CN111146457A - Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound - Google Patents
Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound Download PDFInfo
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Abstract
The invention belongs to the field of fuel cell electrocatalysts, and provides a preparation method and application of a porous composite material containing a bimetallic macrocyclic compound and used as an oxygen reduction electrocatalyst. Stirring transition metal salt, a nitrogen-containing organic ligand and a metal macrocyclic compound according to a certain proportion at 0-80 ℃ by adopting a simple solution reaction, reacting for a certain time to enable the metal macrocyclic compound to be embedded into a pore channel formed by the metal salt and the organic ligand to be used as a precursor material, and carrying out high-temperature heat treatment to obtain the final catalyst. The material has high porosity, is embedded with metal macrocyclic compound, obviously improves the active site density, and avoids particle agglomeration and pore collapse in the high-temperature pyrolysis process. Compared with the traditional non-noble metal electrocatalyst, the material has higher oxygen reduction catalytic activity under both acidic and alkaline conditions.
Description
Technical Field
The invention belongs to the field of fuel cell electrocatalysts, and particularly relates to preparation and application of a porous composite material electrocatalyst containing a bimetallic macrocyclic compound.
Background
With the rapid development of the world economy, the traditional fossil fuels such as coal, oil, natural gas and the like face shortage and bring serious environmental problems, and the future energy sources are bound to develop towards the directions of cleanness, high efficiency, no pollution and sustainability. The fuel cell is widely used as a device capable of directly converting chemical energy into electric energy, wherein a new automobile industry using the polymer electrolyte membrane fuel cell as power is in the beginning of large-scale commercialization due to the advantages of environmental friendliness, high energy conversion efficiency, high power density, low operation noise and the like, but the realization of a complete replacement of the conventional fuel vehicle still faces a great challenge.
The rate of the cathode side Oxygen Reduction Reaction (ORR) is slow and requires a large amount of catalyst to accelerate its reaction progress. The platinum catalyst widely used at present has limited reserves and high price, and cannot meet the future development trend of fuel cell automobiles. Therefore, the development of low-cost, high-activity and long-life non-noble metal electrocatalyst is an important way to promote the research and development of the electrocatalyst. Non-noble metal electrocatalysts currently under investigation can be broadly classified into non-metal electrocatalysts, transition metal carbon, nitrogen, oxides, and transition metal-nitrogen-carbon electrocatalysts. Among them, the material of transition metal-nitrogen-carbon structure is a non-noble metal electrocatalyst hopefully to be practically applied to the polymer electrolyte membrane fuel cell, and the material can be prepared from precursors with abundant reserves and low price, and the electrocatalytic oxygen reduction activity is kept at a high level under both acidic and alkaline conditions.
In the transition metal-nitrogen-carbon electrocatalyst, metal macrocyclic compounds such as porphyrin, phthalocyanine and the like integrate a metal center, a carbon source and a nitrogen source, the coordination environment of the center metal and nitrogen provides an effective precursor for preparing the metal-nitrogen-carbon material, and the coordination effect of the metal and nitrogen can effectively reduce the agglomeration of metal atoms in the heat treatment process. In 2013, Joo et al combined an Ordered Mesoporous Silica (OMS) template with a metalloporphyrin precursor by nano-casting, and established a three-dimensional network structure of a porphyrin carbon skeleton by heat treatment to obtain a bimetallic ordered mesoporous carbon material (Scientific Reports,2013,3, 2715). However, the subsequent template removal step in the template preparation process is complicated, and impurities are easily introduced into the system. In 2017, Song et al uniformly supported ferriporphyrin (FeTMPPCl) on a carbon carrier in a rotary evaporation manner, and obtained the nitrogen-doped graphene-wrapped core-shell structure electrocatalyst after heat treatment. The electrocatalyst showed superior activity under ampholyte conditions (Advanced Functional Materials,2017,27, 3). However, for the carbon-supported metalloporphyrin phthalocyanine material, the stability is poor, and porphyrin and phthalocyanine are easy to be gathered into a block after pyrolysis. For the Metal Organic Frameworks (MOFs) widely used at present, the MOFs is mainly formed by connecting organic ligands and metal ions through coordination bonds and contains rich pore channels. In 2015, Feng et al directly heat-treat a covalent porous network structure formed by alternately arranging iron-centered and cobalt-centered porphyrins through coupling reaction to obtain a covalent organic framework material PCN-FeCo/C, and regularly and orderly combine two different metal centers together, thereby effectively improving the electrocatalytic activity of the material (Advanced Materials,2015,27, 3431). A double-ligand strategy is applied to Chinese and the like, zinc salt and iron salt are used as metal sources, a metal organic framework polymer with uniformly distributed iron, nitrogen and carbon is invented, a Fe-Nx/C type acidic oxygen reduction catalyst is obtained through high-temperature carbonization, and the oxygen reduction activity of the catalyst is regulated and controlled by regulating and controlling the contents of two organic ligands (201910798129.4). However, the preparation process of the MOFs material is complex, and high temperature and high pressure conditions are mostly required, so that the MOFs material is difficult to be applied on a large scale.
