CN108054392B - Preparation method and application of biological bionic oxygen reduction electrocatalyst based on metal macrocyclic compound - Google Patents
Preparation method and application of biological bionic oxygen reduction electrocatalyst based on metal macrocyclic compound Download PDFInfo
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- CN108054392B CN108054392B CN201711370053.2A CN201711370053A CN108054392B CN 108054392 B CN108054392 B CN 108054392B CN 201711370053 A CN201711370053 A CN 201711370053A CN 108054392 B CN108054392 B CN 108054392B
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Abstract
The invention provides a preparation method and application of a metal macrocyclic compound-based biomimetic oxygen reduction electrocatalyst, belonging to the technical field of proton exchange membrane fuel cell catalysts. Dispersing a carbon material in a solvent, adding an aromatic fused ring compound, performing ultrasonic treatment, stirring for 2-48 h, performing suction filtration, washing until filtrate is colorless and clear, and drying a product to obtain an aromatic fused ring compound carbon-adsorption intermediate product. Dispersing the obtained aromatic condensed ring compound carbon adsorption compound in a solution, adding a metal macrocyclic compound under the condition of inert gas nitrogen or argon, stirring for 1-48 h at the temperature of 25-100 ℃, filtering and washing until filtrate is colorless, and drying. Thus obtaining the metal macrocyclic compound/aromatic fused ring compound/carbon electrocatalyst. The preparation method is simple to operate, easy to control and mild in condition, and the prepared metal macrocyclic compound/aromatic fused ring compound/carbon electrocatalyst has high oxygen reduction activity and can be used for proton exchange membrane fuel cells.
Description
Technical Field
The invention belongs to the technical field of proton exchange membrane fuel cell electrocatalysts, and relates to a preparation method and application of a metal macrocyclic compound/nitrogen heterocyclic ring functionalized aromatic fused ring compound/carbon electrocatalysts.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have received a great deal of attention due to their advantages of high power density, fast start-up, environmental friendliness, etc. The platinum-based electrocatalyst is one of the core materials of the PEMFC, but the platinum is used in large amount and expensive, which limits the wide application of the PEMFC. One of the solutions is to develop a non-noble metal electrocatalyst with low cost, high efficiency and high stability to replace the platinum-based electrocatalyst in order to promote the commercialization process of PEMFCs.
It is well known that biological enzymes have extremely high catalytic activity and selectivity in organisms. Wherein the cytochrome C oxidase, cytochrome P450 enzyme, etc. mainly contain metalloporphyrin macrocycleThe oxygen reductase to be catalyzed has excellent capability of catalyzing oxygen reduction reaction, and provides a great number of biomimetic references for us, such as introducing nitrogen heterocycles such as imidazole and pyridine and the like on metalloporphyrin as axial ligands of metal macrocyclic compounds and the like. Wei et al fix imidazole groups on the surface of carbon nanotubes by covalent bond linkage, and then load ferriporphyrin on the imidazole groups of carbon nanotubes by axial coordination of metalloporphyrin and imidazole groups, and the obtained electrocatalyst has high oxygen reduction activity and good durability (Angew. chem.,2014,126, 6777-D6781). Cao et al supported pyridine on carbon materials through covalent bonds, and then complexed iron phthalocyanine using axial ligand action as well, have higher oxygen reduction activity and better durability (Nature Communications,2013,4, 2076-. However, the experimental method is complicated by fixing covalent bonds on the carbon nanotubes, the substitution efficiency of the covalent bonds is low, and the derivatization of the covalent bonds leads to the original SP on the original carbon nanotubes2Hybridized large pi bond to SP3Hybridization destroys the conductive ability of the original carbon material.
