CN111146452A - Porphyrin zeolite imidazole framework hybrid electrocatalyst and preparation method and application thereof - Google Patents
Porphyrin zeolite imidazole framework hybrid electrocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a porphyrin zeolite imidazole framework hybrid electrocatalyst, a preparation method and application thereof, and belongs to the technical field of polymer electrolyte membrane fuel cells. The preparation method comprises the following steps: 1) dissolving porphyrin in an aqueous solution of 2-methylimidazole to obtain a solution A, adding a zinc acetate solution into the solution A to obtain a green precipitate, performing solid-liquid separation, drying, and grinding to obtain green powder; 2) carrying out heat treatment on the product obtained in the step 1) at the temperature of 500-900 ℃ for 2h in the inert gas atmosphere to obtain the non-noble metal electrocatalyst. The method has the advantages of low cost of raw materials, simple method, short time consumption, reaction at room temperature and easy amplification synthesis; environmental protection and avoids the use of organic solvents.
Description
Technical Field
The invention relates to a porphyrin zeolite imidazole framework hybrid electrocatalyst, a preparation method and application thereof, and belongs to the technical field of polymer electrolyte membrane fuel cells.
Background
The polymer electrolyte membrane fuel cell is a high-efficiency and clean energy conversion device. At present, the cathodic oxygen reduction reaction can not get rid of the use of the platinum-based noble metal electrocatalyst, and the large-scale commercial application of the platinum-based noble metal electrocatalyst can not be fully realized. Therefore, the research on the non-noble metal electrocatalyst with low cost, high activity and high stability is an important subject of research by researchers. Among a variety of non-noble metal electrocatalysts, electrocatalysts derived from porphyrin-based and Metal Organic Framework (MOFs) -based precursors have attracted much attention because of having metal-nitrogen intrinsic active centers and high oxygen reduction activity. Zeolite imidazole material (ZIF-8) belongs to a porous material similar to zeolite crystal, and has the advantages of adjustable pore structure, high specific surface area, special geometric structure and the like, so that the zeolite imidazole material is widely applied to the fields of biology, gas adsorption, electrochemistry and the like in recent years.
In order to obtain an electrocatalyst with better electrocatalytic oxygen reduction performance, porphyrin and MOFs are combined, so that a non-noble metal electrocatalyst is constructed, which has mutually compensated and mutually promoted electrocatalytic oxygen reduction activity, and the method is also a method which is rarely reported. At present, materials based on combination of porphyrin MOFs are mainly divided into two types: the other is that porphyrin is used as ligand to coordinate with metal ions to form an MOFs structure, and porphyrin molecules directly participate in the formation of the MOFs structure; the other is that porphyrin molecules are encapsulated into MOFs, the MOFs material plays a role of providing a carrier of porphyrin, and the porphyrin molecules do not participate in the formation of the MOFs. Jiang et al used FeTCPP as a ligand to coordinate with zirconium ions, synthesized a porphyrin-based MOFs material Fe-PCN through a hydrothermal reaction, and pyrolyzed at high temperature for an electrocatalytic oxygen reduction reaction, and had higher oxygen reduction activity in an alkaline medium (Angew Chem Int Ed,2018,57, 8525-. Wangzonghua et al invented a preparation method (201610407974.0) of a ferriporphyrin chloride/methylene blue @ metal organic framework composite material electrode, and FeTCPP was encapsulated in Zn MOF by a one-pot method, and methylene blue was adsorbed in an aqueous solution, as an electrode material, and has a good application in the field of electrochemical biosensing (201510767727.7). Zhang Juan et al invented an application of Hemin @ Zn-MOF material in catalytic oxidation, utilizing the force between the exposed free group of Zn-MOF and heme to fix the heme on the Zn-MOF material, which can stably exist in the environment with pH value ranging from 1-10 (201910406158.1), the method is that firstly the MOF material is synthesized, then guest porphyrin molecules are introduced into the MOF material, because the MOF material still has some exposed functional groups on its surface after being formed, and these functional groups are utilized to interact with the carboxyl of the heme molecule to connect the two materials. Wei et al report that a solid phase milling method encapsulates Fe-TPP molecules in rho-ZIF materials (a ZIF with rho-topological structure, with a pore size of 2.2nm) to prepare non-noble metal electrocatalysts and have high oxygen reduction activity in alkaline solutions (Nano Energy,2018,52,29-37), and the method uses ZIF materials with larger pore sizes, so that Fe-TPP molecules can be successfully introduced into the pore structures.
