CN115275230A - Heteroatom-loaded polymetallic porphyrin material, synthesis method thereof and application thereof in zinc-air battery - Google Patents
Heteroatom-loaded polymetallic porphyrin material, synthesis method thereof and application thereof in zinc-air battery Download PDFInfo
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- CN115275230A CN115275230A CN202210950540.0A CN202210950540A CN115275230A CN 115275230 A CN115275230 A CN 115275230A CN 202210950540 A CN202210950540 A CN 202210950540A CN 115275230 A CN115275230 A CN 115275230A
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- heteroatom
- loaded
- porphyrin
- polymetaphorin
- transition metal
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 51
- 238000001308 synthesis method Methods 0.000 title description 2
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 150000004033 porphyrin derivatives Chemical class 0.000 claims abstract description 8
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- 230000002194 synthesizing effect Effects 0.000 claims abstract 7
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- -1 amino-substituted benzene ring Chemical group 0.000 claims description 19
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 16
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Images
Classifications
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
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- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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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
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- 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
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Abstract
The invention discloses a heteroatom-loaded polymetallic porphyrin material, a synthetic method thereof and application thereof in a zinc-air battery. The heteroatom-loaded polymetaphorin material has the following repeating structural unit:
wherein R is a conjugated connecting unit containing a heteroatom; m is a transition metal element. The preparation method of the material comprises the steps of firstly synthesizing the porphyrin derivative doped with the heteroatom, then carrying out self-polymerization through oxidation, and coordinating with transition metal ions through a solvothermal method to obtain the polymetallic porphyrin material loaded with the heteroatom, wherein the polymetallic porphyrin material is used as an air cathode of a zinc-air battery and shows excellent difunctional activity in alkaline electrolyte.
Description
Technical Field
The invention relates to a catalytic material, in particular to a heteroatom-loaded polymetallic porphyrin material, a synthetic method and application thereof in a zinc-air battery, and belongs to the technical field of zinc-air batteries.
Background
The exponential increase in world energy demand and the rapid consumption of fossil fuels have stimulated the development of human society and the advancement of technology, and therefore, the development of new renewable energy storage and conversion devices is a strategic goal of energy transformation in all countries of the world. Among new-generation new energy devices, zinc-air batteries driven by an Oxygen Reduction Reaction (ORR) and an Oxygen Evolution Reaction (OER) as a discharging/charging process have been receiving wide attention from researchers due to their advantages of low price, high energy density, and environmental friendliness. However, slow ORR and OER kinetics on zinc-air battery air cathodes severely hamper their practical application and development.
Researchers have found that precious metals such as platinum, iridium, ruthenium, etc. have high ORR or OER catalytic capability, but the disadvantages of high price, limited reserves, and poor durability limit the large-scale application of zinc-air batteries. At present, the research and application of porphyrin polymer have related development in the field of electrocatalysis. Porphyrin macromolecules providing tetracoordinated M-N for metal ions 4 The structure has the unique electronic characteristics of high atom utilization rate, good selectivity and the like, and due to the high designability of the porphyrin molecular structure, heteroatom functional groups are respectively connected with porphyrin rings to obtain polymer materials with different conjugated structures. To date, preliminary studies have been made on the use of porphyrin polymers as electrocatalysts, and in chinese patent (CN 111342057A), metalloporphyrin and sulfur-doped graphene are compounded to obtain a multifunctional electrocatalyst, but the S source is not introduced in situ, and the active sites of heteroatom doping and ORR and OER are not completely understood. In Chinese patent (CN 110137516B), the solvent thermal reaction condition is adopted, and the doped Sn (OH) is used X Under the condition of mixed solvent of 5,10,15, 20-tetra (amino) phenyl porphyrin, 2, 6-dimethyl pyridine and ferric trichloride, acetic acid is catalyzed and condensed, and high-temperature carbonization is carried out to synthesize the covalent organic polymer loaded by Sn-Fe, however, after the method is carried out high-temperature treatment, metal particles are agglomerated, metal particles are introduced, and the atom utilization is reducedAnd (4) the ratio. In Chinese patent (CN 113802145A), iron salt and porphyrin monomer are added into an organic solvent, a mixed toluene solution of fullerene is added after the reaction is completed, and then the mixture is washed, dried and pyrolyzed in a hydrogen/argon mixed gas to obtain the metal-modified fullerene/porphyrin catalyst.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide a heteroatom-loaded polymetaphorin material, which has a space conjugated cross-linked structure, wherein a large amount of heteroatoms (N and S) are accurately doped on a conjugated cross-linked organic framework, the chemical activity of the conjugated cross-linked organic framework is essentially changed due to the high heteroatom doping amount, a large amount of adsorption active sites of oxygen molecules and oxygen intermediates are generated, and simultaneously metal ions are coordinated with porphyrin through complexation to form four-coordinated M-N 4 The catalytic active sites maximally improve the utilization rate of catalytic active metal elements, effectively regulate the interaction between the catalytic active sites and oxygen intermediates, greatly improve the conductivity and stability of the material due to the conjugated cross-linked organic framework structure, and the whole material shows the comprehensive properties of strong adsorption capacity of oxygen molecules and oxygen intermediates, high catalytic activity, high conductivity, good stability and the like, so that the material is particularly suitable for being used as an air cathode catalyst of a zinc-air battery.
