CN105348303A - Porphyrin two-dimension covalent organic framework conjugated polymer, and preparation method and application thereof - Google Patents
Porphyrin two-dimension covalent organic framework conjugated polymer, and preparation method and application thereof Download PDFInfo
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- CN105348303A CN105348303A CN201510777231.8A CN201510777231A CN105348303A CN 105348303 A CN105348303 A CN 105348303A CN 201510777231 A CN201510777231 A CN 201510777231A CN 105348303 A CN105348303 A CN 105348303A
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- porphyrin
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 82
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000013310 covalent-organic framework Substances 0.000 title abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 74
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000011889 copper foil Substances 0.000 claims description 20
- CWGZUDCLBKTFEM-UHFFFAOYSA-N 5,10,15,20-tetrakis(4-ethynylphenyl)-21,23-dihydroporphyrin Chemical compound C#Cc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C#C)c2ccc([nH]2)c(-c2ccc(cc2)C#C)c2ccc(n2)c(-c2ccc(cc2)C#C)c2ccc1[nH]2 CWGZUDCLBKTFEM-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- JCIVIRQSXLTMEF-UHFFFAOYSA-N iodoethyne Chemical group IC#C JCIVIRQSXLTMEF-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 8
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract 3
- 239000010406 cathode material Substances 0.000 abstract 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 16
- 239000010409 thin film Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 239000013474 COF-1 Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000021615 conjugation Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- -1 MnIII ion Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000029058 respiratory gaseous exchange Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- SSTXWISONYDDTI-UHFFFAOYSA-N C(#C)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical class C(#C)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 SSTXWISONYDDTI-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910016884 MnIII Inorganic materials 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention belongs to the fields of a metal ion battery and a super capacitor, and concretely relates to a porphyrin two-dimension covalent organic framework conjugated polymer, and a preparation method and an application thereof. A structural formula of the porphyrin two-dimension covalent organic framework conjugated polymer is shown in formula (I), wherein m=0 or 1, n=0 or 1. The porphyrin two-dimension covalent organic framework conjugated polymer can be directly used as a cathode material of the metal ion battery and the super capacitor, so that the cathode material shows excellent properties, which include good cycle performance, high specific capacity and excellent rate capability; the polymer powder also has the same effects and properties, and can be used as a cathode material of other metal ion (sodium, potassium, zinc, nickel, etc.) batteries and super capacitors.
Description
Technical field
The invention belongs to metal ion battery and ultracapacitor field, be specifically related to a kind of porphyrin two dimension covalency organic frame conjugated polymers, its preparation method and application.
Background technology
In recent years, lithium ion battery is widely used in (Kim, YS in portable electric appts gradually; Xie, Y.N; Wen, X.N; Wang, S.H; Kim, S.J; Song, HK; Wang, Z.L, NanoEnergy14,77 – 86 (2015)).The electrode materials with height ratio capacity, excellent high rate performance and more long circulation life is the vital determinative improving battery performance.Inorganic and carbon based negative electrodes material causes the extensive concern of people.From TiS in 1976
2be used as negative material (Whittingham, M.S.Electrochemicalenergystorageandintercalationchemistr y.Science192,1226 – 1227 (1976)), the inorganic negative material of various high-energy-density, as Si, Co
3o
4, Fe
3o
4and SnO
2attract the attention of researchist.Although have high theoretical capacity, inorganic negative material itself has its significantly deficiency: the volumetric expansion of embedding lithium process induction, and the loss of a large amount of irreversible capacities caused thus, the reduction of initial coulomb efficiency, poor cyclical stability etc.Graphite (372mAh/g) is typically as the conventional carbon sill of lithium ion battery negative, but more difficult quick increased requirement (Tarascon, the J.M. meeting battery of its lower theoretical specific capacity; Armand, M., Nature, 414 (6861), 359-367 (2001)).Other carbon based negative electrodes material, the research as carbon nanotube, Graphene, nano carbon-base matrix material is risen gradually.Conductive conjugated polymer has good chemical stability and semiconducting behavior, is the organic semiconductor material that there is application future a class pole.
Covalent organic frame material (CovalentOrganicFrameworks, COFs) be the porous crystalline material with clear and definite structure and pore size distribution, have broad application prospects in atmosphere storage, catalysis, separation, optics and chemical sensitisation etc.
CN103934026A discloses organic covalency polymeric material of a kind of porous metal porphyrin and preparation method thereof and purposes.This polymeric material is with tetrakisaminophenyl porphyrin for basic raw material, by with cyanuric chloride in a mild condition reactive polymeric be porous organic covalency polymeric material CPF-1.Take CPF-1 as underlying carrier, by with manganese metal reactant salt, synthesized metalloporphyrin organic covalency polymeric material Mn-CPF-1 of porphyrin large ring loaded metal MnIII ion further.The organic covalency polymeric material of this porous metal porphyrin is applied to catalysis epoxidation alkene and catalyzed oxidation aromatic yl paraffin, and reaction conditions is gentle, pollution-free, good stability, cost is low, and catalyzer can simply recycle and reuse, transformation efficiency is high, the selectivity of product is high, and aftertreatment is simple.