In view of the above, the reported preparation methods of non-noble metal electrocatalysts derived from porphyrin-bound metal-organic framework materials need to be improved as follows: 1. the preparation method is simplified, the utilization rate of porphyrin is improved, and the preparation cost is reduced; 2. the density of oxygen reduction active sites is increased, and the oxygen reduction activity is improved.
So far, no relevant patent report exists for synthesizing a porphyrin ZIF-8 hybrid material based on a system taking complete water as a solvent and applying the hybrid material to the field of electrocatalytic oxygen reduction.
Disclosure of Invention
The electrocatalyst prepared by the invention has a inherited microporous structure and a high specific surface area (850 m)2(g), high oxygen reduction activity site density (iron content of 4.5 wt%), and good oxygen reduction activity in both acidic and alkaline electrolytes. The preparation method fully utilizes the self-assembly acting force between porphyrin molecules with carboxyl and negative charges and structural units forming the ZIF-8 material, so that the porphyrin molecules are introduced into micropores and nanocages of the ZIF-8, the pyrolyzed material inherits a large number of micropore structures of the ZIF-8, and the metal center of the porphyrin is not aggregated, so that the utilization rate of the porphyrin is improved. Meanwhile, the preparation method does not need any complex steps of secondary heat treatment, acid washing and the like, and the use of an organic solvent, is an environment-friendly method capable of large-scale preparation, and solves the problems.
The invention provides a preparation method of a porphyrin zeolite imidazole framework hybrid electrocatalyst, which comprises the following steps: 1) preparation of porphyrin and zeolite imidazole framework self-assembly hybrid precursor porphyrin @ ZIF-8: dissolving porphyrin in an aqueous solution of 2-methylimidazole to obtain a solution A, adding a zinc acetate solution into the solution A to obtain a green precipitate, performing solid-liquid separation, drying, and grinding to obtain green powder; 2) preparation of porphyrin @ ZIF-8 hybrid precursor-derived electrocatalyst: carrying out heat treatment on the product obtained in the step 1) at the temperature of 500-900 ℃ for 2h in the inert gas atmosphere to obtain the non-noble metal electrocatalyst.
The porphyrin is preferably at least one of 5,10,15, 20-tetra (4-carboxyphenyl) ferriporphyrin, 5,10,15, 20-tetra (4-carboxyphenyl) cobalt porphyrin, 5,10,15, 20-tetra (4-carboxyphenyl) copper porphyrin, 5,10,15, 20-tetra (4-carboxyphenyl) manganoporphyrin, Protoporphyrin cobalt chloride (Co (III) Protoporphyrin IX chloride), Hemin (Hemin), Protoporphyrin copper chloride (Cu (II) Protoporphyrin IX chloride), Protoporphyrin manganese chloride (Mn (III) Protoporphyrin IXchloride), meso-tetra (4-benzenesulfonic acid group) iron porphyrin, meso-tetra (4-benzenesulfonic acid group) cobalt, meso-tetra (4-benzenesulfonic acid group) manganese porphyrin and meso-tetra (4-benzenesulfonic acid group) copper porphyrin.
The invention preferably has the ratio of the porphyrin to the 2-methylimidazole aqueous solution of 20-100mg/5-50 mL.
The concentration of the 2-methylimidazole aqueous solution is 0.4-2M.
The concentration of the zinc acetate solution is 0.1-0.5M.
In the invention, the volume ratio of the zinc acetate solution to the 2-methylimidazole aqueous solution is preferably 1: 1.
in the invention, the preferable stirring conditions of the zinc acetate solution and the solution A are as follows: stirring for 1-4h at 25-40 ℃.
The temperature of the drying is preferably 65-70 ℃ in the invention.
The invention also aims to provide a porphyrin zeolite imidazole framework hybrid electrocatalyst prepared by the method.
The invention also aims to provide application of the porphyrin zeolite imidazole framework hybrid electrocatalyst in a polymer electrolyte membrane fuel cell.
