CN117430791A - Cationic modified covalent cobalt porphyrin polymer, preparation method thereof and application of electrocatalytic oxygen reduction reaction - Google Patents
Cationic modified covalent cobalt porphyrin polymer, preparation method thereof and application of electrocatalytic oxygen reduction reaction Download PDFInfo
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- CN117430791A CN117430791A CN202311395047.8A CN202311395047A CN117430791A CN 117430791 A CN117430791 A CN 117430791A CN 202311395047 A CN202311395047 A CN 202311395047A CN 117430791 A CN117430791 A CN 117430791A
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- Prior art keywords
- cobalt porphyrin
- porphyrin
- cobalt
- cationic
- benzyl bromide
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- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 52
- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 239000001301 oxygen Substances 0.000 title claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000006722 reduction reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 4
- -1 cationic modified cobalt Chemical class 0.000 claims abstract description 12
- JGUCYLISNORQFW-UHFFFAOYSA-N 1-ethynyl-4-[tris(4-ethynylphenyl)methyl]benzene Chemical compound C1=CC(C#C)=CC=C1C(C=1C=CC(=CC=1)C#C)(C=1C=CC(=CC=1)C#C)C1=CC=C(C#C)C=C1 JGUCYLISNORQFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 150000004032 porphyrins Chemical class 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 239000003446 ligand Substances 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 11
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 6
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 6
- 238000003818 flash chromatography Methods 0.000 claims description 6
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- PVIVWSKQVHYIEI-UHFFFAOYSA-N 2-(bromomethyl)benzaldehyde Chemical compound BrCC1=CC=CC=C1C=O PVIVWSKQVHYIEI-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 claims description 3
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 claims description 3
- 235000010703 Modiola caroliniana Nutrition 0.000 claims description 3
- 244000038561 Modiola caroliniana Species 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
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- 125000000524 functional group Chemical group 0.000 abstract description 2
- CRZONOFOLSLKLM-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C2(=CC=CC=C2)[Co] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C2(=CC=CC=C2)[Co] CRZONOFOLSLKLM-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- YBGIIZGNEOJSRF-UHFFFAOYSA-N 1-bromo-4-[tris(4-bromophenyl)methyl]benzene Chemical compound C1=CC(Br)=CC=C1C(C=1C=CC(Br)=CC=1)(C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 YBGIIZGNEOJSRF-UHFFFAOYSA-N 0.000 description 5
- 125000000304 alkynyl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
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- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 description 3
- 229910020676 Co—N Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
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- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- BWZVWVOEWUSVMS-UHFFFAOYSA-N n,n-dimethylmethanamine;methanol Chemical compound OC.CN(C)C BWZVWVOEWUSVMS-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/37—Metal complexes
- C08G2261/376—Metal complexes of Fe, Co, Ni
Abstract
The invention discloses a cationic modified covalent cobalt porphyrin polymer, a preparation method thereof and application of electrocatalytic oxygen reduction reaction, wherein the cationic modified covalent cobalt porphyrin polymer is formed by introducing cationic functional groups into cobalt porphyrin complex to form cationic modified cobalt porphyrin-5, 15-dibromo-10, 20-bis (2-benzyltrimethyl ammonium hexafluorophosphate) cobalt porphyrin, and then the cationic modified covalent cobalt porphyrin polymer is cross-coupled with a tetra (4-ethynylphenyl) methane connector through a sonocephalic coupling reaction chemical bond. The cobalt porphyrin complex modified by the quaternary ammonium salt cation functional group is carried out on the molecular level, then the positive charge electrostatic effect is successfully introduced near the active center of the covalent polymer in a chemical bond coupling mode, and the cobalt porphyrin complex is used as a cathode catalyst for the electrocatalytic oxygen reduction reaction, so that the cobalt porphyrin complex has better electrocatalytic oxygen reduction reaction performance.
Description
Technical Field
The invention belongs to the technical field of new energy sources such as zinc-air batteries, hydrogen-oxygen fuel batteries and the like, and particularly relates to a cationic modified covalent cobalt porphyrin polymer formed by coupling a cobalt porphyrin complex with a cationic electrostatic action group with a tetraphenyl methane connector through a sonocephalic coupling reaction, and the cationic modified covalent cobalt porphyrin polymer is applied to an electrocatalytic oxygen reduction reaction.
Background
The demand for renewable and environmentally friendly energy has increased over the last decades. Fuel cells and metal-air cells that use oxygen reduction (ORR) as the cathode have become the next key technology to solve energy problems due to their high energy density and reliability (chord. Chem. Rev.,2023,474,214854). Since the oxygen reduction reaction involves a four-electron four-proton reduction process, the kinetics are slow and efficient catalyst participation is required. However, the high-efficiency noble metal catalyst is rare in reserves and expensive, and is not suitable for wide application, so that development of a high-efficiency stable non-noble metal-based ORR catalyst is imperative.