Meanwhile, the multi-metal based material has more excellent catalytic activity than a material containing only a single metal. Two or more metal complexes provide a greater diversity of active sites, and the possible synergistic effects thereof also contribute to the improvement in catalyst activity.
Therefore, it is important to develop a non-noble metal electrocatalyst with low cost, simple preparation process, and high activity and stability.
Disclosure of Invention
In order to solve the technical problems, the invention prepares a porous catalyst containing bimetallic macrocyclic compound with excellent performance and a specific structure, combines the metal macrocyclic compound such as porphyrin phthalocyanine and the like with a nitrogen-containing ligand and metal salts such as zinc salt and the like, and obtains the porous non-noble metal electrocatalyst which contains the metal macrocyclic compound in pores and has high active site density by adjusting a preparation mode and key parameters and observing heat treatment conditions.
The technical scheme of the invention is as follows:
in a first aspect, the present invention provides a method for preparing a porous composite electrocatalyst based on bimetallic macrocycles, said catalyst being prepared by the steps of:
(1) synthesis of a precursor containing a bimetallic macrocyclic compound:
dissolving an organic ligand in deionized water or an organic solvent, and performing ultrasonic homogenization to obtain a solution A;
dissolving transition metal salt in deionized water or an organic solvent, and performing ultrasonic homogenization to obtain a solution B;
dissolving a metal macrocyclic compound containing iron and a metal macrocyclic compound containing cobalt in an organic solvent, and performing ultrasonic homogenization to obtain a solution C;
pouring the solution C into the solution A in a stirring state, and performing ultrasonic homogenization to obtain a solution D;
pouring the solution B into the solution D in a stirring state at the temperature of 0-80 ℃, and reacting for 4-24 hours at normal pressure;
the solvent in the solution A is the same as that in the solution B;
the preparation conditions are only solution reactions at normal pressure, and are distinguished from hydrothermal or solvothermal reactions at high pressure.
(2) Preparation of a porous composite catalyst based on a bimetallic macrocyclic compound: in the step (1), after the reaction is finished, performing suction filtration and drying, grinding the dried sample to obtain a metal macrocyclic compound and metal organic framework composite material, placing the composite material in a tubular furnace, roasting in an inert atmosphere, heating to 800-1000 ℃ at a speed of 2-10 ℃/min, performing constant-temperature heat treatment for 1-4 h, cooling to room temperature, taking out, and grinding to obtain the porous composite material electrocatalyst based on the bimetallic macrocyclic compound.
Preferably, in the step (1), a surfactant is added when the solution A is prepared; when the solvent of the solution A is an organic solvent, the solvent of the solution C is the same as that of the solution A.