The invention has the beneficial effects that:
1) porphyrin molecules are used as a structure guiding template, so that the ZIF-8 material performs nucleation and growth around the porphyrin molecules, and finally the porphyrin molecules are coated in micropores and nanocages of the material to form the porphyrin @ ZIF-8 hybrid precursor. Porphyrin molecules with carboxyl functional groups have hydrogen bonding effect with 2-methylimidazole serving as a ligand of the ZIF-8 material, and have coordination effect with metal ions Zn serving as the ZIF-8 material; porphyrin molecules with negative charges have electrostatic interaction with metal ions Zn constituting the ZIF-8 material. Based on the self-assembly interaction between the porphyrin molecules and the construction units of the ZIF-8 material, the porphyrin molecules are embedded into the pores and nanocages of the ZIF-8 material. So that porphyrin molecules are not easy to fall off, and the porphyrin @ ZIF-8 hybrid material with stable structure is formed. The monatomic electrocatalyst with high active site density is obtained after one-step high-temperature heat treatment, the micropore structure of the prepared electrocatalyst is greatly reserved, the collapse phenomenon caused by the high-temperature heat treatment is avoided, the micropore structure of the ZIF-8 also provides the supporting and isolating function for porphyrin molecules, and the pyrolyzed electrocatalyst does not contain large particles such as metal or metal oxide with poor activity and the like. The prepared electrocatalyst has higher oxygen reduction activity in both acidic and alkaline electrolytes. The preparation process of the catalyst does not need to be carried out at high temperature, the reaction time is short, any secondary heat treatment and acid treatment are not needed, the use of an organic solvent is avoided, and the preparation process of the non-noble metal electrocatalyst is simplified.
2) According to the method, porphyrin and the zeolite imidazole framework material are combined by a molecular self-assembly technology, the formed hybrid precursor inherits the characteristics of the two materials, the zeolite imidazole framework material provides a porphyrin molecule carrier, and meanwhile, porphyrin molecules also promote a microporous structure for supporting the zeolite imidazole framework material, so that the structure collapse is prevented. As porphyrin molecules are introduced into the nano cage and the micropores of the ZIF-8, the microporous structure plays a role in protecting and isolating the porphyrin molecules in the high-temperature pyrolysis process, so that low-activity metal particles formed by aggregation of metal centers are prevented, and the monatomic electrocatalyst is prepared. The porphyrin molecules in the ZIF-8 pore structure play a role in supporting and stabilizing the micropore structure, so that the micropore structure of the ZIF-8 subjected to high-temperature heat treatment is not collapsed and is still reserved in a large amount, and a large amount of metal-nitrogen-carbon oxygen reduction active centers are uniformly supported in the large amount of micropore structures, so that the synthesized electrocatalyst has high-density oxygen reduction active centers and is more favorable for electrocatalytic oxygen reduction reaction.
3) The preparation raw materials have low cost, the method is simple, the time consumption is short, the reaction is carried out at room temperature, and the scale-up synthesis is easy; environmental protection and avoids the use of organic solvents.
Drawings
The invention is illustrated in the accompanying figure 7,
FIG. 1 is a TEM image of Hemin and ZIF-8 self-assembled hybrid electrocatalyst in example 1;
FIG. 2 is an X-ray diffraction pattern of Hemin, ZIF-8 and Hemin @ ZIF-8 hybrid precursors of example 1;
FIG. 3 is a graph of the specific surface areas of ZIF-8 and Hemin @ ZIF-8 hybrid precursors of example 1;
FIG. 4 is an oxygen reduction polarization curve of the electrocatalysts Hemin @ ZIF-8-900, ZIF-8, neat Hemin powder and commercial Pt/C prepared in example 1 in an acid electrolyte;
FIG. 5 is an oxygen reduction polarization curve under acidic conditions for the electrocatalyst FeP @ ZIF-8-900 prepared in comparative example 1 and the electrocatalyst Hemin @ ZIF-8-900 prepared in example 2;
FIG. 6 is an oxygen reduction polarization curve under acidic conditions for the electrocatalyst H-FeP @ ZIF-8-800 prepared in comparative example 2 and the electrocatalyst Hemin @ ZIF-8-900 prepared in example 2;
FIG. 7 is an oxygen reduction polarization curve under acidic conditions for the electrocatalyst 1-FeP @ ZIF-8-900 prepared in comparative example 3 and the electrocatalyst Hemin @ ZIF-8-900 prepared in example 2.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
Adding 100mg of hemin into 50mL of 2M 2-methylimidazole aqueous solution at 40 ℃, performing ultrasonic homogenization to obtain solution A, adding 50mL of 0.5M zinc acetate aqueous solution into the solution A which is continuously stirred, continuously stirring for 1h, performing suction filtration on the obtained green precipitate, drying in an oven at 65 ℃, and grinding into green powder;
and (3) taking 500mg of green powder to carry out heat treatment for 2h at 900 ℃ under the argon atmosphere to obtain the Hemin @ ZIF-8-900 hybrid electrocatalyst.
