CN112397734A - High-density Fe-N4Preparation method and application of active site oxygen reduction electrocatalyst - Google Patents
High-density Fe-N4Preparation method and application of active site oxygen reduction electrocatalyst Download PDFInfo
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Abstract
The invention provides high-density Fe-N4A preparation method and application of an active site oxygen reduction electrocatalyst belong to the field of polymer electrolyte membrane fuel cell catalysts. Uniformly dispersing metal zirconium salt in a solvent, wherein Zr in the zirconium salt4+Adding two macrocyclic compounds including macrocyclic compound I, metal macrocyclic compound II and organic acid into solvent at concentration of 2-8mg/ml, ultrasonic treating at 20-40 deg.C for 10-30min, reacting at 120 deg.C for 8-12h, vacuum filtering, washing until the filtrate is colorless, oven drying, and pyrolyzing at 600-900 deg.C for 1-2h to obtain high-density Fe-N4An active site oxygen reduction electrocatalyst. The method is simple to operate, easy to control and environment-friendly, and the prepared high-density Fe-N is4The active site oxygen reduction electrocatalyst has excellent oxygen reduction activity and can be used for polymer electrolyte membrane fuel cells.
Description
Technical Field
The invention relates to the field of a polymer electrolyte membrane fuel cell cathode oxygen reduction electrocatalyst, in particular to high-density Fe-N4A preparation method and application of an active site oxygen reduction electrocatalyst.
Background
Since the recent development of industrialization, the massive and unreasonable use of non-renewable fossil fuels such as coal, oil and natural gas has led to global nitrogen, sulfur and carbon (NO) containingx、SOxCO), etc., causing a series of global concerns such as global temperature rise, environmental deterioration, human health, global energy crisis, etc. Therefore, the development of environment-friendly, sustainable, safe and efficient energy technology is urgently needed. Polymer Electrolyte Membrane Fuel Cells (PEMFCs) have received attention from various countries in the world, because they have the advantages of high energy conversion efficiency, environmental friendliness, rapid start at room temperature, no electrolyte loss, high specific power and specific energy, and the like.
High activity, high stability electrocatalysts are one of the important building materials for PEMFCs. The advent of platinum (Pt) -based catalysts has greatly facilitated the development of fuel cells, driving practical applications for fuel cells. However, the low global reserves of Pt result in relatively high prices, and in addition, Pt-based electrocatalysts have poor stability (easy dissolution and reaggregation) and poor resistance to reactants (e.g., methanol) under practical conditions of fuel cells, which make electrocatalysts one of the key factors hindering the commercialization of fuel cells. In the face of the above problems, scientists propose two strategies, the first: development of Pt-M1(M1Can be Pd, Au and other noble metals, can also be Fe, Co, Ni and other transition metals) material, reduces the consumption of Pt and simultaneously improves the catalytic activity and the durability of the electrocatalyst through shape control and alloy development; the second strategy is: development of non-noble metal oxygen reduction electrocatalysts, in which M is2-N-C(M2Mainly transition metals such as Fe, Co, Mn, etc.) based non-noble metal electrocatalysts have gained wide attention due to their advantages such as low cost, high activity, high durability, methanol resistance, etc.
In the last 60 th century, Jasinski first reported N4After the chelate phthalocyanine cobalt has oxygen reduction activity in alkaline electrolyte, a new field of non-noble metal oxygen reduction electrocatalyst research is opened. (Nature,1964,201,1212-1213) since then, numerous M's based on metallophthalocyanines and metalloporphyrin-like macrocycles2-N-C non-nobleThe metal oxygen reduction electrocatalyst is widely studied and reported. Such as: the Wei group obtained electrocatalysts with higher oxygen reduction activity and better durability by loading ferriporphyrin on carbon materials through covalent bonds (angelw. chem.,2014,126, 6777-6781). Metallomacrocycles due to their unique M2-N4The structure of the oxygen reduction electrocatalyst is a good precursor of a non-noble metal oxygen reduction electrocatalyst, at present, the preparation principle of the oxygen reduction electrocatalyst based on metal phthalocyanine or metalloporphyrin macrocyclic compounds is mainly to finish intermolecular accumulation (such as pi-pi effect, positive and negative charge interaction and hydrogen bonds) through a plurality of acting forces, and then the material stability is improved through high-temperature pyrolysis and carbonization in an inert atmosphere, however, uncontrollable property in the pyrolysis process can often cause metal aggregation, and the utilization rate of the material is reduced. Therefore, a strategy is needed to improve the utilization rate of the metal macrocyclic compound in the process of preparing the oxygen reduction electrocatalyst, and the occurrence of Metal Organic Frameworks (MOFs) realizes the accumulation of the metal phthalocyanine or metalloporphyrin macrocyclic compound from disordered molecules to ordered molecular arrangement.