The invention simplifies and optimizes the preparation method, and tries a method for fixing the metal macrocyclic compound by utilizing an axial ligand for the non-covalent bond functionalized carbon nano material. There are many reports that aromatic fused ring compounds (e.g., pyrene, anthracene) can undergo irreversible adsorption through strong pi-pi interaction with carbon materials (Nanoscience and Nanotechnology,2007,7, 3081-3088). By functionalizing the nitrogen heterocyclic ring of the aromatic fused ring compound, the aromatic fused ring compound has the capability of complexing a metal macrocyclic compound, so that the metal macrocyclic compound can be stably complexed on the nitrogen heterocyclic ring compound under the condition of not damaging the conductivity of a carbon material, and the oxygen reduction catalytic capability of the aromatic fused ring compound is enhanced.
Disclosure of Invention
The invention aims to provide a preparation method and application of a metal macrocyclic compound/nitrogen heterocyclic ring functionalized aromatic fused ring compound/carbon bionic electrocatalyst, and the method is simple to operate, easy to control and mild in condition. The metal macrocyclic compound/nitrogen heterocyclic ring functionalized aromatic condensed ring compound/carbon bionic electrocatalyst takes a carbon material with high specific surface area and high conductivity as a carrier, and takes a nitrogen heterocyclic ring functionalized aromatic condensed ring compound as a bridging structure, so that on one hand, irreversible adsorption can be generated through the strong pi-pi interaction of the condensed ring aromatic structure and a carbon material bond, nitrogen heterocyclic ring functionalization is carried out on the carbon material on the premise of not damaging the conductivity of the carbon material, and on the other hand, the nitrogen heterocyclic ring structure carries out coordination complexation on the metal macrocyclic compound to form a bionic oxygen reduction catalytic active center. The prepared metal macrocyclic compound/nitrogen heterocyclic ring functionalized aromatic condensed ring compound/carbon bionic electrocatalyst has better oxygen reduction comprehensive performance and can be used for proton exchange membrane fuel cells.
The technical scheme of the invention is as follows:
a preparation method of a biological bionic oxygen reduction electrocatalyst based on a metal macrocyclic compound comprises the following steps:
uniformly dispersing a carbon material in a solution, wherein the concentration of the carbon material in the solution is 0.1-100 mg/ml, adding a nitrogen heterocyclic ring functionalized aromatic condensed ring compound, and controlling the concentration of the nitrogen heterocyclic ring functionalized aromatic condensed ring compound in the solution to be 0.1-100 mg/ml; carrying out ultrasonic treatment for 0.1-5h at the temperature of-20-30 ℃, stirring for 2-48 h, carrying out suction filtration, washing until filtrate is colorless, and drying a product to obtain an aromatic fused ring compound carbon-adsorption intermediate product; dispersing the obtained intermediate product in a solution, adding a metal macrocyclic compound under the condition of inert gas nitrogen or argon, stirring for 1-48 h at 25-100 ℃, filtering and washing until filtrate is colorless, and drying to obtain the biomimetic oxygen reduction electrocatalyst based on the metal macrocyclic compound;
the mass ratio of the nitrogen heterocyclic ring functionalized aromatic condensed ring compound to the carbon material is more than 0.01: 1;
the mass ratio of the metal macrocyclic compound to the nitrogen heterocyclic ring functionalized aromatic condensed ring compound is more than 0.1: 1.
The nitrogen heterocyclic ring functionalized aromatic condensed ring compound is shown as a structural formula A-F, wherein n is 0-10;
in the single substitution condition, the positions of the substituted pyrenyl or anthryl containing imidazole or pyridine substituents are carbon numbers 1, 2 and 3 in the structural formula; wherein the imidazolyl group in the structural formula A, B, D, E has a structural formula shown as a linking mode in the structural formula; the substitution position of the pyridine in C and F may be ortho, meta or para with respect to the pyridine "N";
in the case of polysubstitution, the carbons 1-10 on the pyrenyl or the anthracenyl can be replaced by functional groups containing imidazole, pyridine or a mixture of the imidazole and the pyridine, and the number of the substituent groups is more than or equal to 2;
the metal macrocyclic compound is one or a mixture of more than two of metal tetraphenylporphyrin, tetramethoxyphenylporphyrin, tetra (4-carboxyphenyl) porphyrin, hemin, 2, 6-difluorotetraphenylporphyrin and metal phthalocyanine, wherein the metal is iron or cobalt.