Metalloporphyrin/carboloy-based catalysts have definite and controllable molecular structures, and macrocyclic centers can stabilize high-valence metal ions, so that the metalloporphyrin/carboloy-based catalysts are widely applied to ORR and are widely used for researching structure-activity relationships and catalytic reaction mechanisms (chem. Rev.,2017,117,3717-3797). Cationic electrostatic action on metal complexes CO 2 Promotion in RR has been demonstrated to stabilize CO by introducing cationic electrostatic groups 2 The intermediate product, which improves the catalytic performance, is a very important performance control strategy (J.Am.chem.Soc., 2016,138,16639-16644; angew.chem.int.ed.,2022,61, e 202209702; chin.J.catalyst., 2022,43,3089-3094.; escace, 2022,2,623-631). Similarly, it has been reported in the literature that modification of the auxiliary electrostatic groups around porphyrins also stabilizes the central metal with O 2 The combined metal-superoxide anion intermediates, in turn, enhance the ORR performance of the catalyst (J.Am.chem.Soc., 2020,142,13426-13434; J.Am.chem.Soc.,2021,143,11423-11434; chem.Sci.,2019,10,9692-9698; inorg.chem.,2020,59,17402-17414; phys.chem.Phys., 2023,25,4604-4610).
Porphyrin-based covalent polymer material (POF) has the advantages of unique periodic topological structure, high specific surface area, adjustable pore diameter, chemical stability and the like, and can regulate and control the electronic structure and conjugated system of a metal active catalytic center through microenvironment, so that the porphyrin-based covalent polymer material is always active in the fields of efficient and environment-friendly energy conversion and catalysis (chem.Soc.rev.,2021,50,2540-2581; energy environ. Sci.,2018,11,1723-1729; adv.function.mate, 2019,29,190130; adv.sci.,2023,10,2206239; coord.chem.rev.,2022,464,214563.). In recent years, based on the catalytic properties of cationic electrostatic interactions, researchers have successfully modified them in polymers and in CO 2 RR and ORR exhibit excellent performance (J. Mater. Chem. A,2022,10,22781-22790; nat. Commun.,2023,14,3800; adv. Mater.,2022,34,2110496; angew. Chem. Int. Ed.,2022,61, e202212162; angew. Chem. Int. Ed.,2023,62, e 202215687). However, in the way of covalent polymer coupling and then modification, the formed cationic electrostatic functional groups are mostly positioned on the connector of the covalent polymer, so that on one hand, the modification reaction cannot be completely carried out (namely, all the sites on the connector are introduced with cationic groups), on the other hand, the modified cationic groups are far away from the catalytic active center of the polymer, the generated electrostatic effect is weaker, and the catalytic reaction performance of the catalytic active center cannot be improved.
Disclosure of Invention
The invention aims to provide a cationic electrostatically-modified Co porphyrin compound which is cross-coupled with corresponding tetraphenylmethane to form a cationic-modified covalent cobalt porphyrin polymer (N) + COP) while providing it with an application of electrocatalytic oxygen reduction reactions.
In view of the above, the structural formula of the cationic modified covalent cobalt porphyrin polymer provided by the invention is shown as follows:
wherein n represents the number of anions and the number is the same as the number of cations.
The synthetic route and the specific preparation method of the cation modified covalent cobalt porphyrin polymer are as follows:
step 1: adding 2- (bromomethyl) benzaldehyde and 2,2' -dipyrromethene into methylene dichloride, stirring at normal temperature under the condition of argon shading for 15-20 minutes, adding trifluoroacetic acid, reacting for 30-40 minutes, adding 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, stirring for 30-40 minutes, adding triethylamine for neutralization, and separating and purifying by flash column chromatography to obtain a 5, 15-bis (2-benzyl bromide) porphyrin ligand with the following structural formula;
step 2: adding the 5, 15-di (2-benzyl bromide) porphyrin ligand and zinc acetate dihydrate in the step 1 into tetrahydrofuran, refluxing in a dark place for 3-4 hours at 65-75 ℃, and obtaining 5, 15-di (2-benzyl bromide) zinc porphyrin after separation and purification by rapid column chromatography;
step 3: under anhydrous and anaerobic operation, dissolving 5, 15-bis (2-benzyl bromide) zinc porphyrin in the step 2 in chloroform, adding pyridine and N-bromosuccinimide at 0 ℃, reacting for 30-40 minutes, adding methanol for quenching, rotating and evaporating a solvent, and separating and purifying by flash column chromatography to obtain a purple solid; dissolving the purple solid in acetone, adding hydrochloric acid, stirring at room temperature for reaction for 2-3 hours, rotationally evaporating the solvent, extracting with pure water and dichloromethane, and performing rapid column chromatography separation and purification to obtain 5, 15-dibromo-10, 20-di (2-benzyl bromide) porphyrin ligand;