MOFs are organic-inorganic hybrid materials formed by organic ligands and metal ions or multi-core metal clusters through coordination bonds, and have well-defined topological structures in geometry and crystallography due to the coordination bond connection with strong guidance. The MOFs have the characteristics of porosity, easy functionalization, good designability, high specific surface area and the like. Two important constituent units of the MOFs, namely metal ions or clusters and organic ligands, provide multiple possibilities for the synthesis of the materials. With the intensive research on synthesis and structural characterization, more and more MOFs materials are found and applied to optics, magnetics and electrics, and have application values in the fields of catalysis, gas storage, separation and the like.
MOFs materials have rapidly developed, and in 2008, the Xu team reports for the first time that MOF-5 is used as a precursor, a porous carbon carrier is prepared after high-temperature pyrolysis and is applied to the field OF oxygen reduction (JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2008,130(16): 5390-5391.). The MOFs has stable structure, and after the MOFs is pyrolyzed and carbonized at high temperature, the conductivity of the MOFs can be greatly improved, the porous characteristic is kept, and O is facilitated2The transmission of (2) is easy to occur in the four-electron reduction process, the catalytic activity is improved, and H generated by two electrons is reduced2O2Species attack the active sites of the catalyst, and the service life of electrocatalysis is prolonged.
With the development of the MOFs materials, scientists have realized that a series of zirconium-based metal cluster MOFs (angelw.chem.int.ed.2012, 51,10307-10310) are synthesized by taking a macrocyclic compound as an organic ligand of the MOFs, and are gradually applied to the field of electrocatalysis. Such as: zr for 2017 ginger and Syngnathus team6The cluster is a metal cluster, m-tetra (4-carboxyphenyl) porphin (TCPP) is used as a ligand, a PCN-224MOFs material is synthesized, a catalyst with a stable structure is obtained through Fe and Co metal salt adsorption, high-temperature pyrolysis and acid cleaning etching, and the durability of the catalyst is greatly improved (ChemSusChem,2017,10, 1-7). Through the combination with MOFs structure, although the activity and the durability of the metal macrocyclic compound are greatly improved, the catalytic activity of the electrocatalyst prepared by the method can not meet the activity requirement of the PEMFCs, and the electrocatalyst is difficult to be applied to a proton exchange membrane fuel cell. Therefore, there is an urgent need for a strategy to increase the density of active sites of electrocatalysts to increase their catalytic activity to accelerate the development of PEMFCs.
Disclosure of Invention
The invention aims to provide high-density Fe-N4The preparation method and the application of the active site oxygen reduction electrocatalyst have the advantages of simple operation, easy control and environmental protection. The high density Fe-N4The active site oxygen reduction electrocatalyst takes two macrocyclic compounds as raw materials, wherein one macrocyclic compound I (named as Zr)6-Porphyrin) and Zr6The metal clusters are combined in the form of ion coordination bonds to form a three-dimensional porous highly-crystalline material, the material has high specific surface area and has two pore diameters of micropores (less than 2nm) and mesopores (2-50nm), and before the MOFs three-dimensional structure is formed, another metal macrocyclic compound II (named as Precursor-porphyrin) with oxygen reduction catalytic capability is connected with Zr through the ion coordination bonds6The metal clusters are combined, the Precursor-porphyrin is synchronously embedded into mesopores of the MOFs material while the MOFs material is synthesized to be used as a catalytic active site, and then the catalyst is prepared by high-temperature pyrolysis carbonizationTo high density Fe-N with excellent oxygen reduction combination properties4An active site oxygen reduction electrocatalyst is suitable for a proton exchange membrane fuel cell.