The second purpose of the invention is to provide a synthetic method of heteroatom-loaded polymetaphorin material, which is characterized in that different heteroatom groups are easily introduced into porphyrin rings by selecting different polymeric monomers to synthesize the material, the fine regulation and control of the catalytic activity of the material are realized by controlling the introduction proportion of transition metal ions, the arrangement and the growth of polymer molecular chains are influenced by changing the polymerization reaction conditions, the structure and the chain length of the polymer are easily regulated, and the method is simple, convenient and effective, has mild conditions and is favorable for large-scale production and application prospect.
The third purpose of the invention is to provide the application of the heteroatom-loaded polymetaphorin catalytic material in the zinc-air battery, and the material is applied to the air cathode of the zinc-air battery and shows excellent electrocatalytic performance in the reaction of Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER).
In order to achieve the technical object, the present invention provides a heteroatom-loaded polymetaphorin material having a repeating structural unit represented by formula 1:
wherein, the first and the second end of the pipe are connected with each other,
r is a conjugated connecting unit containing hetero atoms;
m is a transition metal element.
The heteroatom-loaded polymetallic porphyrin material provided by the invention is in a space conjugated structure formed by the cross-linking of porphyrin units through aryl connecting units, a large conjugated system is taken as an organic framework, the transfer of electrons is facilitated, the conductivity of the material is improved, the stability of the material is improved through a rigid conjugated structure, a large amount of heteroatoms are doped on the organic framework, the adsorption activity of the material on oxygen molecules and oxygen intermediates is greatly improved, the catalytic activity of the material is improved, and the heteroatoms (nitrogen) in a porphyrin ring and transition metal ions form M-N through coordination 4 The catalytic activity sites are ensured by utilizing the periodic repeating structure of porphyrin units in the porphyrin-based polymer material, meanwhile, the fine regulation and control of the catalytic activity of the material can be realized by the heteroatom introduced by the aryl connecting unit, the metal catalytic activity center and the doped heteroatoms (N and S) have special synergistic effect, the electrocatalytic activity is obviously promoted, and the material has excellent bifunctional catalytic ability.
As a preferred embodiment, the heteroatom-containing conjugated linking unit comprises an aromatic heterocycle or an aromatic ring containing a heteroatom substituent. The heteroatom-containing substituent in the aromatic ring containing the heteroatom-containing substituent may be a polar group containing heteroatoms such as oxygen, sulfur, nitrogen, and the like, specifically, a phenolic hydroxyl group, a phenolic mercapto group, an amino group, and the like, and the number of the substituents is not limited, and may be one or two. The substitution position of the substituent is not limited but is not occupiedThe aromatic ring may be a benzene ring or a naphthalene ring, etc., depending on the crosslinking site, and is preferably a benzene ring. In a more preferred embodiment, the heteroatom-substituted aromatic ring is an amino-substituted phenyl group. The aromatic heterocyclic ring can be a five-membered ring or a six-membered ring containing heteroatoms such as oxygen, sulfur, nitrogen and the like, and as a more preferable scheme, the aromatic heterocyclic ring is thienyl. The pair M-N can be realized by introducing different heteroatoms through selecting different conjugated connecting units containing the heteroatoms 4 The catalytic activity of the catalytic active site is effectively regulated. The following are illustrative of several common heteroatom-containing conjugated linking units:
as a preferable mode, the transition metal element is at least one of iron, cobalt, nickel or manganese.
