 6 O) Cl complex was dissolved in 20mL of methanol. Mixing the two dispersions, stirring overnight at room temperature, filtering, and drying to obtain catalyst preform powder.
S103: and (3) putting the catalyst preformed product powder into a porcelain boat, heating to 800 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, and keeping for 2 hours. And then naturally cooling to obtain the FeZn-N/C dissimilar metal atom pair catalyst in the embodiment. Wherein the mass sum of Fe and Zn accounts for 1 percent of the mass of FeZn-N/C dissimilar metal atoms to the catalyst. In the FeZn-N/C dissimilar metal atom pair catalyst in this example, the distance between Fe and Zn in the atom pair was 3.6 angstroms.
(3) The catalyst was tested for the FeZn-N/C metalloid atoms in this example.
The FeZn-N/C dissimilar metal atom pair catalyst in this example was subjected to an oxygen reduction performance test using a rotating disk electrode. The test method was the same as in example 2. The results of the rotating disk electrode tests of FeZn-N/C dissimilar metal atoms versus catalyst are shown in FIG. 9 and Table 5. As can be seen from FIG. 9 and Table 5, the FeZn-N/C metalloid atom pair catalyst in this example is at 0.5M H 2 SO 4 Half-wave potential under the condition of 0764V vs RHE, the half-wave potential dropped only 10mV after 10000 cycles.
TABLE 5
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims, and the description and the drawings can be used for explaining the contents of the claims.
Claims (10)
1. A dissimilar metal atom pair catalyst comprising a support and an active component, wherein the active component is supported on the support, the active component comprises a first metal atom and a second metal atom, the first metal atom is Mn, Fe or Co, the second metal atom is Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and the first metal atom and the second metal atom are different.
2. A dissimilar metal atom pair catalyst as claimed in claim 1, wherein said active component comprises a plurality of atom pairs, each said atom pair comprising one said first metal atom and one said second metal atom.
3. The dissimilar metal atom pair catalyst according to claim 2, wherein the distance between said first metal atom and said second metal atom in each of said atom pairs is from 2 angstroms to 4 angstroms; and/or the presence of a gas in the atmosphere,
the mass percentage of the sum of the first metal atom and the second metal atom is 0.3 to 4 percent in terms of the mass percentage of the dissimilar metal atom to the catalyst; and/or the presence of a gas in the gas,
the carrier comprises at least one of carbon black, activated carbon, carbon nanotubes, graphene, mesoporous carbon, carbon nitride, nitrogen-doped carbon materials and an organic framework.
4. A preparation method of a dissimilar metal atom pair catalyst is characterized by comprising the following steps:
mixing a metal precursor and a carrier in a solvent to prepare a mixture; the metal precursor comprises a first metal atom and a second metal atom, the first metal atom is Mn, Fe or Co, the second metal atom is Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and the first metal atom and the second metal atom are different;
carrying out solid-liquid separation treatment on the mixture to obtain a solid phase serving as a catalyst preform;
and carrying out pyrolysis treatment on the catalyst preform under the protective gas atmosphere.
5. The method for producing a dissimilar metal atom pair catalyst according to claim 4, wherein the metal precursor comprises a metal carbonyl compound including the first metal atom and the second metal atom therein; alternatively, the first and second electrodes may be,
the metal precursor comprises at least one of compounds shown in formulas I-III;
wherein M is 1 And M 2 One of Mn, Fe or Co, the other of Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ru, Rh, Pd, Ir, Pt, Ag or Au, and M 1 And M 2 Different;
n is an integer of 0 to 4; x is a non-metallic group;
R 1 selected from substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 An aryl group; r 4 、R 5 、R 6 、R 11 、R 12 、R 13 、R 14 And R 16 Each independently selected from-H, -D, substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 An aryl group; r 2 And R 3 Each independently selected from-H, -D, substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 Aryl, or R 2 、R 3 And M 2 Connecting to form a ring; r 7 、R 8 、R 9 And R 10 Each independently selected from-H, -D, substituted or unsubstituted C 1 ～C 6 Alkyl, substituted or unsubstituted C 6 ～C 20 Aryl, or R 7 And M 1 Linked to form a ring, R 8 And M 1 Linked to form a ring, R 9 And M 2 Linked to form a ring, R 10 And M 2 Connecting to form a ring; r is 15 Selected from O or S, or R 15 、M 1 、M 2 Are connected.
6. The process of claim 5, wherein formula I is selected from the group consisting of structures of formulas I-1, formula II is selected from the group consisting of structures of formulas II-1, and formula III is selected from the group consisting of structures of formulas III-1:
wherein R is 17 Selected from substituted or unsubstituted C 1 ～C 6 Alkyl, toSubstituted or unsubstituted C 6 ～C 20 And (3) an aryl group.
7. The method for preparing a dissimilar metal atom pair catalyst according to any one of claims 4 to 6, wherein the temperature of the pyrolysis treatment is 300 ℃ to 1000 ℃; and/or the presence of a gas in the gas,
the time of the pyrolysis treatment is 0.5 h-4 h.
8. The method for preparing a catalyst comprising a pair of dissimilar metal atoms according to any one of claims 4 to 6, wherein the solvent comprises at least one of water, an alcohol, an amide and a nitrile.
9. A fuel cell electrode comprising the dissimilar metal atom pair catalyst according to any one of claims 1 to 3 or the dissimilar metal atom pair catalyst produced by the production method according to any one of claims 4 to 8.
10. A fuel cell comprising an anode, a cathode, and an electrolyte, wherein the anode and/or the cathode comprises the dissimilar metal atom pair catalyst of any one of claims 1 to 3; alternatively, the first and second electrodes may be,
the anode and/or the cathode comprise the dissimilar metal atom pair catalyst prepared by the preparation method of any one of claims 4 to 8.
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