step 4: adding the 5, 15-dibromo-10, 20-di (2-benzyl bromide) porphyrin ligand and cobalt acetate tetrahydrate in the step 3 into a mixed solvent of chloroform and methanol, carrying out light-proof reflux reaction for 3-4 hours at 60-70 ℃, and obtaining 5, 15-dibromo-10, 20-di (2-benzyl bromide) cobalt porphyrin after rapid column chromatography separation and purification;
step 5: under the condition of nitrogen operated without water and oxygen, dissolving 5, 15-dibromo-10, 20-bis (2-benzyl bromide) cobalt porphyrin in the step 4 in tetrahydrofuran, adding trimethylamine, stirring at room temperature for 20-24 hours, filtering, collecting precipitate, dissolving with N, N-dimethylformamide, then dripping into saturated ammonium hexafluorophosphate aqueous solution, stirring for 4-6 hours, filtering, eluting the precipitate with diethyl ether, and vacuum drying to obtain mauve solid 5, 15-dibromo-10, 20-bis (2-benzyl trimethyl ammonium hexafluorophosphate) cobalt porphyrin, namely cationic cobalt porphyrin monomer;
step 6: under the condition of nitrogen, dissolving the cationic cobalt porphyrin monomer and tetra (4-ethynylphenyl) methane in the step 5 into N, N-dimethylformamide, adding triethylamine, ditriphenylphosphine palladium dichloride and cuprous iodide, stirring and reacting for 45-50 hours at 65-75 ℃, filtering, flushing with N, N-dimethylformamide, flushing with methanol, and vacuum drying to obtain the cationic modified covalent cobalt porphyrin polymer.
In the step 1, the molar ratio of the 2- (bromomethyl) benzaldehyde to the 2,2' -dipyrromethene to the trifluoroacetic acid to the 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is 1:1-1.2:2-6:2-4.
In the step 2, the molar ratio of the 5, 15-di (2-benzyl bromide) porphyrin ligand to zinc acetate dihydrate is 1:10-20.
In the step 3, the molar ratio of the 5, 15-di (2-benzyl bromide) zinc porphyrin to the N-bromosuccinimide to the pyridine is 1:2-3:1-5.
In the step 4, the molar ratio of the 5, 15-dibromo-10, 20-di (2-benzyl bromide) porphyrin ligand to the cobalt acetate tetrahydrate is 1:10-20.
In the step 5, the molar ratio of the 5, 15-dibromo-10, 20-di (2-benzyl bromide) cobalt porphyrin to the trimethylamine is 1:1-8.
In the step 6, the molar ratio of the cationic cobalt porphyrin monomer to the tetra (4-ethynylphenyl) methane to the triethylamine to the bis-triphenylphosphine palladium dichloride to the cuprous iodide is 1:0.3-0.7:20-50:0.02-0.1:0.02-0.1.
The cationic modified covalent cobalt porphyrin polymer can be used for electrocatalytic oxygen reduction reaction, and the specific application mode is as follows: the cation modified covalent cobalt porphyrin polymer and the carbon material are compounded to be used as a catalyst to be loaded on an electrode, and used as a cathode of an electrocatalytic reaction device, and a carbon rod or a platinum sheet is used as an anode to perform electrocatalytic oxygen reduction reaction in a 1.0mol/LKOH solution.
The beneficial effects of the invention are as follows:
according to the invention, a cobalt porphyrin molecule with quaternary ammonium salt cationic groups modified on the meso position is controllably synthesized by utilizing a molecular design principle, and is skillfully designed into a monomer structure and matched with a corresponding connector. The cobalt porphyrin monomer with cationic electrostatic effect and tetraphenyl methane connector are coupled by alkyne bond to form covalent organic polymer by means of cross coupling reaction of sonogashira head, and cationic electrostatic effect is modified on the polymer definitely and successfully. This design approach has for the first time been the successful introduction of cationic electrostatic effects at locations closer to the catalytic active sites of covalent polymers. Compared with the reported polymer materials, the cationic polymer synthesized by the method has more definite structure and more obvious cationic electrostatic effect on the premise of ensuring the stability of the catalyst, is more stable in the process of catalyzing the oxygen reduction reaction, shows more excellent catalytic performance, and realizes the high efficiency and high stability of the electro-catalytic oxygen reduction reaction of the metalloporphyrin covalent organic polymer. The invention successfully realizes the successful application of the molecular design principle on the polymer material, and verifies the rationality of the molecular catalyst design concept in a heterogeneous system.
Drawings
FIG. 1 is an infrared spectrum of a cationic modified covalent cobalt porphyrin polymer prepared in example 1.
FIG. 2 is a partial X-ray photoelectron spectrum of a cationic modified covalent cobalt porphyrin polymer prepared in example 1.
FIG. 3 is a scanning electron microscope image of a cationically modified covalent cobalt porphyrin polymer prepared in example 1.
FIG. 4 is an infrared spectrum of the phenyl cobalt porphyrin polymer prepared in comparative example 1.