The carbon material is one or a mixture of more than two of carbon black, activated carbon, carbon nanotubes, carbon fibers and graphene.
The solution is one or a mixture of more than two of methanol, ethanol, dichloromethane, acetonitrile, tetrahydrofuran, cyclohexane, toluene and N, N-dimethylformamide.
The biological bionic oxygen reduction electrocatalyst based on the metal macrocyclic compound obtained by the preparation method is applied to a proton exchange membrane fuel cell.
The invention has the beneficial effects that: 1) the carbon is cheap and easy to obtain, the conductivity is good, the aromatic condensed ring compound catalyst is easy to adsorb, and meanwhile, a huge specific surface area can be provided for the catalyst; 2) the nitrogen heterocyclic ring functionalized aromatic condensed ring compound can realize irreversible adsorption on the carbon material and axially complex the metal macrocyclic compound on the premise of not destroying the conductivity of the original carbon material, and is favorable for improving the electron conduction between the metal macrocyclic structure and the carbon material, and 3) the metal macrocyclic compound structure axially coordinated with imidazole or pyridine is closer to the biological enzyme seed structure and has better catalytic activity.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the prepared metal macrocyclic compound/nitrogen heterocyclic ring functionalized aromatic fused ring compound/carbon biomimetic series catalyst.
FIG. 2 is a Thermogravimetric (TG) curve of irreversible adsorption product of compound A obtained in example 1 of the present invention on carbon nanotubes under argon.
FIG. 3 polarization curve of oxygen reduction reaction of final product obtained in example 1 of the present invention, test conditions: 0.1M HClO saturated with oxygen at 25 deg.C4In the test, the potential scanning test is carried out at the scanning speed of 10mV/s and the voltage of 0-1.2V (vs RHE), and the electrode rotating speed is 1600 r/min. The polarization curve shows that the non-noble metal electrocatalyst obtained in example 1 has better oxygen reduction catalytic activity.
Detailed Description
The invention is further described in the following with reference to the drawings and examples, which are intended to illustrate the invention more clearly, but the scope of the invention as claimed is not limited to the scope of the examples presented below.
Example 1:
dispersing 10mg of multi-walled carbon nanotubes and 40mg of compound A (N is 1) in 5ml of N, N-dimethylformamide solution, carrying out ultrasonic treatment at 25 ℃ for 30min, standing at-10 ℃, carrying out suction filtration after 24h, washing with N, N-dimethylformamide until the filtrate is pure and colorless, drying at 65 ℃, dispersing the obtained black powder solid in 10ml of methanol solution, adding 40mg of haematochrome, stirring at 25 ℃ under the condition of nitrogen for 24h, filtering, washing with methanol until the filtrate is colorless, and drying.
Example 2:
dispersing 50mg of multi-walled carbon nanotubes and 30mg of compound B (n ═ 2) in 5ml of tetrahydrofuran solution, carrying out ultrasonic treatment at 25 ℃ for 30min, standing at-10 ℃ for 24h, then carrying out suction filtration, washing with tetrahydrofuran until the filtrate is pure and colorless, drying at 65 ℃, dispersing the obtained black powder solid in 10ml of methanol solution, adding 40mg of cobalt phthalocyanine into the methanol solution, stirring at 55 ℃ under nitrogen for 24h, filtering, washing with methanol until the filtrate is colorless, and drying. The morphology and performance of the obtained catalyst are similar to those of the sample in the embodiment 1, and the catalyst has better comprehensive oxygen reduction performance.