The invention also provides a synthetic method of the heteroatom-loaded polymetallic porphyrin material, which comprises the following steps:
1) Pyrrole and aromatic aldehyde compound are subjected to condensation reaction to obtain porphyrin derivative;
2) Carrying out oxidation polymerization reaction on the porphyrin derivative to obtain a porphyrin-based polymer;
3) Carrying out solvothermal reaction on a porphyrin-based polymer and a transition metal salt to obtain the porphyrin-based polymer;
the aromatic aldehyde compound has a structure represented by formula 2:
wherein R is a conjugated group containing a heteroatom.
In the aromatic aldehyde compound, R can be an aromatic heterocycle or an aromatic ring containing heteroatom substituent. The preferred aromatic aldehyde compound is at least one of p-aminobenzaldehyde, 3-thiophenecarboxaldehyde and 2-thiophenecarboxaldehyde. Porphyrin derivatives with different chemical properties are obtained by selecting different aromatic aldehyde compounds to react with pyrrole, the porphyrin derivatives have excellent metal coordination capacity, transition metal catalytic active sites can be introduced, meanwhile, heteroatom groups are introduced by the aromatic aldehyde compounds, and the synergy exists between the heteroatom groups and the metal catalytic active sites, so that the catalytic activity is enhanced, and the material has the optimal bifunctional catalytic activity.
As a preferred embodiment, the conditions of the condensation reaction are: p-toluenesulfonic acid is used as a catalyst to react for 1 to 3 hours at a temperature of between 80 and 120 ℃. The condensation reaction employs DMF as a solvent.
As a preferred embodiment, the conditions of the oxidative polymerization are: adopting persulfate oxidation system, reacting for 12-24 h at 0-50 ℃. The porphyrin polymer synthesized under the optimized reaction condition has a large conjugated structure and is stable in structure. If the reaction temperature is too low, the polymerization reaction speed is slow, and the molecular chain grows slowly; when the reaction temperature is high, the order of molecular chains is reduced, the specific surface area is reduced, and the active sites are not fully exposed. The persulfate may be at least one of ammonium persulfate, potassium persulfate, and sodium persulfate. The molar ratio of the persulfate to the porphyrin derivative is 1: (6 to 12).
As a preferred embodiment, the solvent thermal reaction conditions are as follows: reacting for 4-12 h at 60-150 ℃. Under the optimized reaction condition, the porphyrin structure has strong coordination capacity to metal ions to form closely-arranged M-N 4 The active sites provide advantages, compared with the conventional catalyst preparation process, the high-temperature annealing step is reduced, and the metal agglomeration caused by pyrolysis is avoided. Too high a reaction temperature can result in carbonization of organic molecules, loss of macromolecular conjugated structures, and too low a temperature is insufficient for the formation of metal-nitrogen bonds.
As a preferred embodiment, the molar ratio of the porphyrin-based polymer to the transition metal salt is 1: (5-10). The transition metal salt is common water-soluble transition metal salt, such as nitrate, chloride, and the like. By introducing transition and porphyrin structure to form M-N 4 The structure and the central metal are beneficial to the adsorption of oxygen intermediates, and the catalytic activity of the material is improved. If gold is not formedBelongs to a catalytic active site, is not beneficial to the adsorption of oxygen molecules, oxygen intermediates and other oxygen substances, and the catalytic performance cannot be improved. The optimized dosage of the transition metal salt can ensure that the porphyrin structure sites are fully complexed with transition metal ions, and the active sites are fully utilized. With a lower proportion of transition metal salts, porphyrin structural sites are not fully complexed with transition metal ions, and the lack of transition metal catalytically active sites results in relatively poor catalytic capabilities. Too high a proportion of metal salts forms too many transition metal catalytically active sites, resulting in competitive masking of the transition metal catalytically active sites and also inhibiting the catalytic activity.