FIG. 5 is a partial X-ray photoelectron spectrum of the phenyl cobalt porphyrin polymer prepared in comparative example 1.
FIG. 6 is a scanning electron microscope image of the phenyl cobalt porphyrin polymer prepared in comparative example 1.
FIG. 7 is a graph of the electrocatalytic oxygen reduction reaction performance of the cationic modified covalent cobalt porphyrin polymer prepared in example 1.
FIG. 8 is a graph of the electrocatalytic oxygen reduction reaction performance of the phenyl cobalt porphyrin polymer prepared in comparative example 1.
FIG. 9 is a graph of the stability of the cationic modified covalent cobalt porphyrin polymer prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the examples.
Example 1
Step 1: 396mg (2 mmol) of 2- (bromomethyl) benzaldehyde and 292mg (2 mmol) of 2,2' -dipyrromethene are added into a 1L round bottom flask filled with 500mL of dichloromethane, and the mixture is stirred at normal temperature under the condition of argon and light shielding for 15 minutes, 0.594mL (8 mmol) of trifluoroacetic acid is added, after stirring and reacting for 30 minutes, 1.362g (6 mmol) of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is added, after stirring for 30 minutes, 1mL of triethylamine is added for neutralization, and stirring is continued for 1 hour; then, the mixed solution of petroleum ether and methylene dichloride with the volume ratio of 1:1 is taken as a developing agent, the mixture is separated by using a rapid column chromatography, and then the solvent is removed by decompression and rotary evaporation, so as to obtain purple solid, namely the 5, 15-di (2-benzyl bromide) porphyrin ligand, with the yield of 32 percent, and the structural characterization is as follows:
1 H NMR(400MHz,Chloroform-d)δ10.32(s,2H),9.38(d,J＝4.5Hz,4H),8.89(d,J＝4.4Hz,4H),8.16(d,J＝7.0Hz,1H),8.10(d,J＝7.1Hz,1H),7.98(t,J＝7.7Hz,2H),7.89(t,J＝7.7Hz,2H),7.72(q,J＝6.8Hz,2H),4.36(s,2H),4.29(s,2H),-3.14(s,2H)。
high resolution mass spectrum HRMS (ESI) m/z: C 34 H 25 Br 2 N 4 ,[M+H] + Theoretical value 649.0423; found 649.0426.
Step 2: adding 32.3mg (0.05 mmol) of 5, 15-bis (2-benzyl bromide) porphyrin ligand and 109.8mg (0.5 mmol) of zinc acetate dihydrate into 20mL of tetrahydrofuran, refluxing at 70 ℃ for 3 hours in a dark place, rotationally evaporating the solvent, extracting with pure water and dichloromethane three times, taking a mixed solution of petroleum ether and dichloromethane with the volume ratio of 1:1 as a developing agent, separating and purifying by flash column chromatography, and removing the solvent by rotary evaporation under reduced pressure to obtain purple solid, namely 5, 15-bis (2-benzyl bromide) zinc porphyrin, wherein the yield is 96 percent, and the structure is characterized in that:
1 H NMR(400MHz,Chloroform-d)δ10.31(d,J＝1.5Hz,2H),9.41(d,J＝4.4Hz,4H),8.95(s,4H),8.16(d,J＝7.5Hz,1H),8.09(t,J＝7.6Hz,1H),7.94(t,J＝7.0Hz,2H),7.85(t,J＝7.6Hz,2H),7.53(q,J＝5.7Hz,2H),4.26(s,2H),4.22(s,2H)。
high resolution mass spectrum HRMS (ESI) m/z: C 34 H 23 Br 2 N 4 Zn,[M+H] + Theoretical value 712.9526; found 712.9526.
Step 3: 35.6mg (0.05 mmol) of 5, 15-bis (2-benzyl bromide) zinc porphyrin is dissolved in 20mL of chloroform under anhydrous and anaerobic operation, the mixture is stirred for 10 minutes at 0 ℃ in a dark place, 0.01mL (0.124 mmol) of pyridine and 18.16mg (0.102 mmol) of N-bromosuccinimide are added for reaction for 30 minutes, 0.5mL of methanol is added for quenching, after the solvent is removed by rotary evaporation under reduced pressure, the solvent is removed by rotary evaporation under reduced pressure after the rapid column chromatography separation and purification by using methylene dichloride as a developing agent, and the solvent is removed by rotary evaporation under reduced pressure, thus obtaining purple solid. Dissolving the purple solid in 20mL of acetone, adding 2mL of concentrated hydrochloric acid, stirring at room temperature for reaction for 2 hours, extracting for three times by using pure water and dichloromethane, taking a mixed solution of petroleum ether and dichloromethane with the volume ratio of 20:1 as a developing agent, separating and purifying by using a rapid neutral alumina column chromatography, and removing a solvent by vacuum rotary evaporation to obtain a purple solid, namely the 5, 15-dibromo-10, 20-di (2-benzyl bromide) porphyrin ligand with the yield of 98%, wherein the structural characterization is as follows:
1 H NMR(400MHz,Chloroform-d)δ9.60(d,J＝4.8Hz,4H),8.69(d,J＝4.6Hz,4H),8.06(d,J＝7.4Hz,1H),8.00(d,J＝7.3Hz,1H),7.92(t,J＝3.9Hz,2H),7.85(t,J＝7.6Hz,2H),7.69(q,J＝6.4Hz,2H),4.24(s,2H),4.18(s,2H),-2.64(s,2H).。
high resolution mass spectrum HRMS (ESI) m/z: C 34 H 23 Br 4 N 4 ,[M+H] + Theoretical value 806.8611; found 806.8614.