In order to achieve the purpose, the technical scheme of the invention is as follows:
high-density Fe-N4The preparation method of the active site oxygen reduction electrocatalyst comprises the following steps:
uniformly dispersing metal salt (zirconium salt) of zirconium in a solvent, wherein Zr in the zirconium salt4+The concentration in the solvent is 2-8mg/ml, and two macrocyclic compounds including macrocyclic compound I (named Zr)6-Porphyrin), a metal macrocyclic compound II (named as Precursor-Porphyrin)) and organic acid, performing ultrasonic treatment for 10-30min at the temperature of 20-40 ℃, reacting for 8-12h at the temperature of 120 ℃, performing suction filtration, washing until the filtrate is colorless, drying, and pyrolyzing for 1-2h at the temperature of 600-4An active site oxygen reduction electrocatalyst;
the macrocyclic compound I (Zr)6-Porphyrin) and a zirconium salt species in a ratio of (0.1-0.4) to 1, preferably 0.37: 1;
the metal macrocyclic compound II (Precurror-Porphyrin) and the macrocyclic compound I (Zr)6-Porphyrin) in a mass ratio of (0.25-1) to 1;
the mass ratio of the organic acid to the zirconium salt is (20-30) to 1;
based on the technical scheme, preferably, the zirconium salt comprises ZrCl4、ZrOCl2·8H2O、ZrO(NO3)2·H2One or more than two of O.
Based on the technical scheme, preferably, the organic acid comprises CH2O2、C2H4O2、C2HF3O2、C3H6O2、C4H8O2、C2H2Cl2O2、C7H6O2、C8H8O2One or a mixture of two or more of them.
Based on the technical scheme, preferably, the macrocyclic compound I (Zr)6-Porphyrin) is a Porphyrin or phthalocyanine having four carboxyl groups in the side chains, wherein the center of said macrocyclic compound is free of and/or includes a metal element, if it is referred to the use of a metalloporphyrin or phthalocyanine, said metal being iron; the metal macrocyclic compound II (Precusor-porphyrin) is hemin (Heme).
Based on the above technical scheme, preferably, the solvent comprises one or a mixture of more than two of ethanol, propanol, isopropanol, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), and N, N-Dimethylacetamide (DMAC).
Based on the technical scheme, the preferable rate of heating to the pyrolysis temperature is 1-10 ℃/min.
The invention also relates to the protection of the high-density Fe-N obtained by the preparation method4An active site oxygen reduction electrocatalyst.
The invention also relates to the protection of the high-density Fe-N4Use of an active site oxygen reduction electrocatalyst in a proton exchange membrane fuel cell.
The invention provides a high-density Fe-N4The preparation method of the active site oxygen reduction electrocatalyst takes two macrocyclic compounds as raw materials, wherein one macrocyclic compound (named as Zr)6-Porphyrin) and Zr6The metal cluster is combined and grown into the MOFs material with a three-dimensional structure in the form of ion coordination bonds, another metal macrocyclic compound (named as Precursor-porphyrin) is used as a Precursor for increasing the density of active sites, the Precursor-porphyrin is embedded into the pore channel of the MOFs material on the basis of not influencing mass transfer, the density of the active sites of the oxygen reduction electrocatalyst is improved, and the high-density Fe-N is prepared by the method4The active site oxygen reduction electrocatalyst exhibits excellent oxygen reduction catalytic activity and stability.
Compared with the prior art, the invention has the outstanding characteristics that: 1) the metal macrocyclic compound with catalytic activity is embedded into the mesopores of the MOFs material which is generated by taking another macrocyclic compound as an organic ligand, so that the active site density of the electrocatalyst is improved(ii) a 2) MOFs are porous, their mesoporous structure is not completely filled with metal macrocycles, and O is still favored2The transmission of (1); 3) the conductivity of MOFs is improved after pyrolysis, and meanwhile, the three-dimensional structure of the MOFs is partially reserved, so that the catalytic activity of oxygen reduction is improved; 4) the utilization of MOFs structure may be beneficial to the four-electron oxygen reduction process, and reduce the generation of H capable of attacking porphyrin ring2O2And the service life of the electrocatalyst is prolonged. 5) The method is simple to operate, easy to control and environment-friendly, and the prepared high-density Fe-N is4The active site oxygen reduction electrocatalyst has excellent oxygen reduction activity and can be used for polymer electrolyte membrane fuel cells.
Drawings
FIG. 1 is an SEM image of an electrocatalyst precursor obtained according to the present invention, wherein a is the electrocatalyst precursor PCN-222 obtained according to comparative example 1; b is the electrocatalyst precursor 20-Heme @ Fe obtained in example 110-PCN-222；
FIG. 2 shows the electrocatalyst precursors PCN-222 obtained in comparative example 1 and 20-Heme @ Fe obtained in example 110-PCN-222 and simulated PCN-222XRD contrast patterns;
FIG. 3 shows the electrocatalyst precursor PCN-222 obtained in comparative example 1, the electrocatalyst precursor 20-Heme @ PCN-222 obtained in example 3, and the electrocatalyst precursor 20-Heme @ Fe obtained in example 110-an aperture profile of PCN-222;
FIG. 4 shows the product PCN-222-700 obtained in comparative example 1, the product 20-Heme @ PCN-222-700 obtained in example 3, and the product 20-Heme @ Fe obtained in example 110ORR polarization plot of PCN-222-700.