As shown in fig. 1, the blood crystal element and ZIF-8 hybrid electrocatalyst is in an amorphous carbon structure, and there is no metal-based nanoparticle that is not favorable for oxygen reduction activity and stability, which proves that the method of this embodiment helps to avoid high-temperature aggregation of metal particles and improve oxygen reduction active site density.
As shown in FIG. 2, after Hemin molecules were introduced into the ZIF-8 material, the peak positions of the characteristic peaks of X-ray diffraction were not changed, and Hemin peaks were not observed, which proved that Hemin molecules were uniformly dispersed in the ZIF-8 material without aggregation, and that the introduction of Hemin molecules did not change the crystal structure of ZIF-8.
As shown in FIG. 3, the pore diameter of the pure ZIF-8 material is mainly concentrated around 1.2nm, and when Hemin molecules are introduced, the peak around 1.2nm disappears, and the micropore structure in the surface ZIF-8 material is occupied by the Hemin molecules, so that micropores are filled, and the fact that the Hemin molecules are introduced into the micropore structure of the ZIF-8 material is proved.
As shown in fig. 4, a standard three-electrode system is used to test the oxygen reduction activity of the electrocatalyst, a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the Hemin @ ZIF-8-900 hybrid electrocatalyst is prepared into a thin-film working electrode under the following test conditions: 0.1mol/L HClO saturated with oxygen at 25 DEG C4In the water solution, potential scanning test is carried out under the voltage of 0-1.2V (vs RHE), the half-wave potential of the electrocatalyst is calculated to be 0.826V (vs RHE), and the half-wave potential is very close to that of commercial platinum carbon, which shows that the oxygen reduction activity is better. The half-wave potentials of other comparative samples are all lower than Hemin @ ZIF-8-900 hybrid electrocatalysts.
Example 2
Adding 100mg of meso-tetra (4-benzenesulfonyl) porphyrin cobalt into 10mL of 0.4M 2-methylimidazole aqueous solution at 25 ℃, performing ultrasonic homogenization to obtain a solution A, adding 10mL of 0.1M zinc acetate aqueous solution into the solution A which is continuously stirred, continuously stirring for 1h, performing suction filtration on the obtained green precipitate, drying in an oven at 65 ℃, and grinding into green powder;
200mg of green powder is taken to be thermally treated for 2h at 900 ℃ under the argon atmosphere to obtain CoTPPS4@ ZIF-8-900 hybrid electrocatalyst.
Example 3
Adding 20mg of protoporphyrin cobalt chloride into 10mL of 0.8M 2-methylimidazole aqueous solution at 40 ℃, performing ultrasonic homogenization to obtain solution A, adding 10mL of 0.2M zinc acetate aqueous solution into the solution A which is continuously stirred, continuously stirring for 4 hours, performing suction filtration on the obtained green precipitate, drying in an oven at 65 ℃, and grinding into green powder;
and (3) carrying out heat treatment on 100mg of green powder at 800 ℃ for 2h under the argon atmosphere to obtain the CoP @ ZIF-8-800 hybrid electrocatalyst.
Example 4
Adding 30mg of 5,10,15, 20-tetra (4-carboxyphenyl) copper porphyrin into 10mL of 0.8M 2-methylimidazole water solution at 30 ℃, performing ultrasonic homogenization to obtain a solution A, adding 10mL of 0.2M zinc acetate water solution into the solution A which is continuously stirred, continuously stirring for 4 hours, performing suction filtration on the obtained green precipitate, drying in a 65 ℃ oven, and grinding into green powder;
and (3) taking 50mg of green powder, and carrying out heat treatment at 700 ℃ for 2h under the argon atmosphere to obtain the CuCPP @ ZIF-8-700 hybrid electrocatalyst.