Step 4: 40.3mg (0.05 mmol) of 5, 15-dibromo-10, 20-di (2-benzyl bromide) porphyrin ligand and 124.5mg (0.5 mmol) of cobalt acetate tetrahydrate are added into a mixed solvent of 10mL of chloroform and 10mL of methanol, reflux reaction is carried out for 3 hours under the dark condition at 65 ℃, after the solvent is removed by decompression rotary evaporation, the mixed solution of petroleum ether and methylene chloride with the volume ratio of 1:2 is used as a developing agent for extraction three times, after rapid neutral alumina column chromatography separation and purification, the solvent is removed by decompression rotary evaporation, and red solid is obtained, namely 5, 15-dibromo-10, 20-di (2-benzyl bromide) cobalt porphyrin, the yield is 96 percent, and the structural characteristics are as follows:
high resolution mass spectrum HRMS (ESI) m/z: C 34 H 21 Br 4 N 4 Co,[M+H] + Theoretical value 863.7795; found 863.7789.
Step 5: under the argon condition of anhydrous and anaerobic operation, 43.2mg (0.05 mmol) of 5, 15-dibromo-10, 20-di (2-benzyl bromide) cobalt porphyrin is dissolved in 20mL of tetrahydrofuran, 0.1mL of 2M trimethylamine methanol solution is added, the mixture is stirred for 24 hours at room temperature, the precipitate is collected after filtration, 2mL of N-dimethylformamide is used for dissolving the precipitate, the precipitate is slowly dripped into saturated ammonium hexafluorophosphate aqueous solution, the mixture is stirred for 5 hours, the mixture is filtered, the precipitate is leached by diethyl ether and then vacuum-dried to obtain mauve solid 5, 15-dibromo-10, 20-di (2-benzyl trimethyl ammonium hexafluorophosphate) cobalt porphyrin, namely cationic cobalt porphyrin monomer, the yield is 65 percent, and the structure is characterized as follows:
high resolution mass spectrum HRMS (ESI) m/z: [ C 40 H 38 Br 2 N 6 Co] 2+ ,[M] 2+ Theoretical value 410.5413; found 410.5415.
Step 6: 82mg (0.1 mmol) of cationic cobalt porphyrin monomer and 20.8mg (0.05 mmol) of tetra (4-ethynylphenyl) methane are dissolved in 10mLN, N-dimethylformamide under the nitrogen condition, 0.2mL (2.23 mmol) of triethylamine is added, 5.6mg (8 mu mol) of ditriphenylphosphine palladium dichloride and 1.5mg (8 mu mol) of cuprous iodide are added, stirring reaction is carried out for 48 hours at 70 ℃, after filtration, the precipitate is washed three times by N, N-dimethylformamide, washed three times by methanol, and vacuum drying is carried out at 60 ℃, so that the obtained black solid is the cationic modified covalent cobalt porphyrin polymer.
Tetra (4-ethynylphenyl) methane (TEPM) and the obtained cationic cobalt porphyrin monomer (N) are subjected to infrared spectrum + -Co), cationic modified covalent cobalt porphyrin polymer (N) + -COP) as shown in FIG. 1, the linker TEPM was at 3283cm -1 And 2108cm -1 Characteristic peaks of terminal hydrogen with alkynyl when combined with N + Synthesis of N by Co chemical bond coupling + The characteristic peak of terminal hydrogen of-COP, alkynyl disappears, and N + Infrared spectrum of-COP and N + The characteristic peaks at other parts of the infrared spectrogram of Co are uniform and corresponding to each other, which proves that N + COP synthesis was successful. At N + In the X-ray photoelectron spectroscopy analysis test of the COP, N + The COP catalyst shows two characteristic peaks of bivalent Co ions in a Co 2p region, which are respectively attributed to Co 2p 3/2 (780.2 eV) and Co 2p 1/2 (795.5 eV) (CCS chem.,2022, 4:2959-2967), consistent with the coordination and electronic structure of Co in monomeric cobalt porphyrin, as shown in FIG. 2. In the N1s spectrum, the cationic modified covalent cobalt porphyrin polymer exhibited a characteristic peak at 398.5eV attributed to Co-N and an additional characteristic peak at 402.5eV attributed to the N atom in the quaternary ammonium salt (Adv.Mater., 2022,34:2110496;Angew.Chem.Int.Ed.,2022, 61:e202212162), thus demonstrating that at N + The presence of quaternary ammonium cations in the COP, further demonstrates that cationic groups remain on the cobalt porphyrin structure after the coupled polymerization. Testing N with a scanning electron microscope + -COP), as shown in fig. 3, N + The COP shows as uniform 400nm microspheres, demonstrating the successful synthesis of the polymer.