Detailed Description
The invention is further described in the following with reference to the drawings and examples, which are provided only for the purpose of illustrating the invention more clearly, but the scope of the invention as claimed is not limited to the scope of the embodiments presented below.
Example 1
40mg of ZrOCl2·8H2O was dispersed in 8mL of DMF solution, and 650mg of benzoic acid, 20mg of Heme, 30mg of meso-tetrakis (4-carboxy) were addedPhenyl) Porphine (TCPP), 10mg meso-tetra (4-carboxyphenyl) porphine ferric chloride (Fe-TCPP), performing ultrasonic treatment at 25 ℃ for 30min, reacting at 120 ℃ for 12h, performing suction filtration, washing until the filtrate is colorless, and drying at 65 ℃ to obtain a precursor of the electrocatalyst, which is recorded as 20-Heme @ Fe10-PCN-222, heating the precursor to 700 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain black powder solid, which is recorded as 20-Heme @ Fe10-PCN-222-700。
As shown in FIG. 1, prepared was the electrocatalyst precursor 20-Heme @ Fe obtained in example 110The PCN-222 is rod-shaped and uniform in size and is in accordance with the morphology of the original PCN-222 of the electrocatalyst precursor obtained in example 2, but its size is reduced.
As shown in fig. 2, the XRD diffraction peak of the precursor of the prepared electrocatalyst is consistent with the peak position of the simulated MOFs, which indicates that the introduction of Heme does not result in the structure of MOFs, and the obtained precursor is a highly crystalline material.
As shown in FIG. 3, prepared was the electrocatalyst precursor 20-Heme @ Fe obtained in example 110The pore size distributions of the PCN-222, the initial PCN-222 of the electrocatalyst precursor obtained in example 2, and the 20-Heme @ PCN-222 of the electrocatalyst precursor obtained in example 4 show that the prepared precursors both have both micropores and mesopores, and that, when the Heme is introduced, the obtained precursor 20-Heme @ Fe10The mesoporous volume of-PCN-222 and 20-Heme @ PCN-222 is reduced, and the fact that the Heme is embedded into the mesopores of the MOFs is directly proved.
Referring to fig. 4, the electrochemical performance of the oxygen reduction reaction test is measured by a standard three-electrode method, the catalyst is made into a thin-film working electrode, and the test conditions are as follows: 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 activity of the electrocatalyst is gradually increased along with the introduction of the Heme and the Fe-TCPP, which shows that the introduction of the Heme and the Fe-TCPP gradually increases the density of active sites of the electrocatalyst, and improves the catalytic activity of the electrocatalyst.
Comparative example 1
40mg of ZrOCl2·8H2O is dispersed inAdding 650mg of benzoic acid and 40mg of TCPP into 8mL of DMF solution, performing ultrasonic treatment at 25 ℃ for 30min, reacting at 120 ℃ for 12h, performing suction filtration, washing until the filtrate is colorless, drying at 65 ℃ to obtain a precursor of the electrocatalyst, recording the precursor as PCN-222, heating the precursor to 700 ℃ at the rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain black powder solid, recording the black powder solid as PCN-222-700.
Example 2
40mg of ZrOCl2·8H2Dispersing O in 8mL of DMF solution, adding 650mg of benzoic acid 10mg of Heme and 40mg of TCPP, performing ultrasonic treatment at 25 ℃ for 30min, performing suction filtration at 120 ℃ for 12h, washing until the filtrate is colorless, drying at 65 ℃ to obtain a precursor of the electrocatalyst, recording the precursor as 10-Heme @ PCN-222, heating the precursor to 700 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain a black powder solid, recording the black powder solid as 10-Heme @ PCN-222-700.
Example 3
40mg of ZrOCl2·8H2Dispersing O in 8mL of DMF solution, adding 650mg of benzoic acid 20mg of Heme and 40mg of TCPP, performing ultrasonic treatment at 25 ℃ for 30min, reacting at 120 ℃ for 12h, performing suction filtration, washing until the filtrate is colorless, drying at 65 ℃ to obtain a precursor of the electrocatalyst, recording the precursor as 20-Heme @ PCN-222, heating the precursor to 700 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain a black powder solid, recording the black powder solid as 20-Heme @ PCN-222-700.