Preferably, the organic ligand is one of 2-methylimidazole, benzimidazole, trimesic acid, ethylene diamine tetraacetic acid, 1, 4-bis (1-pyrazol-4-yl) benzene, N-4-pyridyl-4-pyridylamine, 1, 4-phthalic acid, 2-methyl terephthalic acid, 1, 10-phenanthroline-4-carboxylic acid, 3- (4H-1,2, 4-triazol-4-yl) benzoic acid and meso-tetra (4-carboxyphenyl) porphine ferric chloride;
preferably, the iron-containing metal macrocyclic compound is one of iron porphyrin, tetraphenyl iron porphyrin, tetramethoxyphenyl iron porphyrin, iron phthalocyanine, sulfonated iron phthalocyanine; the cobalt-containing metal macrocyclic compound is one of cobalt porphyrin, tetraphenyl cobalt porphyrin, tetramethoxyphenyl cobalt porphyrin, cobalt phthalocyanine and sulfonated cobalt phthalocyanine;
preferably, the organic solvent is one or more of methanol, ethanol, isopropanol, ethylene glycol, N-dimethylformamide, N-dimethylacetamide, N-dibutylformamide, N-diethylacetamide, N-methylpyrrolidone, toluene, acetonitrile, acetone, ethylenediamine;
preferably, the transition metal salt is one or more of chlorides, nitrates, acetates or sulfates of Mn, Fe, Co, Ni, Cu, Zn.
Preferably, the surfactant is one or more of sodium dodecyl sulfate, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and hexadecyl trimethyl ammonium bromide.
Preferably, the transition metal salt comprises one of chloride, nitrate, acetate or sulfate of Zn.
Preferably, the concentration ratio of the transition metal salt to the organic ligand is 1:2 to 1: 20; the ratio of the iron-containing metal macrocycle to the cobalt-containing metal macrocycle is 1:1-4: 1; the concentration of the metal macrocyclic compound in the total solution of the reaction is 0.1 to 20mM, and the total solution is a solution obtained by pouring the solution B into the solution D under stirring.
In a second aspect, the present invention provides an electrocatalyst based on bimetallic macrocycles, said catalyst being obtained by the above preparation process.
In a third aspect, the present invention provides the use of an electrocatalyst based on bimetallic macrocycles for use in the field of cathodes for acidic or alkaline fuel cells.
Advantageous effects
(1) The preparation method provided by the invention has the advantages of simple operation of the preparation process, rich raw material sources and low preparation cost.
(2) According to the preparation method provided by the invention, the metal macrocyclic compound is combined with the nitrogen-containing organic ligand and the metal salt, the material with high porosity and high specific surface area is obtained by utilizing the coordination of the metal salt and the organic ligand, and then the metal macrocyclic compound is doped into the pore canal of the material, so that the number and density of active sites are obviously improved, the structural collapse and particle agglomeration caused by high-temperature heat treatment are reduced, and the oxygen reduction catalytic activity of the catalyst is obviously improved.
(3) The non-noble metal electrocatalyst prepared by the preparation method provided by the invention has good ORR catalytic performance under both acidic and alkaline conditions, and can be used as a cathode (ORR) catalyst of acidic and alkaline fuel cells (metal-containing air cells).
(4) Because the material constructed by the metal salt and the nitrogen-containing ligand has higher porosity, the metal macrocyclic compound contained in the material can obviously improve the density of active sites and avoid the agglomeration of metal particles in the high-temperature pyrolysis process; meanwhile, due to the existence of the metal macrocyclic compound in the pores, the collapse of the pores is prevented to a certain extent in the high-temperature heat treatment process; and under the high temperature condition, zinc volatilizes and forms pores, thereby effectively improving the porosity of the material.
(5) The synthesis conditions of the material constructed by the metal salt and the nitrogen-containing ligand are relatively mild, and the preparation process of the catalyst does not need any acid treatment, so that the preparation process of the non-noble metal electrocatalyst is simplified to a certain extent.
(6) The electrocatalyst prepared by the method not only has ORR activity superior to that of a commercial platinum-carbon catalyst under alkaline conditions, but also can be comparable to that of the commercial platinum-carbon catalyst in an acidic environment. The excellent performance of the material is benefited by the special structure, the structure increases the density of oxygen reduction active sites, and has large specific surface area, and the material transmission and charge transfer are accelerated.
Drawings
FIG. 1(a) is an oxygen reduction polarization curve under acidic conditions for the catalysts of examples 1, 5, 6 of the present invention and comparative example 6.
FIG. 1(b) is an oxygen reduction polarization curve under basic conditions for the catalysts of examples 1, 5, 6 of the present invention and comparative example 6.
FIG. 2(a) is a graph showing the oxygen reduction polarization curves under acidic conditions of catalysts having different proportions of porphyrin iron and porphyrin cobalt in examples 1 to 4 of the present invention and comparative examples 1 and 5.