In a preferred embodiment, the solvent thermal reaction uses at least one of N, N-dimethylformamide, methanol, ethanol, chloroform, and acetone as a solvent.
The invention also provides an application of the heteroatom-loaded polymetallic porphyrin catalytic material as an air cathode catalyst of a zinc-air battery.
The heteroatom-loaded polymetallic porphyrin catalytic material disclosed by the invention is applied as an air cathode catalyst of a zinc-air battery, and shows dual catalytic activities of ORR and OER.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects;
1) The heteroatom-loaded polymetallic porphyrin catalytic material provided by the invention is formed by the cross-linking of porphyrin units through conjugated connecting units, and the heteroatom and transition metal are doped in the organic framework at the same time, so that the whole material has the comprehensive properties of strong adsorption capacity of oxygen molecules and oxygen intermediates, high catalytic activity, high conductivity, good stability and the like. The conjugated crosslinked organic framework structure of the material greatly improves the conductivity and stability of the material, a large number of heteroatoms (N and S) are accurately doped on the conjugated crosslinked organic framework, the chemical activity of the conjugated crosslinked organic framework is essentially changed due to the high heteroatom doping amount, a large number of adsorption active sites of oxygen molecules and oxygen intermediates are generated, and simultaneously metal ions are coordinated with porphyrin through complexation to form four-coordinated M-N 4 The catalytic active sites maximally improve the utilization rate of the catalytic active metal elements and are effective at the same timeThe interaction between the catalytic active site and the oxygen intermediate is regulated, so that the whole material shows the comprehensive properties of strong adsorption capacity of oxygen molecules and the oxygen intermediate, high catalytic activity, high conductivity, good stability and the like, and is particularly suitable for being used as an air cathode catalyst of a zinc-air battery.
2) The preparation method of the heteroatom-loaded polymetallic porphyrin catalytic material provided by the invention is simple, the reaction condition is mild and controllable, the catalytic activity of the material is easily finely adjusted by changing the type and the amount of the metal salt and the polymerization monomer, and compared with the existing traditional preparation method of the metal-nitrogen-carbon material, the heteroatom-loaded polymetallic porphyrin catalytic material does not need high-temperature pyrolysis, and the agglomeration of metal sites is avoided.
3) The polymetallic porphyrin with the fine control heteroatom loading prepared by the invention is used as an air cathode catalytic material of a zinc-air battery, and shows excellent ORR and OER dual-functional activity.
Drawings
FIG. 1 is an ORR polarization curve in 0.1M KOH and OER polarization curve in 1M KOH of the N atom-loaded polyporphyrin prepared in example 1 of the present invention.
FIG. 2 is an ORR polarization curve in 0.1M KOH and an OER polarization curve in 1M KOH of the N-atom-loaded polypobaloporphyrin prepared in example 2 of the present invention.
FIG. 3 shows N-loaded poly (iron cobalt porphyrin) and Pt/C + IrO according to example 3 of the present invention 2 ORR polarization curve in 0.1M KOH versus OER polarization curve in 1M KOH versus.
FIG. 4 is a Fourier infrared transform spectrum of N-atom-loaded polyferrocobalt porphyrin prepared in example 3 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, which should not be construed as limiting the scope of the invention.
Example 1 (comparative example)
Preparation of a polyporphyrin catalyst loaded with N atoms:
dissolving pyrrole (1.44 mmol) and p-aminobenzaldehyde (1.44 mmol) in 30mL of N, N-dimethylformamide, adding p-toluenesulfonic acid (1.44 mmol) and refluxing at 100 ℃ for 2h to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin; dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin in 100mL of 1M hydrochloric acid, reacting at 40 ℃ for 16h by using potassium persulfate (9.6 mmol), generating black precipitate after 1min of reaction, washing off excessive oxidant by using 1M hydrochloric acid, and filtering to obtain the N atom-loaded polyporphyrin catalyst.