Example 4
40mg of ZrOCl2·8H2Dispersing O in 8mL of DMF solution, adding 650mg of benzoic acid 30mg of Heme and 40mg of TCPP, performing ultrasonic treatment at 25 ℃ for 30min, reacting at 120 ℃ for 12h, performing suction filtration, washing until the filtrate is colorless, drying at 65 ℃ to obtain a precursor of the electrocatalyst, recording the precursor as 30-Heme @ PCN-222, raising the temperature of the precursor to 700 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2h to finally obtain a black powder solid, recording the black powder solid as 30-Heme @ PCN-222-700.
Example 5
40mg of ZrOCl2·8H2Dispersing O in 8mL DMF solution, adding 650mg benzoic acid 40mg Heme, 40mg TCPP, performing ultrasonic treatment at 25 deg.C for 30min, reacting at 120 deg.C for 12 hr, vacuum filtering, washing until the filtrate is colorless, and oven drying at 65 deg.CObtaining a precursor of the electrocatalyst, which is marked as 40-Heme @ PCN-222, heating the precursor to 700 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain a black powder solid, which is marked as 40-Heme @ PCN-222-700.
Example 6
40mg of ZrOCl2·8H2Dispersing O in 8mL DMF solution, adding 650mg benzoic acid 20mg Heme, 35TCPP and 5mg Fe-TCPP, performing ultrasonic treatment at 25 ℃ for 30min, reacting at 120 ℃ for 12h, performing suction filtration, washing until the filtrate is colorless, and drying at 65 ℃ to obtain a precursor of the electrocatalyst, which is recorded as 20-He @ me Fe5-PCN-222, heating the precursor to 700 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain black powder solid, which is recorded as 20-Heme @ Fe5-PCN-222-700。
Example 7
40mg of ZrOCl2·8H2Dispersing O in 8mL DMF solution, adding 650mg benzoic acid 20mg Heme, 20TCPP and 20mg Fe-TCPP, performing ultrasonic treatment at 25 ℃ for 30min, reacting at 120 ℃ for 12h, performing suction filtration, washing until the filtrate is colorless, and drying at 65 ℃ to obtain a precursor of the electrocatalyst, which is recorded as 20-He @ me Fe20-PCN-222, heating the precursor to 700 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain black powder solid, which is recorded as 20-Heme @ Fe20-PCN-222-700。
Example 8
40mg of ZrOCl2·8H2Dispersing O in 8mL DMF solution, adding 650mg benzoic acid 20mg Heme, 10TCPP and 30mg Fe-TCPP, performing ultrasonic treatment at 25 ℃ for 30min, reacting at 120 ℃ for 12h, performing suction filtration, washing until the filtrate is colorless, and drying at 65 ℃ to obtain a precursor of the electrocatalyst, which is recorded as 20-He @ me Fe30-PCN-222, heating the precursor to 700 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain black powder solid, which is recorded as 20-Heme @ Fe30-PCN-222-700。
Example 9
40mg of ZrOCl2·8H2Dispersing O in 8mL DMF solution, adding 650mg benzoic acid 20mg Heme, 40mg Fe-TCPP, performing ultrasonic treatment at 25 deg.C for 30min, reacting at 120 deg.C for 12h, vacuum filtering, washing until the filtrate is colorless, oven drying at 65 deg.CObtaining the precursor of the electrocatalyst, which is recorded as 20-Heme @ Fe40-PCN-222, heating the precursor to 700 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain black powder solid, which is recorded as 20-Heme @ Fe40-PCN-222-700。
Claims (9)
1. High-density Fe-N4The preparation method of the active site oxygen reduction electrocatalyst is characterized by comprising the following steps of:
uniformly dispersing zirconium salt in a solvent, adding a macrocyclic compound I, a metal macrocyclic compound II and an organic acid, carrying out ultrasonic treatment for 10-30min at the temperature of 20-40 ℃, reacting for 8-12h at the temperature of 120 ℃, carrying out suction filtration, washing until filtrate is colorless, drying, and pyrolyzing for 1-2h at the temperature of 600-900 ℃ to obtain high-density Fe-N4An active site oxygen reduction electrocatalyst;
the mass ratio of the macrocyclic compound I to the zirconium salt is 0.1-0.4: 1;
the mass ratio of the metal macrocyclic compound II to the macrocyclic compound I is 0.25-1: 1;
the mass ratio of the organic acid to the zirconium salt is 20-30: 1.