Comparative example 1
Step 1: 252.1mg (2 mmol) of 3-trimethylsilyl propiolic aldehyde and 444.6mg (2 mmol) of 5-phenyl dipyrromethene are added into a 1L round bottom flask filled with 600mL of redistilled DCM, argon is introduced to remove oxygen for 15 min, 0.594mL (8 mmol) of trifluoroacetic acid is added in the dark, stirring reaction is continued at room temperature for 30 min, 681mg (3 mmol) of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) is then added, stirring is continued for 30 min, the solvent is removed by reduced pressure distillation, the crude product is separated, PE: DCM=1:1 is taken as eluent, the crude product is obtained by column chromatography purification, the solvent is removed by reduced pressure distillation, methanol is added for recrystallization, and the dark purple solid is obtained by filtration, namely 5, 15-bis (phenyl) -10, 20-bis (trimethylsilylethynyl) porphyrin ligand, the yield is 22%, the structure is characterized as follows:
1 H NMR(CDCl 3 ,400MHz):δ＝9.61(d,4H),8.82(d,4H),8.18(d,4H),7.78(q,6H),0.60(s,18H),-2.20(s,2H)。
HRMS(ESI)m/z:C 42 H 39 N 4 Si 2 ,[M+H] + theoretical value 655.2708; found 655.2721.
Step 2: adding 32.7mg (0.05 mmol) of 5, 15-bis (phenyl) -10, 20-bis (trimethylsilylethynyl) porphyrin ligand and 124.5mg (0.5 mmol) of cobalt acetate tetrahydrate into a 100mL flask, adding 15mL of chloroform and 15mL of methanol, heating the obtained mixed solution to 70 ℃ to react for 5 hours, decompressing and distilling to remove the solvent, extracting with water and DCM for three times to obtain a crude product, taking a mixed solution of PE: DCM=1:1 as a developing agent, separating and purifying by flash column chromatography, decompressing and distilling to remove the solvent to obtain purple solid, namely 5, 15-bis (phenyl) -10, 20-bis (trimethylsilylethynyl) cobalt porphyrin, wherein the yield is 98%, and the structure is characterized as follows:
HRMS(ESI)m/z:C 42 H 37 CoN 4 Si 2 ,[M+H] + theoretical value 712.1883; found 712.1882.
Step 3: 35.6mg (0.05 mmol) of 5, 15-bis (phenyl) -10, 20-bis (trimethylsilylethynyl) cobalt porphyrin, 10mL of anhydrous THF are added to a 50mL Schlenk flask under nitrogen, 180. Mu.L of a 1M solution of tetrabutylammonium fluoride (TBAF) in THF are slowly added and the resulting solution is stirred at room temperature for a further 3 hours. After the reaction is finished, 10mL of water is added to generate a precipitate, the precipitate is filtered and collected, and the purple black solid 5, 15-di (phenyl) -10, 20-di (ethynyl) cobalt porphyrin is obtained after vacuum drying, namely phenyl cobalt porphyrin monomer, the yield is 96%, and the structural characterization is as follows:
HRMS(ESI)m/z:C 36 H 21 CoN 4 ,[M+H] + theoretical value 568.1093; found 568.1094.
Step 4: 56.8mg (0.1 mmol) of phenylcobalt porphyrin monomer and 31.8mg (0.05 mmol) of tetrakis (4-bromophenyl) methane (TBPM), 10mLN, N-Dimethylformamide (DMF) were added to a 50mL Schlenk flask under nitrogen protection, 3mL of Triethylamine (TEA) was added, 5.6mg (8. Mu. Mol) of ditriphenylphosphine palladium dichloride and 1.5mg (8. Mu. Mol) of cuprous iodide were further added, and after sealing the tube, the mixed solution was heated to 70℃and stirred for 48 hours. After the reaction was completed, the temperature was lowered to room temperature, the mixture was filtered, and the precipitate was collected and washed three times with DMF and three times with methanol (MeOH). Finally, the solid matter is dried in vacuum at 60 ℃ to obtain black solid, namely the phenyl cobalt porphyrin polymer.