Example 3:
dispersing 20mg of graphene and 100mg of compound C (n-4) in 5ml of cyclohexane solution, carrying out ultrasonic treatment at 25 ℃ for 120min, standing at 20 ℃ for 48h, carrying out suction filtration, washing the cyclohexane until the filtrate is pure and colorless, drying at 65 ℃, dispersing the obtained black powder solid in 10ml of cyclohexane solution, adding 40mg of tetramethoxyphenyl ferriporphyrin, stirring at 80 ℃ for 12h under the condition of nitrogen, filtering, washing the cyclohexane until the filtrate is colorless, and drying. The morphology and performance of the obtained catalyst are similar to those of the sample in the embodiment 1, and the catalyst has better comprehensive oxygen reduction performance.
Example 4:
dispersing 100mg of carbon black and 200mg of compound E (n ═ 5) in 10ml of dichloromethane solution, carrying out ultrasonic treatment at 25 ℃ for 30min, standing at 0 ℃ for 12h, then carrying out suction filtration, washing the dichloromethane until the filtrate is pure and colorless, drying at 65 ℃, dispersing the obtained black powder solid in 10ml, adding 20mg of iron phthalocyanine into the dichloromethane solution, stirring at 45 ℃ under nitrogen for 24h, filtering the dichloromethane, washing until the filtrate is colorless, and drying. The morphology and performance of the obtained catalyst are similar to those of the sample in the embodiment 1, and the catalyst has better comprehensive oxygen reduction performance.
Example 5:
dispersing 30mg of carbon fiber and 2mg of compound F (n ═ 7) in 20ml of dichloromethane solution, carrying out ultrasonic treatment at 25 ℃ for 20min, standing at-20 ℃ for 6h, carrying out suction filtration, washing the dichloromethane until the filtrate is pure and colorless, drying at 65 ℃, dispersing the obtained black powder solid in 50ml of dichloromethane solution, adding 20mg of tetra (4-carboxyphenyl) cobalt porphyrin into the dichloromethane solution, stirring at 45 ℃ under nitrogen for 2h, filtering, washing the filtrate with tetrahydrofuran until the filtrate is colorless, and drying. The morphology and performance of the obtained catalyst are similar to those of the sample in the embodiment 1, and the catalyst has better comprehensive oxygen reduction performance.
Example 6:
dispersing 40mg of carbon black and 500mg of compound H (n ═ 9) in 10ml of toluene solution, carrying out ultrasonic treatment at 25 ℃ for 10min, standing at 0 ℃ for 24H, carrying out suction filtration, washing with dichloromethane until the filtrate is pure and colorless, drying at 65 ℃, dispersing the obtained black powder solid in 10ml of toluene solution, adding 10mg of tetraphenylporphyrin into the toluene solution, stirring at 25 ℃ for 8H under the condition of nitrogen, filtering, washing with toluene until the filtrate is colorless, and drying. The morphology and performance of the obtained catalyst are similar to those of the sample in the embodiment 1, and the catalyst has better comprehensive oxygen reduction performance.
Example 7:
dispersing 5mg of single-walled carbon nanotube and 100mg of compound D (n is 10) in 10ml of toluene solution, carrying out ultrasonic treatment at 25 ℃ for 10min, standing at 0 ℃ for 24h, then carrying out suction filtration, washing with methanol until the filtrate is pure and colorless, drying at 65 ℃, dispersing the obtained black powder solid in 10ml of toluene solution, adding 10mg of 2, 6-difluorotetraphenylporphyrin into the toluene solution, stirring at 25 ℃ under nitrogen for 24h, filtering, washing with toluene until the filtrate is colorless, and drying. The morphology and performance of the obtained catalyst are similar to those of the sample in the embodiment 1, and the catalyst has better comprehensive oxygen reduction performance.
