CN112397734B - 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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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 67
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 45
- 239000001301 oxygen Substances 0.000 title claims abstract description 45
- 230000009467 reduction Effects 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title abstract description 9
- 150000002678 macrocyclic compounds Chemical class 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 239000000446 fuel Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 229910002556 Fe–N4 Inorganic materials 0.000 claims abstract description 10
- 150000003754 zirconium Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000004032 porphyrins Chemical class 0.000 claims description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 2
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 claims description 2
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- BTIJJDXEELBZFS-QDUVMHSLSA-K hemin Chemical compound CC1=C(CCC(O)=O)C(C=C2C(CCC(O)=O)=C(C)\C(N2[Fe](Cl)N23)=C\4)=N\C1=C/C2=C(C)C(C=C)=C3\C=C/1C(C)=C(C=C)C/4=N\1 BTIJJDXEELBZFS-QDUVMHSLSA-K 0.000 claims description 2
- 229940025294 hemin Drugs 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000005518 polymer electrolyte Substances 0.000 abstract description 5
- 230000010757 Reduction Activity Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000000643 oven drying Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 44
- 239000012621 metal-organic framework Substances 0.000 description 27
- 238000006722 reduction reaction Methods 0.000 description 27
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 20
- 239000013097 PCN-222 Substances 0.000 description 15
- 150000003278 haem Chemical class 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 239000005711 Benzoic acid Substances 0.000 description 10
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 10
- 235000010233 benzoic acid Nutrition 0.000 description 10
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000011161 development Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 4-carboxyphenyl Chemical group 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000013260 porous coordination network Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241001478428 Syngnathus Species 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 238000002050 diffraction method Methods 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229920003240 metallophthalocyanine polymer Polymers 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides high-density Fe-N4Preparation method of active site oxygen reduction electrocatalyst and active site oxygen reduction electrocatalystThe application belongs 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 (readily soluble and reaggregable) and poor resistance to the reactants (e.g., methanol) under practical conditions of fuel cells, which are problematic in thatThe electrocatalyst becomes one of the key factors that hinder 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 macrocycles2the-N-C non-noble metal oxygen reduction electrocatalyst is widely researched 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 an electrocatalyst to increase itCatalytic 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 high-density Fe-N with excellent oxygen reduction comprehensive performance is prepared by high-temperature pyrolysis carbonization4An 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 generated by taking another macrocyclic compound as an organic ligand, so that the active site density of the electrocatalyst is improved; 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 ZrOCl2·8H2Dispersing O in 8mL of DMF solution, adding 650mg of benzoic acid 20mg of Heme, 30mg of meso-tetra (4-carboxyphenyl) porphin (TCPP) and 10mg of meso-tetra (4-carboxyphenyl) porphin 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 110PCN 222, initial PCN 222 of the electrocatalyst precursor obtained in example 2 andas can be seen from the pore size distribution of the electrocatalyst precursor 20-Heme @ PCN-222 obtained in example 4, the prepared precursor has both micropores and mesopores, and in addition, 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 ZrOCl2·8H2Dispersing O in 8mL of DMF solution, adding 650mg of benzoic acid 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 PCN-222, heating the precursor to 700 ℃ at the rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain a black powder solid, recording the black powder solid as PCN-222-one 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 DMF solution, adding 650mg benzoic acid 20mg Heme, 40mg TCPP, performing ultrasonic treatment at 25 deg.C for 30min, reacting at 120 deg.C for 12h, filtering, washingWashing the filtrate until the filtrate is colorless, drying the filtrate at 65 ℃ to obtain a precursor of the electrocatalyst, which is recorded as 20-Heme @ PCN-222, heating the precursor to 700 ℃ at a temperature rise rate of 5 ℃/min, and keeping the temperature for 2h to finally obtain a black powder solid, which is recorded 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 of DMF solution, adding 650mg of benzoic acid 40mg 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 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, recording the black powder solid 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 the precursor of the electrocatalystRecorded as 20-Heme @ 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 ℃ 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, and recording the precursor as 20-Heme Fe @ 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 (6)
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;
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 I is free of metal elements and/or comprises metal elements, and the metal is iron; the metal macrocyclic compound II is hemin;
the zirconium salt is ZrCl4、ZrOCl2·8H2O、ZrO(NO3)2·H2One or more than two of O;
the organic acid is CH2O2、C2H4O2、C2HF3O2、C3H6O2、C4H8O2、C2H2Cl2O2、C7H6O2、C8H8O2One or a mixture of two or more of them.
2. 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.
3. 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.
4. 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.
5. High density Fe-N produced by the production method according to any one of claims 1 to 44Active site oxygen reduction electrocatalysisAn oxidizing agent.
6. High density Fe-N according to claim 54Use of an active site oxygen reduction electrocatalyst in a fuel cell.
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