The activity of the N-atom-loaded polyporphyrin catalyst is detected by a three-electrode system, wherein a rotating disk electrode is used as a working electrode, a platinum mesh electrode is used as a counter electrode, and a silver chloride electrode is used as a reference electrode. The specific working electrode manufacturing steps are as follows: 2.5mg of the sample and 2.5mg of acetylene black were dispersed in 800. Mu.L of an isopropyl alcohol solution, 40. Mu.L of a 5% Nafion solution and 160. Mu.L of an aqueous solution were added, and the catalyst ink was ultrasonically dispersed for 30min to uniformly disperse the catalyst in the solution. 10 μ L of catalyst ink was coated on a rotating disk electrode and electrochemical tests were performed using an electrolyte into which saturated oxygen was introduced, selecting a fixed potential range and the rotation rate of the disk electrode.
As shown in FIG. 1, E in ORR polarization curve of N atom-loaded polyporphyrin catalyst prepared in example 1 1/2 0.63V and small limiting current density, 10mAcm in OER polarization curve -2 The potential of (2) is 1.88V, and it is clear that the electrocatalytic performance of a pure N atom-loaded polyporphyrin catalyst is general. This is mainly due to the poor conductivity of the porphyrin polymer and the lack of active sites.
Example 2
Preparation of N atom-loaded cobaltoporphyrin:
dissolving pyrrole (1.44 mmol) and p-aminobenzaldehyde (1.44 mmol) in 30mL of N, N-dimethylformamide, adding p-toluenesulfonic acid (1.44 mmol) and refluxing at 100 ℃ for 2h to obtain 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin; dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin (1.2 mmol) in 100mL of 0.5M hydrochloric acid, reacting for 12h at 20 ℃ by using ammonium persulfate (13.2 mmol), generating black precipitate after 1min of reaction, washing off excessive oxidant by using 1M hydrochloric acid, and filtering to obtain the poly-porphyrin loaded with N atoms; n atom-loaded polyporphyrin (100 mg) and cobalt nitrate hexahydrate (9.6 mmol) were dissolved in 50mL of methanol, refluxed at 67 ℃ for 8h, and the organic solvent was removed by rotary evaporation to obtain N atom-loaded polyporphyrin.
The activity of the N-atom-loaded cobalt porphyrin catalyst is detected by a three-electrode system, wherein a rotating disc electrode is used as a working electrode, a platinum mesh electrode is used as a counter electrode, and a silver chloride electrode is used as a reference electrode. The specific working electrode manufacturing steps are as follows: 2.5mg of the sample and 2.5mg of acetylene black were dispersed in 800. Mu.L of an isopropyl alcohol solution, 40. Mu.L of a 5% Nafion solution and 160. Mu.L of an aqueous solution were added, and the catalyst ink was ultrasonically dispersed for 30min to uniformly disperse the catalyst in the solution. 10 μ L of catalyst ink was coated on a rotating disk electrode and electrochemical tests were performed using an electrolyte into which saturated oxygen was introduced, selecting a fixed potential range and the rotation rate of the disk electrode.
As shown in FIG. 2, E in ORR polarization curve of N atom-loaded polypobalporphyrin catalyst prepared in example 2 1/2 0.80V and a significant increase in the limiting current density, which means that the metal sites can significantly improve the kinetics of the oxygen reduction reaction and the conductivity of the material. 10mA cm in OER polarization curve -2 The potential of the catalyst is 1.73V, and compared with the comprehensive electrocatalysis performance of a metal-free catalyst, the comprehensive electrocatalysis performance of the catalyst is obviously improved.
Example 3
Preparing poly (iron cobalt porphyrin) loaded with N atoms:
dissolving pyrrole (1.44 mmol) and p-aminobenzaldehyde (1.44 mmol) in 30mL of N, N-dimethylformamide, adding p-toluenesulfonic acid (1.44 mmol) and refluxing at 100 ℃ for 2h to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin; dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin (1.2 mmol) in 100mL of 1M hydrochloric acid, reacting at 0 ℃ for 12h by using ammonium persulfate (14.4 mmol), generating black precipitate after 1min of reaction, washing off excessive oxidant by using 1M hydrochloric acid, and filtering to obtain the N atom-loaded polyporphyrin; dissolving poly-porphyrin (100 mg) loaded with N atoms, cobalt nitrate hexahydrate (6 mmol) and ferric nitrate nonahydrate (6 mmol) in 50mL of N, N-dimethylformamide, refluxing at 153 ℃ for 4h, and removing the organic solvent by rotary evaporation to obtain the poly-iron-cobalt porphyrin catalyst loaded with N atoms.