FIG. 2(b) is a graph showing the oxygen reduction polarization curves under basic conditions of the catalysts having different proportions of porphyrin iron and porphyrin cobalt in examples 1 to 4 of the present invention and comparative examples 1 and 5.
FIG. 3(a) is an oxygen reduction polarization curve under acidic conditions for comparative examples 1-4 of the present invention with different porphyrin iron loading catalysts and a commercial 20% Pt/C catalyst.
FIG. 3(b) is an oxygen reduction polarization curve under basic conditions for comparative examples 1-4 of the present invention with different porphyrin iron loading catalysts and a commercial 20% Pt/C catalyst.
FIG. 4(a) is an oxygen reduction polarization curve under acidic conditions for the catalyst of comparative example 7 of the present invention versus a commercial 20% Pt/C catalyst.
FIG. 4(b) is an oxygen reduction polarization curve under basic conditions for the catalyst of comparative example 7 of the present invention versus a commercial 20% Pt/C catalyst.
FIG. 5 is an oxygen reduction polarization curve of the catalyst of example 1 of the present invention versus a commercial 20% Pt/C catalyst under basic conditions.
Detailed Description
The following embodiments are further described by way of examples, but not limited to the following examples, with reference to the accompanying drawings and technical solutions.
Example 1
Preparing 10mL of 10mM 2-methylimidazole aqueous solution at room temperature (25 ℃) and carrying out ultrasonic homogenization; preparing 10mL2.5mM zinc acetate aqueous solution and carrying out ultrasonic homogenization; dissolving 2mL of solution containing 22.5mg of porphyrin iron and 7.5mg of porphyrin cobalt in 2mL of N, N-Dimethylformamide (DMF), and performing ultrasonic treatment uniformly;
pouring 2mL of N, N-Dimethylformamide (DMF) solution containing 22.5mg of porphyrin iron and 7.5mg of porphyrin cobalt into 10mL of 10mM aqueous solution of 2-methylimidazole, carrying out ultrasonic treatment for 15min, pouring 10mL of 2.5mM aqueous solution of zinc acetate into the continuously stirred mixed solution, reacting for 8h at normal pressure, carrying out suction filtration, and drying; grinding the dried sample to obtain a metal macrocyclic compound and an organic porous composite material, placing the composite material in a tubular furnace, roasting in argon atmosphere, heating to 900 ℃ at the speed of 2-10 ℃/min, carrying out constant-temperature heat treatment for 2h, cooling to room temperature, taking out, grinding to obtain a porous composite material electrocatalyst Fe based on the metal macrocyclic compound: co 3: 1-900 ℃.
The obtained electrocatalyst was prepared in basic (0.1M KOH) and acidic (0.1M HClO)4) RDE (rotating disk electrode) performance tests were performed in a standard three-electrode electrochemical cell under conditions. The glassy carbon electrode dripped with the catalyst is used as a working electrode, the graphite rod is used as a counter electrode, Hg/HgO (1M NaOH) is used as a reference electrode in an alkaline system, saturated calomel is used as a reference electrode in an acidic system, and the loading capacity of the catalyst on the electrode provided by the embodiment is 0.6mg/cm2。
All potentials in the present invention are RHE potentials. 20 wt% Pt/C electrocatalyst was used as a control at a loading of 20 μ gpt·cm-2. Testing N at 25 deg.C2Saturated or O2Saturated 0.1M aqueous KOH or 0.1M HClO4In aqueous solution. At a positive scan rate of 100mV · s-1Under the conditions of (a), a Cyclic Voltammetry (CV) curve of the catalyst was tested. When the spin rate was 1600rpm, the positive scan rate was 10mV · s-1The ORR polarization curve was tested. The electrochemical test conditions in examples 2 to 6 and comparative examples 1 to 7 were the same as in example 1.
Example 2
(different from the ratio of porphyrin iron and porphyrin cobalt in the metal macrocycle in example 1, the other steps are the same):
2mL of N, N-Dimethylformamide (DMF) solution containing 20mg of porphyrin iron and 10mg of porphyrin cobalt was poured into 10mL of 10mM 2-methylimidazole aqueous solution at room temperature (25 ℃), subjected to ultrasonic treatment for 15min, 10mL of 2.5mM zinc acetate aqueous solution was poured into the above mixed solution with stirring, and subjected to reaction at normal pressure for 8 hours, suction filtration and drying. And then carrying out heat treatment for 2h at 900 ℃ in an argon atmosphere to obtain an electrocatalyst Fe: co 2: 1-900 ℃.