2. High density Fe-N according to claim 14The preparation method of the active site oxygen reduction electrocatalyst is characterized in that the organic acid is CH2O2、C2H4O2、C2HF3O2、C3H6O2、C4H8O2、C2H2Cl2O2、C7H6O2、C8H8O2One or a mixture of two or more of them.
3. A high density Fe-N according to claim 1 or 24The preparation method of the active site oxygen reduction electrocatalyst is characterized in that the macrocyclic compound I is porphyrin or phthalocyanine or porphin with four carboxyl groups on the side chain, wherein the center of the macrocyclic compound INo metal element and/or metal element, wherein the metal is iron; the metal macrocyclic compound II is hemin.
4. High density Fe-N according to claim 14The preparation method of the active site oxygen reduction electrocatalyst is characterized in that the zirconium salt is ZrCl4、ZrOCl2·8H2O、ZrO(NO3)2·H2One or more than two of O.
5. High density Fe-N according to claim 14The preparation method of the active site oxygen reduction electrocatalyst is characterized in that the solvent is one or a mixture of more than two of ethanol, propanol, isopropanol, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
6. High density Fe-N according to claim 14The preparation method of the active site oxygen reduction electrocatalyst is characterized in that the concentration of zirconium in a solvent in the zirconium salt is 2-8 mg/ml.
7. High density Fe-N according to claim 14The preparation method of the active site oxygen reduction electrocatalyst is characterized in that the rate of heating to the pyrolysis temperature is 1-10 ℃/min.
8. High density Fe-N produced by the production method according to any one of claims 1 to 74An active site oxygen reduction electrocatalyst.
9. High density Fe-N according to claim 84Use of an active site oxygen reduction electrocatalyst in a fuel cell.
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Cited By (2)
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| CN113889630A (en) * | 2021-09-29 | 2022-01-04 | 陕西科技大学 | Preparation method of composite structure oxygen reduction electrocatalyst for fuel cell cathode |
| CN114284514A (en) * | 2021-12-27 | 2022-04-05 | 格林美股份有限公司 | Fuel cell electrocatalyst Pt3M-N/C and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011114783A1 (en) * | 2010-03-16 | 2011-09-22 | 凸版印刷株式会社 | Process for production of cathode catalyst layer for fuel cell, cathode catalyst layer, and membrane electrode assembly for solid polymer fuel cell |
| CN104478905A (en) * | 2014-12-15 | 2015-04-01 | 江西师范大学 | Novel copper-hemin organic frame structure with three-dimensional porous ball-flower structure and preparation method of novel copper-hemin organic frame structure |
| CN106876730A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | The porous carbon-supported base metal elctro-catalyst of N doping is prepared and electro-catalysis application |
| CN107056793A (en) * | 2017-05-17 | 2017-08-18 | 西北师范大学 | A kind of method that high-yield and high-efficiency synthesizes TNPP, TAPP |
| CN111129524A (en) * | 2019-12-27 | 2020-05-08 | 大连理工大学 | Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst and preparation method and application thereof |
-
2020
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011114783A1 (en) * | 2010-03-16 | 2011-09-22 | 凸版印刷株式会社 | Process for production of cathode catalyst layer for fuel cell, cathode catalyst layer, and membrane electrode assembly for solid polymer fuel cell |
| CN104478905A (en) * | 2014-12-15 | 2015-04-01 | 江西师范大学 | Novel copper-hemin organic frame structure with three-dimensional porous ball-flower structure and preparation method of novel copper-hemin organic frame structure |
| CN106876730A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | The porous carbon-supported base metal elctro-catalyst of N doping is prepared and electro-catalysis application |
| CN107056793A (en) * | 2017-05-17 | 2017-08-18 | 西北师范大学 | A kind of method that high-yield and high-efficiency synthesizes TNPP, TAPP |
| CN111129524A (en) * | 2019-12-27 | 2020-05-08 | 大连理工大学 | Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113889630A (en) * | 2021-09-29 | 2022-01-04 | 陕西科技大学 | Preparation method of composite structure oxygen reduction electrocatalyst for fuel cell cathode |
| CN114284514A (en) * | 2021-12-27 | 2022-04-05 | 格林美股份有限公司 | Fuel cell electrocatalyst Pt3M-N/C and preparation method thereof |
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