The activity of the N-atom-loaded polyferrocobalt porphyrin catalyst is detected by a three-electrode system, wherein a rotary disc electrode is used as a working electrode, a platinum mesh electrode is used as a counter electrode, and a silver chloride electrode is used as a reference electrode. The specific working electrode manufacturing steps are as follows: 2.5mg of the sample and 2.5mg of acetylene black were dispersed in 800. Mu.L of an isopropyl alcohol solution, 40. Mu.L of a 5% Nafion solution and 160. Mu.L of an aqueous solution were added, and the catalyst ink was ultrasonically dispersed for 30min to uniformly disperse the catalyst in the solution. 10 μ L of catalyst ink was coated on a rotating disk electrode and electrochemical tests were performed using an electrolyte into which saturated oxygen was introduced, selecting a fixed potential range and the rotation rate of the disk electrode.
As shown in FIG. 3, E in ORR polarization curve of N atom-loaded polyperrocobalt porphyrin catalyst prepared in example 3 1/2 0.77V, E of oxygen reduction reaction decreased with cobalt content in the sample 1/2 With negative shift of limiting current density, 10mAcm in OER polarization curve -2 The potential of (a) reaches 1.59V, and simultaneously, the potential has the maximum current density, which indicates the strengthening mechanism of the catalytic performance of the oxygen evolution reaction by the synergistic effect between the bimetallic sites of iron and cobalt. For comparison, pt/C + IrO 2 E of the catalyst 1/2 And 10mAcm -2 The potential of the catalyst is smaller than that of the poly (iron cobalt porphyrin) catalyst loaded with N atoms, which shows that the catalyst has the same Pt/C + IrO 2 The catalyst has equivalent and even more excellent catalytic performance.
FIG. 4 shows a Fourier transform infrared spectrum of N-loaded polyferrocobalt porphyrin at a peak position of 1511cm -1 And 1350cm -1 Corresponding to the vibration of the large ring framework of the porphyrin material, and is 1251cm -1 And 1171cm -1 Corresponds to a stretching vibration of the C-N bond at 894cm -1 The peak position at corresponds to the metal ligand vibration.
Example 4
Preparing poly (iron cobalt porphyrin) loaded with S atoms:
pyrrole (1.44 mmol) and 3-trypan formaldehyde (1.44 mmol) were dissolved in 30mL of N, N-dimethylformamide, p-toluenesulfonic acid (1.44 mmol) was added and refluxed at 100 ℃ for 2h to give 5,10,15, 20-tetrakis (3-thienyl) porphyrin; dissolving 5,10,15, 20-tetra (3-thienyl) porphyrin (1.2 mmol) in 100mL of 1M hydrochloric acid, reacting for 14h at 30 ℃ by using potassium persulfate (10.8 mmol), generating black precipitate after 1min of reaction, washing off excessive oxidant by using 1M hydrochloric acid, and filtering to obtain the polyporphyrin loaded with S atoms; dissolving the polyporphyrin (100 mg) loaded with the S atom, cobalt nitrate hexahydrate (6 mmol) and ferric nitrate nonahydrate (6 mmol) in 50mL of acetone, refluxing at 80 ℃ for 7h, and removing the organic solvent by rotary evaporation to obtain the polyporphyrin catalyst loaded with the S atom. Electrochemical test results show that the polyferro-cobalt porphyrin containing the pentacyclic thiophene S unit has stronger ORR activity than polyferro-cobalt porphyrin loaded with N atoms, and the reason is that in the embodiment, the S element is introduced into the catalyst in situ, and can also be used as a catalytic active site and shorten the diffusion distance of an oxygen intermediate, so that the ORR performance is greatly improved.