Example 5
Adding 30mg of meso-tetra (4-benzenesulfonyl) manganese porphyrin into 5mL of 1.2M 2-methylimidazole aqueous solution at 25 ℃, performing ultrasonic homogenization to obtain a solution A, adding 5mL of 0.3M zinc acetate aqueous solution into the solution A which is continuously stirred, continuously stirring for 2 hours, performing suction filtration on the obtained green precipitate, drying in an oven at 65 ℃, and grinding into green powder;
taking 50mg of green powder, and carrying out heat treatment for 2h at 500 ℃ in an argon atmosphere to obtain MnTPPS4@ ZIF-8-500 hybrid electrocatalyst.
Example 6
Adding 30mg of meso-tetra (4-benzenesulfonyl) porphyrin manganese and 30mg of hemin into 5mL of 1.2M 2-methylimidazole aqueous solution at 25 ℃, carrying out uniform ultrasonic treatment to obtain solution A, adding 5mL of 0.3M zinc acetate aqueous solution into the solution A which is continuously stirred, continuously stirring for 2 hours, carrying out suction filtration on the obtained green precipitate, drying in a 65 ℃ oven, and grinding into green powder;
and (3) taking 50mg of green powder, and carrying out heat treatment at 800 ℃ for 2h under the argon atmosphere to obtain the MnFeP @ ZIF-8-800 hybrid electrocatalyst.
Comparative example 1
Adding 30mg of hemin into 5mL of 1.2M 2-methylimidazole methanol solution at 25 ℃, performing ultrasonic homogenization to obtain solution A, adding 5mL of 0.3M zinc acetate methanol solution into the solution A which is continuously stirred, continuously stirring for 2 hours, performing suction filtration on the obtained green precipitate, drying in an oven at 65 ℃, and grinding into green powder;
and (3) taking 50mg of green powder, and carrying out heat treatment at 900 ℃ for 2h in an argon atmosphere to obtain the FeP @ ZIF-8-900 hybrid electrocatalyst.
As shown in fig. 5, a standard three-electrode system is used to test the oxygen reduction activity of the electrocatalyst, a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the FeP @ ZIF-8-900 hybrid electrocatalyst is prepared into a thin film working electrode under the following test conditions: 0.1mol/L HClO saturated with oxygen at 25 DEG C4In the aqueous solution, potential scanning test is carried out under the voltage of 0-1.2V (vs RHE), the half-wave potential of the electrocatalyst is calculated to be 0.7V (vs RHE), which is far lower than that of the sample in the example 1, and the product can not be synthesized by using methanol as the solvent.
Comparative example 2
Adding 30mg of hemin into 5mL of 1.2M 2-methylimidazole aqueous solution at 140 ℃, performing ultrasonic homogenization to obtain solution A, adding 5mL of 0.3M zinc acetate aqueous solution into the solution A which is continuously stirred, continuously stirring for 2 hours, performing suction filtration on the obtained green precipitate, drying in an oven at 65 ℃, and grinding into green powder;
and (3) taking 50mg of green powder, and carrying out heat treatment at 800 ℃ for 2H under the argon atmosphere to obtain the H-FeP @ ZIF-8-800 hybrid electrocatalyst.
From FIG. 6, the oxygen reduction activity of the electrocatalyst was tested using a standard three-electrode system with a carbon rod as the counter electrode and a saturated calomel electrode as the counter electrodeThe reference electrode is a thin film working electrode prepared from the H-FeP @ ZIF-8-800 hybrid electrocatalyst, and the test conditions are as follows: 0.1mol/L HClO saturated with oxygen at 25 DEG C4In the aqueous solution, potential scanning test is carried out under the voltage of 0-1.2V (vs RHE), the half-wave potential of the electrocatalyst is calculated to be 0.75V (vs RHE), which is far lower than that of the sample in the example 1, and the product cannot be synthesized by adopting a hydrothermal high-temperature high-pressure method.
Comparative example 3
Adding 30mg of hemin into 5mL of 8.0M 2-methylimidazole methanol solution at 25 ℃, performing ultrasonic homogenization to obtain solution A, adding 5mL of 2.0M zinc acetate methanol solution into the solution A which is continuously stirred, continuously stirring for 2 hours, performing suction filtration on the obtained green precipitate, drying in an oven at 65 ℃, and grinding into green powder;
and (3) taking 50mg of green powder, and carrying out heat treatment at 900 ℃ for 2h in an argon atmosphere to obtain the 1-FeP @ ZIF-8-900 hybrid electrocatalyst.