Examples 3 to 4
The preparation method is different from the preparation method of the metal macrocyclic compound porphyrin iron and porphyrin cobalt in the embodiment 1, and other steps are the same, so that the electrocatalyst Fe: co 1: 1. fe: co 4: 1.
as shown in fig. 2a and b, when Fe: co 1: 1. fe: co 2: 1. fe: co 3: 1. fe: co 4:1, the catalyst has higher half-wave potential under both acidic and alkaline environments.
Example 5:
(same as in example 1 except for the heat treatment temperature)
2mL of a solution of 22.5mg of iron porphyrin and 7.5mg of cobalt porphyrin in N, N-Dimethylformamide (DMF) was poured into 10mL of a 10mM aqueous solution of 2-methylimidazole at room temperature (25 ℃ C.), sonicated for 15min, 10mL of a 2.5mM aqueous solution of zinc acetate was poured into the above mixed solution with constant stirring, and the mixture was reacted at normal pressure for 8 hours, filtered with suction and dried. And then carrying out heat treatment for 2h at 800 ℃ in an argon atmosphere to obtain an electrocatalyst Fe: co 3: 1-800 ℃.
Example 6:
(same as in example 5 except for the heat treatment temperature)
2mL of a solution of 22.5mg of iron porphyrin and 7.5mg of cobalt porphyrin in N, N-Dimethylformamide (DMF) was poured into 10mL of a 10mM aqueous solution of 2-methylimidazole at room temperature (25 ℃ C.), sonicated for 15min, 10mL of a 2.5mM aqueous solution of zinc nitrate was poured into the above mixed solution with constant stirring, and the mixture was reacted at normal pressure for 8 hours, filtered with suction and dried. And then carrying out heat treatment for 2h at 1000 ℃ in an argon atmosphere to obtain an electrocatalyst Fe: co 3: 1-1000 ℃.
As shown in fig. 1a and b, when the heat treatment temperature is 800 ℃, 900 ℃ and 1000 ℃, the catalyst has higher half-wave potential under both acidic and alkaline environments.
Comparative example 1
(same procedure as in example 1 except for the kind of the metal macrocycle)
2mL of N, N-Dimethylformamide (DMF) solution containing 30mg of iron porphyrin is poured into 10mL of 10mM aqueous solution of 2-methylimidazole at room temperature (25 ℃), the mixture is subjected to ultrasonic treatment for 15min, 10mL of 2.5mM aqueous solution of zinc acetate is poured into the continuously stirred mixed solution, the mixture is subjected to reaction at normal pressure for 8h, and the reaction solution is subjected to suction filtration and drying. Then the mixture is thermally treated for 2 hours under the argon atmosphere at 900 ℃ to obtain 30mg-FeP of the electrocatalyst.
Comparative example 2
(same as in comparative example 1 except for the concentration of the metal macrocycle)
2mL of N, N-Dimethylformamide (DMF) solution containing 60mg of iron porphyrin is poured into 10mL of 10mM aqueous solution of 2-methylimidazole at room temperature (25 ℃), the mixture is subjected to ultrasonic treatment for 15min, 10mL of 2.5mM aqueous solution of zinc acetate is poured into the continuously stirred mixed solution, the mixture is subjected to reaction at normal pressure for 8h, and the reaction solution is subjected to suction filtration and drying. Then the mixture is thermally treated for 2 hours under the argon atmosphere at 900 ℃ to obtain 60mg-FeP of the electrocatalyst.
Comparative examples 3 to 4
The preparation method is different from the concentration of the metal macrocyclic compound porphyrin iron in the comparative example 1, and other steps are the same, so that 40mg-FeP and 50mg-FeP of the electrocatalyst are obtained.
As shown in FIGS. 3a and b, when only porphyrin iron is added, no matter how small the amount is 30-60 mg, in alkaline environment, the half-wave potential similar to or even exceeding that of commercial Pt/C can be obtained, whereas in acidic environment, the half-wave potential is obviously inferior to that of commercial Pt/C. This demonstrates that superior performance cannot be obtained with the incorporation of a single metal macrocyclic compound alone.