Example 5
Preparing poly cobalt manganese porphyrin loaded with S atoms:
pyrrole (1.44 mmol) and 3-trypan formaldehyde (1.44 mmol) were dissolved in 30mL of N, N-dimethylformamide and p-toluenesulfonic acid (1.44 mmol) was added at 100 ℃ under reflux for 2h to give 5,10,15, 20-tetrakis (2-thienyl) porphyrin; dissolving 5,10,15, 20-tetra (2-thienyl) porphyrin (1.2 mmol) in 100mL of 1M hydrochloric acid, reacting for 19 hours at 30 ℃ by using ammonium persulfate (10.8 mmol), generating black precipitate after 1min of reaction, washing off redundant oxidant by using 1M hydrochloric acid, and filtering to obtain the polyporphyrin loaded with S atoms; dissolving the polyporphyrin (100 mg) loaded with the S atom, cobalt nitrate hexahydrate (6 mmol) and manganese nitrate tetrahydrate (6 mmol) in 50mL of chloroform, refluxing at 65 ℃ for 9h, and removing the organic solvent by rotary evaporation to obtain the poly-cobalt-manganese porphyrin loaded with the S atom. In the cobalt-manganese bimetallic porphyrin loaded with the S atoms obtained in the embodiment, the catalysts of different central metals have different oxygen adsorption energies, the adsorption energy of the Fe site to the oxygen molecule is strongest, the adsorption energy of the Co site is second, the adsorption energy of the Mn and Ni sites to the oxygen molecule is relatively weaker, the point to be supplemented is that the adsorption energy is not stronger or better, and the excessively strong adsorption energy means that reactants are difficult to desorb, and the catalytic performance is adjusted by changing the type of the central metal. Electrochemical test results show that the ORR activity of the poly-cobalt-manganese-porphyrin catalyst is reduced and the OER activity is improved compared with that of a poly-iron-cobalt-porphyrin catalyst, and the reason is that the oxygen reduction activity of Mn species is lower than that of Fe species.
Claims (10)
1. A heteroatom-loaded polymetaphorin material, characterized in that: has a repeating structural unit represented by formula 1:
wherein, the first and the second end of the pipe are connected with each other,
r is a conjugated connecting unit containing hetero atoms;
m is a transition metal element.
2. The heteroatom-loaded polymetaphorin material of claim 1, wherein:
the conjugated connecting unit containing the heteroatom comprises an aromatic heterocycle or an aromatic ring containing a heteroatom substituent;
the transition metal element is at least one of iron, cobalt, nickel or manganese.
3. The heteroatom-loaded polymetaphorin material of claim 2, wherein: the aromatic ring containing the heteroatom substituent is an amino-substituted benzene ring; the aromatic heterocycle is a thiophene ring.
4. A method of synthesizing a heteroatom-loaded polymetaphorphyrin material of any one of claims 1 to 3, wherein: the method comprises the following steps:
1) Pyrrole and aromatic aldehyde compound are subjected to condensation reaction to obtain porphyrin derivative;
2) Carrying out oxidation polymerization reaction on the porphyrin derivative to obtain a porphyrin-based polymer;
3) Carrying out solvothermal reaction on a porphyrin-based polymer and a transition metal salt to obtain the porphyrin-based polymer;
the aromatic aldehyde compound has a structure represented by formula 2:
wherein R is a conjugated group containing a heteroatom.
5. The method for synthesizing a heteroatom-loaded polymetaphosphorylic material of claim 1, wherein the method comprises the steps of: the conditions of the condensation reaction are as follows: adopting p-toluenesulfonic acid as a catalyst to react for 1 to 3 hours at a temperature of between 80 and 120 ℃.
6. The method for synthesizing the heteroatom-loaded polymetaphorin material of claim 1, wherein: the conditions of the oxidative polymerization are as follows: adopting persulfate oxidation system, reacting for 12-24 h at 0-50 ℃.
7. The method for synthesizing the heteroatom-loaded polymetaphorin material of claim 1, wherein: the conditions of the solvothermal reaction are as follows: reacting for 4-12 h at 60-150 ℃.
8. The method for synthesizing a heteroatom-loaded polymetaphosphorylic material of claim 1, wherein the method comprises the steps of: the molar ratio of the porphyrin-based polymer to the transition metal salt is 1: (5-10).
9. The method for synthesizing the heteroatom-loaded polymetaphorin material of claim 1, wherein: the solvent thermal reaction adopts at least one of N, N-dimethylformamide, methanol, ethanol, chloroform and acetone as a solvent.
10. The use of the heteroatom-supported polymetaphorin catalytic material of claim 1, wherein: the catalyst is applied as an air cathode catalyst of a zinc-air battery.
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