From fig. 7, a standard three-electrode system is used to test the oxygen reduction activity of the electrocatalyst, a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the 1-FeP @ ZIF-8-900 hybrid electrocatalyst is prepared into a thin film working electrode under the test conditions that: 0.1mol/L HClO saturated with oxygen at 25 DEG C4In aqueous solution, potential scan test is carried out under the voltage of 0-1.2V (vs RHE), and the half-wave potential of the electrocatalyst is calculated to be 0.72V (vs RHE) which is far lower than that of the sample in the example 1, which shows that the product of the invention can not be synthesized by adopting the condition of exceeding the concentration range of zinc acetate in the application.
Claims (10)
1. A preparation method of a porphyrin zeolite imidazole framework hybrid electrocatalyst is characterized by comprising the following steps: the preparation method comprises the following steps:
1) preparation of porphyrin and zeolite imidazole framework self-assembly hybrid precursor porphyrin @ ZIF-8: dissolving porphyrin in an aqueous solution of 2-methylimidazole to obtain a solution A, adding a zinc acetate solution into the solution A to obtain a green precipitate, performing solid-liquid separation, drying, and grinding to obtain green powder;
2) preparation of porphyrin @ ZIF-8 hybrid precursor-derived electrocatalyst: carrying out heat treatment on the product obtained in the step 1) at the temperature of 500-900 ℃ for 2h in the inert gas atmosphere to obtain the non-noble metal electrocatalyst.
2. The method of preparing a hybrid electrocatalyst with porphyrin zeolite imidazole framework according to claim 1, wherein: the porphyrin is at least one of 5,10,15, 20-tetra (4-carboxyphenyl) ferriporphyrin, 5,10,15, 20-tetra (4-carboxyphenyl) cobalt porphyrin, 5,10,15, 20-tetra (4-carboxyphenyl) copper porphyrin, 5,10,15, 20-tetra (4-carboxyphenyl) manganoporphyrin, protoporphyrin cobalt chloride, hemin, protoporphyrin copper chloride, protoporphyrin manganese chloride, meso-tetra (4-benzenesulfonyl) porphyrin iron, meso-tetra (4-benzenesulfonyl) porphyrin cobalt, meso-tetra (4-benzenesulfonyl) porphyrin manganese and meso-tetra (4-benzenesulfonyl) porphyrin copper.
3. The method of preparing a hybrid electrocatalyst with porphyrin zeolite imidazole framework according to claim 2, wherein: the ratio of the porphyrin to the 2-methylimidazole aqueous solution is 20-100mg/5-50 mL.
4. The method of preparing a hybrid electrocatalyst with porphyrin zeolite imidazole framework according to claim 3, wherein: the concentration of the 2-methylimidazole aqueous solution is 0.4-2M.
5. The method of preparing the porphyrin zeolite imidazole-framework hybrid electrocatalyst according to claim 4, wherein: the concentration of the zinc acetate solution is 0.1-0.5M.
6. The method of preparing the porphyrin zeolite imidazole-framework hybrid electrocatalyst according to claim 5, wherein: the volume ratio of the zinc acetate solution to the 2-methylimidazole aqueous solution is 1: 1.
7. the method of preparing the porphyrin zeolite imidazole-framework hybrid electrocatalyst according to claim 6, wherein: the stirring conditions of the zinc acetate solution and the solution A are as follows: stirring for 1-4h at 25-40 ℃.
8. The method of preparing a hybrid electrocatalyst with porphyrin zeolite imidazole framework according to claim 7, wherein: the drying temperature is 65-70 ℃.
9. A porphyrin zeolite imidazole framework hybrid electrocatalyst prepared by the process of claim 1, 2, 3, 4, 5, 6, 7 or 8.
10. Use of the porphyrin zeolite imidazole framework hybrid electrocatalyst according to claim 9 in polymer electrolyte membrane fuel cells.
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| CN111957336A (en) * | 2020-08-06 | 2020-11-20 | 济南大学 | Preparation method of ZIF-8-derived Fe-N-C oxygen reduction electrocatalyst |
| CN112038646A (en) * | 2020-09-14 | 2020-12-04 | 陈建夫 | Preparation method of catalyst for methanol fuel cell |
| CN112331869A (en) * | 2020-11-06 | 2021-02-05 | 五邑大学 | Cobalt-nitrogen double-doped hybrid carbon material and preparation method thereof |
| CN113745539A (en) * | 2021-09-03 | 2021-12-03 | 大连理工大学 | Fluorine-containing non-noble metal oxygen reduction electrocatalyst and preparation method and application thereof |
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