Characterization of the linker tetrakis (4-bromophenyl) methane (TBPM), the resulting phenylcobalt porphyrin monomer (Co-H) and the phenylCo porphyrin polymer (COP) was performed by IR spectroscopy, as shown in FIG. 4, co-H was at 3265cm -1 And 2101cm -1 The characteristic peak of the terminal hydrogen of the alkynyl is arranged, when the terminal hydrogen of the alkynyl is coupled with a TBPM chemical bond of a connector to synthesize COP, the characteristic peak of the terminal hydrogen of the alkynyl disappears, and the characteristic peaks of the infrared spectrogram of the COP and the infrared spectrogram of Co-H at other positions are in one-to-one correspondence, so that the COP synthesis is proved to be successful. In the analysis and test of the X-ray photoelectron spectrum of COP, the COP catalyst shows two characteristic peaks of bivalent Co ions in a Co 2p region, and the characteristic peaks are respectively attributed to Co 2p 3/2 (780.2 eV) and Co 2p 1/2 (795.5 eV) (CCS chem.,2022, 4:2959-2967), consistent with the coordination and electronic structure of Co in monomeric cobalt porphyrin, as shown in FIG. 5. In the N1s spectrum, the phenyl cobalt porphyrin polymer exhibited a characteristic peak at 398.5eV attributed to Co-N, which, in summary, demonstrated that cobalt porphyrin remained intact in the COP. Microscopic images of COP were tested using scanning electron microscopy, as shown in fig. 6, with COP showing as uniform 400nm microspheres, demonstrating successful synthesis of the polymer.
Example 2
Cationic modified covalent cobalt porphyrin polymer (N) + -COP) electrocatalytic oxygen reduction reaction applications
Since cobalt porphyrin polymer materials are inherently less conductive, it is desirable to increase the conductivity of the catalyst for electrocatalytic testing with the aid of carbon materials. Taking 2mg N + adding-COP and 2mg Carbon Nanotube (CNT) into a mixed solution of 0.48mL isopropanol and 0.48mL water, adding 40. Mu.L of 0.5% Nafion solution, and performing ultrasonic treatment for 30 min to obtain 20. Mu.L of mixed suspension solution, uniformly dripping the mixed suspension solution on a clean glassy carbon electrode (0.125 cm) 2 ) Air-drying at room temperature to obtain N + -COP loading the electrodes of the CNTs. Simultaneous production ofThe electrodes with COP loaded CNTs were compared.
In the electrocatalytic oxygen reduction test, N is respectively used as + The electrode of the COP load CNT and the electrode of the COP load CNT are used as cathode working electrodes, a carbon rod electrode and a saturated Ag/AgCl electrode are respectively used as counter electrodes and reference electrodes, and 0.1M KOH solution is used as electrolyte solution for electrochemical oxygen reduction test. As shown in FIG. 7, the left graph shows N under argon and oxygen conditions, respectively + Cyclic Voltammetry (CV) of COP, it can be seen that under oxygen saturation conditions N + The COP shows electrocatalytic oxygen reduction properties, with a peak potential of 0.78V (vs RHE); the right graph shows the rotating disk electrode test (RRDE) under oxygen saturation conditions, N at 1600rpm + The COP electrocatalytic oxygen reduction reaction performance is good, and the half-wave potential is 0.81V (vs RHE). In fig. 8, the left graph is Cyclic Voltammetry (CV) of COP under argon and oxygen conditions, respectively, it can be seen that COP shows electrocatalytic oxygen reduction performance under oxygen saturation conditions, with peak potential at 0.74V (vs RHE); the right graph shows the rotating disk electrode test (RRDE) under oxygen saturation conditions, with good COP electrocatalytic oxygen reduction reaction performance at 1600rpm, and a half-wave potential of 0.78V (vs RHE). Thus, cationic modified covalent cobalt porphyrin polymer (N + -COP) is better than phenyl cobalt porphyrin polymer (COP) and is also better than most simple cobalt porphyrin molecular catalysts.
As shown in FIG. 9, the left panel shows N after 2000 cycles of the electrocatalytic oxygen reduction reaction test + The performance of the COP catalyst can still be kept at a high level; in the right-hand electrocatalytic oxygen reduction electrolysis experiments, N + The COP is electrolyzed for 10 hours under constant potential of 0.36V (vs RHE), the current is only attenuated to 94% before and after electrolysis, and good performance can be maintained.
To sum up, N + In the electrocatalytic oxygen reduction reaction, the COP not only shows higher catalytic performance in cobalt porphyrin system, but also has good stability.
Claims (9)
1. The cationic modified covalent cobalt porphyrin polymer is characterized by having the following structural formula:
wherein n represents the number of anions and the number is the same as the number of cations.