Claims (6)
1. A preparation method of a biological bionic oxygen reduction electrocatalyst based on a metal macrocyclic compound is characterized by comprising the following steps:
uniformly dispersing a carbon material in a solution, wherein the concentration of the carbon material in the solution is 0.1-100 mg/ml, adding a nitrogen heterocyclic ring functionalized aromatic condensed ring compound, and controlling the concentration of the nitrogen heterocyclic ring functionalized aromatic condensed ring compound in the solution to be 0.1-100 mg/ml; carrying out ultrasonic treatment for 0.1-5h at the temperature of-20-30 ℃, stirring for 2-48 h, carrying out suction filtration, washing until filtrate is colorless, and drying a product to obtain an aromatic fused ring compound carbon-adsorption intermediate product; dispersing the obtained intermediate product in a solution, adding a metal macrocyclic compound under the condition of inert gas nitrogen or argon, stirring for 1-48 h at 25-100 ℃, filtering and washing until filtrate is colorless, and drying to obtain the biomimetic oxygen reduction electrocatalyst based on the metal macrocyclic compound;
the metal macrocyclic compound is connected with the nitrogen heterocyclic ring functionalized aromatic condensed ring compound through a coordination bond;
the mass ratio of the nitrogen heterocyclic ring functionalized aromatic condensed ring compound to the carbon material is more than 0.01: 1;
the mass ratio of the metal macrocyclic compound to the nitrogen heterocyclic ring functionalized aromatic condensed ring compound is more than 0.1: 1;
the nitrogen heterocyclic ring functionalized aromatic condensed ring compound is shown as a structural formula A-F, wherein n is 0-10;
in the single substitution case, the positions of the substituted pyrenyl or anthryl of the substituent group are carbon numbers 1, 2 and 3 in the structural formula; wherein the imidazolyl group in the structural formula A, B, D, E has a structural formula shown as a linking mode in the structural formula; the substitution position of the pyridine in C and F is ortho, meta or para relative to the pyridine 'N';
in the case of polysubstitution, the carbons 1-10 on the pyrenyl or the anthracenyl can be replaced by functional groups containing imidazole, pyridine or a mixture of the imidazole and the pyridine, and the number of the substituent groups is more than or equal to 2;
2. the method according to claim 1, wherein the metal macrocyclic compound is one or more of metal tetraphenylporphyrin, tetramethoxyphenylporphyrin, tetra (4-carboxyphenyl) porphyrin, hemin, 2, 6-difluorotetraphenylporphyrin and metal phthalocyanine, and wherein the metal is iron or cobalt.
3. The method according to claim 1, wherein the carbon material is one or a mixture of two or more of carbon black, activated carbon, carbon nanotubes, carbon fibers, and graphene.
4. The method according to claim 2, wherein the carbon material is one or a mixture of two or more of carbon black, activated carbon, carbon nanotubes, carbon fibers, and graphene.
5. The method according to claim 1, 2, 3 or 4, wherein the solution is one or a mixture of two or more of methanol, ethanol, dichloromethane, acetonitrile, tetrahydrofuran, cyclohexane, toluene and N, N-dimethylformamide.
6. The biomimetic oxygen reduction electrocatalyst based on metal macrocyclic compound obtained by the preparation method of any one of claims 1 to 5 is applied to proton exchange membrane fuel cells.
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| CN110208323B (en) * | 2019-05-30 | 2021-12-07 | 济南大学 | Organic-inorganic composite material for detecting nitrogen dioxide and gas sensor |
| CN111146452B (en) * | 2019-12-27 | 2021-10-22 | 大连理工大学 | Porphyrin zeolite imidazole framework hybrid electrocatalyst and preparation method and application thereof |
| CN111146457B (en) * | 2019-12-27 | 2021-05-04 | 大连理工大学 | Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound |
| CN111370712A (en) * | 2020-02-24 | 2020-07-03 | 中南大学 | Preparation method of high-activity electrochemical oxygen reduction catalyst |
| CN112366325A (en) * | 2020-11-10 | 2021-02-12 | 河北工业大学 | Preparation method and application of carbon nanotube loaded iron phthalocyanine composite material with adjustable functional groups |
| CN113072547B (en) * | 2021-03-31 | 2022-10-21 | 广东工业大学 | Compound and triplet-triplet annihilation up-conversion system |
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