Comparative example 5
(different from the ratio of porphyrin iron and porphyrin cobalt in the metal macrocycle in example 1, the other steps are the same):
2mL of N, N-Dimethylformamide (DMF) solution containing 30mg of cobalt porphyrin at room temperature (25 ℃) is poured into 10mL of 10mM aqueous solution of 2-methylimidazole by ultrasonic treatment for 15min, 10mL of 2.5mM aqueous solution of zinc acetate is poured into the continuously stirred mixed solution, the reaction is carried out for 8h under normal pressure, and the mixture is filtered, filtered and dried. And then carrying out heat treatment for 2h at 900 ℃ in an argon atmosphere to obtain an electrocatalyst Fe: co ═ 0: 1-900 ℃.
As shown in fig. 2a and b, when Fe: co ═ 0: 1. fe: co 1: 0, the half-wave potential of the catalyst is reduced in both acidic and basic environments. This demonstrates that superior performance cannot be obtained with the incorporation of a single metal macrocyclic compound alone.
Comparative example 6
(same as in example 1 except for the heat treatment temperature)
2mL of a solution of 22.5mg of iron porphyrin and 7.5mg of cobalt porphyrin in N, N-Dimethylformamide (DMF) was poured into 10mL of a 10mM aqueous solution of 2-methylimidazole at room temperature (25 ℃ C.), sonicated for 15min, 10mL of a 2.5mM aqueous solution of zinc nitrate was poured into the above mixed solution with constant stirring, and the mixture was reacted at normal pressure for 8 hours, filtered with suction and dried. And then carrying out heat treatment for 2h at 700 ℃ in an argon atmosphere to obtain an electrocatalyst Fe: co 3: 1-700 ℃.
As shown in fig. 1a and b, when the heat treatment temperature is 700 ℃, the half-wave potential of the catalyst is obviously reduced compared with the catalyst under the same condition in the invention under the acidic or alkaline environment. This indicates that the catalyst of the present invention does not provide excellent performance when heat treated at 700 ℃.
Comparative example 7
(different from the reaction in example 1, the other steps are the same)
2mL of N, N-Dimethylformamide (DMF) solution containing 22.5mg of porphyrin iron and 7.5mg of porphyrin cobalt is poured into 10mL of 10mM 2-methylimidazole aqueous solution at room temperature (25 ℃), the mixture is subjected to ultrasonic treatment for 15min, 10mL of 2.5mM zinc acetate aqueous solution is poured into the continuously stirred mixed solution, the mixture is stirred for 30min, the mixture is moved to a hydrothermal reaction kettle to react for 8h at 120 ℃, and the mixture is filtered, filtered and dried. And then carrying out heat treatment for 2h at 900 ℃ in an argon atmosphere to obtain an electrocatalyst Fe: co 3: 1-hydrothermal.
As shown in fig. 4a and b, the catalysts synthesized by hydrothermal method have a large difference in half-wave potential from Pt/C in both acidic and basic conditions, and also have a difference in ORR activity from the catalysts under the same conditions as described in the present invention. This indicates that the catalyst of the present invention must be reacted in a solution at normal pressure, and a high pressure hydrothermal method cannot be used.
Claims (8)
1. A preparation method of a porous composite material electrocatalyst based on a bimetallic macrocyclic compound is characterized in that the preparation steps of the catalyst are as follows:
(1) synthesis of precursors of metal-containing macrocyclic compounds:
dissolving an organic ligand in deionized water or an organic solvent, and performing ultrasonic homogenization to obtain a solution A;
dissolving transition metal salt in deionized water or an organic solvent, and performing ultrasonic homogenization to obtain a solution B;
dissolving a metal macrocyclic compound containing iron and a metal macrocyclic compound containing cobalt in an organic solvent, and performing ultrasonic homogenization to obtain a solution C;
pouring the solution C into the solution A in a stirring state, and performing ultrasonic homogenization to obtain a solution D;
pouring the solution B into the solution D in a stirring state at the temperature of 0-80 ℃, and reacting for 4-24 hours at normal pressure;
the solvent in the solution A is the same as that in the solution B;
(2) preparation of a porous composite catalyst based on a bimetallic macrocyclic compound: in the step (1), after the reaction is finished, performing suction filtration and drying, grinding the dried sample to obtain a composite material of the metal macrocyclic compound nitrogen-containing ligand and the transition metal salt, roasting the composite material in an inert atmosphere, heating to 800-1000 ℃ at the speed of 2-10 ℃/min, performing constant-temperature heat treatment for 1-4 h, cooling to room temperature, taking out and grinding to obtain the porous composite material electrocatalyst based on the bimetallic macrocyclic compound.