2. A method of preparing a cationic modified covalent cobalt porphyrin polymer according to claim 1, comprising the steps of:
step 1: adding 2- (bromomethyl) benzaldehyde and 2,2' -dipyrromethene into methylene dichloride, stirring at normal temperature under the condition of argon shading for 15-20 minutes, adding trifluoroacetic acid, reacting for 30-40 minutes, adding 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, stirring for 30-40 minutes, adding triethylamine for neutralization, and separating and purifying by flash column chromatography to obtain a 5, 15-bis (2-benzyl bromide) porphyrin ligand with the following structural formula;
step 2: adding the 5, 15-di (2-benzyl bromide) porphyrin ligand and zinc acetate dihydrate in the step 1 into tetrahydrofuran, refluxing in a dark place at 65-75 ℃ for 3-4 hours, and separating and purifying by rapid column chromatography to obtain 5, 15-di (2-benzyl bromide) zinc porphyrin with the structural formula shown below;
step 3: under anhydrous and anaerobic operation, dissolving 5, 15-bis (2-benzyl bromide) zinc porphyrin in the step 2 in chloroform, adding pyridine and N-bromosuccinimide at 0 ℃, reacting for 30-40 minutes, adding methanol for quenching, rotating and evaporating a solvent, and separating and purifying by flash column chromatography to obtain a purple solid; dissolving the purple solid in acetone, adding hydrochloric acid, stirring at room temperature for reaction for 2-3 hours, rotationally evaporating the solvent, extracting with pure water and dichloromethane, and performing rapid column chromatography separation and purification to obtain a 5, 15-dibromo-10, 20-di (2-benzyl bromide) porphyrin ligand with the structural formula shown in the specification;
step 4: adding the 5, 15-dibromo-10, 20-di (2-benzyl bromide) porphyrin ligand and cobalt acetate tetrahydrate in the step 3 into a mixed solvent of chloroform and methanol, carrying out light-proof reflux reaction for 3-4 hours at 60-70 ℃, and obtaining 5, 15-dibromo-10, 20-di (2-benzyl bromide) cobalt porphyrin with the structural formula shown in the specification after separation and purification by rapid column chromatography;
step 5: under the condition of nitrogen operated without water and oxygen, dissolving 5, 15-dibromo-10, 20-di (2-benzyl bromide) cobalt porphyrin in the step 4 into tetrahydrofuran, adding trimethylamine, stirring at room temperature for 20-24 hours, filtering, collecting precipitate, dissolving with N, N-dimethylformamide, then dropwise adding the solution into saturated ammonium hexafluorophosphate aqueous solution, stirring for 4-6 hours, filtering, eluting the precipitate with diethyl ether, and vacuum drying to obtain mauve solid, namely 5, 15-dibromo-10, 20-di (2-benzyl trimethyl ammonium hexafluorophosphate) cobalt porphyrin with the following structural formula, namely cationic cobalt porphyrin monomer;
step 6: under the condition of nitrogen, dissolving the cationic cobalt porphyrin monomer and tetra (4-ethynylphenyl) methane in the step 5 into N, N-dimethylformamide, adding triethylamine, ditriphenylphosphine palladium dichloride and cuprous iodide, stirring and reacting for 45-50 hours at 65-75 ℃, filtering, flushing with N, N-dimethylformamide, flushing with methanol, and vacuum drying to obtain the cationic modified covalent cobalt porphyrin polymer.
3. The method of preparing a cationic modified covalent cobalt porphyrin polymer according to claim 2, wherein: in the step 1, the molar ratio of the 2- (bromomethyl) benzaldehyde to the 2,2' -dipyrromethene to the trifluoroacetic acid to the 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is 1:1-1.2:2-6:2-4.
4. The method of preparing a cationic modified covalent cobalt porphyrin polymer according to claim 2, wherein: in the step 2, the molar ratio of the 5, 15-di (2-benzyl bromide) porphyrin ligand to the zinc acetate dihydrate is 1:10-20.
5. The method of preparing a cationic modified covalent cobalt porphyrin polymer according to claim 2, wherein: in the step 3, the molar ratio of the 5, 15-di (2-benzyl bromide) zinc porphyrin to the N-bromosuccinimide to the pyridine is 1:2-3:1-5.
6. The method of preparing a cationic modified covalent cobalt porphyrin polymer according to claim 2, wherein: in the step 4, the molar ratio of the 5, 15-dibromo-10, 20-di (2-benzyl bromide) porphyrin ligand to the cobalt acetate tetrahydrate is 1:10-20.
7. The method of preparing a cationic modified covalent cobalt porphyrin polymer according to claim 2, wherein: in the step 5, the molar ratio of the 5, 15-dibromo-10, 20-di (2-benzyl bromide) cobalt porphyrin to the trimethylamine is 1:1-8.
8. The method of preparing a cationic modified covalent cobalt porphyrin polymer according to claim 2, wherein: in the step 6, the mole ratio of the cationic cobalt porphyrin monomer, the tetra (4-ethynylphenyl) methane, the triethylamine, the bis-triphenylphosphine palladium dichloride and the cuprous iodide is 1:0.3-0.7:20-50:0.02-0.1:0.02-0.1.
9. Use of the cationic modified covalent cobalt porphyrin polymer of claim 1 in electrocatalytic oxygen reduction reactions.
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