2. The method according to claim 1, wherein in the step (1), a surfactant is added when the solution A is prepared; when the solvent of the solution A is an organic solvent, the solvent of the solution C is the same as that of the solution A.
3. The production method according to claim 1,
the organic ligand is one of 2-methylimidazole, benzimidazole, trimesic acid, ethylene diamine tetraacetic acid, 1, 4-di (1-pyrazol-4-yl) benzene, N-4-pyridyl-4-pyridylamine, 1, 4-phthalic acid, 2-methyl terephthalic acid, 1, 10-phenanthroline-4-formic acid, 3- (4H-1,2, 4-triazole-4-yl) benzoic acid and meso-tetra (4-carboxyphenyl) porphine ferric chloride;
the iron-containing metal macrocyclic compound is one of porphyrin iron, tetraphenyl iron porphyrin, tetramethoxyphenyl porphyrin iron, phthalocyanine iron and sulfonated phthalocyanine iron; the cobalt-containing metal macrocyclic compound is one of cobalt porphyrin, tetraphenyl cobalt porphyrin, tetramethoxyphenyl cobalt porphyrin, cobalt phthalocyanine and sulfonated cobalt phthalocyanine;
the organic solvent is one or more of methanol, ethanol, isopropanol, ethylene glycol, N-dimethylformamide, N-dimethylacetamide, N-dibutylformamide, N-diethylacetamide, N-methylpyrrolidone, toluene, acetonitrile, acetone and ethylenediamine;
the transition metal salt is one or more of chlorides, nitrates, acetates or sulfates of Mn, Fe, Co, Ni, Cu and Zn.
4. The method of claim 2, wherein the surfactant is one of sodium dodecyl sulfate, polyvinylpyrrolidone, sodium dodecylbenzenesulfonate, and cetyltrimethylammonium bromide.
5. The method according to claim 3, wherein the transition metal salt includes one of a chloride, a nitrate, an acetate, or a sulfate of Zn.
6. The method according to claim 1, wherein the concentration ratio of the transition metal salt to the organic ligand is 1:2 to 1: 20; the ratio of the iron-containing metal macrocycle to the cobalt-containing metal macrocycle is 1:1-4: 1; the concentration of the metal macrocycle in the total reaction solution is between 0.1 and 20 mM.
7. An electrocatalyst based on a metal macrocycle, characterised in that it is obtained by a process according to any one of claims 1 to 6.
8. Use of an electrocatalyst based on metal macrocycles, characterized in that the catalyst according to claim 7 is used in the field of cathodes for acidic or alkaline fuel cells.
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| CN111841547A (en) * | 2020-07-31 | 2020-10-30 | 青岛创启汇能新材料科技有限公司 | Composite material, preparation method thereof and catalyst prepared from composite material |
| CN112002909A (en) * | 2020-08-24 | 2020-11-27 | 广西师范大学 | Preparation method of Zn-Cu-N-based co-doped carbon composite material |
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| CN115188977B (en) * | 2022-07-21 | 2024-05-14 | 大连理工大学 | High specific surface area metal-nitrogen-carbon oxygen reduction electrocatalyst, preparation method thereof and application thereof in fuel cell |
| CN115332590A (en) * | 2022-08-04 | 2022-11-11 | 大连理工大学 | Membrane electrode with hydrogen dissipation layer and preparation method and application thereof |
| CN115548352A (en) * | 2022-09-28 | 2022-12-30 | 大连理工大学 | Method for improving durability of metal-nitrogen-carbon electrocatalyst and application of metal-nitrogen-carbon electrocatalyst in field of fuel cells |
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