Zhejiang University Ph.D. Dissertation " design and synthesis of metalloporphyrin frame material and applied research " discloses a kind of metal-5,10,15, the synthesis of 20-tetra-ethynyl phenyl porphyrin (M-TEPP) and based on metal-5,10, the synthesis of the covalent linkage organic framework materials of 15,20-tetra-ethynyl phenyl porphyrin.
The present inventor, after carrying out a large amount of tests, has synthesized based on 5, and 10,15,20-tetra-(4-ethynyl phenyl) porphyrin there is height ratio capacity, the porphyrin of excellent high rate performance and overlength cycle life two dimension covalency organic frame conjugated polymers, thus complete the present invention.
Summary of the invention
The first object of the present invention is just to provide a kind of porphyrin two dimension covalency organic frame conjugated polymers, this polymkeric substance has height ratio capacity, excellent high rate performance and overlength cycle life, can directly apply in metal ion battery or ultracapacitor as electrode materials.
The second object of the present invention is to provide the preparation method of described porphyrin two dimension covalency organic frame conjugated polymers.
The third object of the present invention is to provide the application of described porphyrin two dimension covalency organic frame conjugated polymers.
For realizing the first object of the present invention, the present invention adopts following technical scheme:
A kind of porphyrin two dimension covalency organic frame conjugated polymers, wherein, the structural formula of described porphyrin two dimension covalency organic frame conjugated polymers is:
Wherein
m=0 or 1, n=0 or 1.
Further, described porphyrin two dimension covalency organic frame conjugated polymers is 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin and Isosorbide-5-Nitrae-diiodo-benzene, Isosorbide-5-Nitrae-two iodo-1,3-diacetylene or 1, the two-dimentional covalency organic frame conjugated polymers of 4-bis-(2-iodoacetylene base) benzene copolymerization, or 5,10, the two-dimentional covalency organic frame conjugated polymers of 15,20-tetra-(4-ethynyl phenyl) porphyrin autohemagglutination.
Further, 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin and Isosorbide-5-Nitrae-diiodo-benzene, iodo-1, the 3-diacetylene of Isosorbide-5-Nitrae-two or Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene distinguish the ratio copolymerization of 1:2 in molar ratio.
For realizing the second object of the present invention, the present invention adopts following technical scheme:
A preparation method for porphyrin two dimension covalency organic frame conjugated polymers of the present invention, the method is: by 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin respectively with Isosorbide-5-Nitrae-diiodo-benzene, Isosorbide-5-Nitrae-two iodo-1,3-diacetylene or 1,4-bis-(2-iodoacetylene base) benzene carries out copolymerization, or by 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin carries out autohemagglutination.
Further, the mol ratio of 5,10,15,20-tetra-described (4-ethynyl phenyl) porphyrins and Isosorbide-5-Nitrae-diiodo-benzene, iodo-1, the 3-diacetylene of Isosorbide-5-Nitrae-two or Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene is 1:2.
Specifically, described preparation method comprises the steps:
1) Copper Foil or copper sheet are processed;
2) Copper Foil processed or copper sheet are placed in the container filling organic solution, after nitrogen protection, 5 are added in container, 10,15,20-tetra-(4-ethynyl phenyl) porphyrin, carries out back flow reaction under nitrogen protection, reaction terminates rear washing metal, obtains porphyrin two dimension covalency organic frame conjugated polymers;
Or the Copper Foil processed or copper sheet are placed in the container filling organic solution, after nitrogen protection, in container, add catalyzer; logical nitrogen protection under room temperature, then in container, add 5,10; 15,20-tetra-(4-ethynyl phenyl) porphyrin and Isosorbide-5-Nitrae-diiodo-benzene, 1; 4-bis-iodo-1; 3-diacetylene or Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene, back flow reaction under nitrogen protection; reaction terminates rear washing Copper Foil or copper sheet, obtains porphyrin two dimension covalency organic frame conjugated polymers.
Specifically, the preparation method of porphyrin two dimension covalency organic frame conjugated polymers of the present invention is by 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin generation self-polymeric reaction or by 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin and 1,4-diiodo-benzene, 1, iodo-1, the 3-diacetylene of 4-bis-or Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene generation copolyreaction.
When the preparation method of described porphyrin two dimension covalency organic frame conjugated polymers is by 5,10,15, during 20-tetra-(4-ethynyl phenyl) porphyrin generation self-polymeric reaction, step 1) preferably Copper Foil is processed, like this 5,10, in the self-polymeric reaction of 15,20-tetra-(4-ethynyl phenyl) porphyrin, Copper Foil can play the dual function of catalysis and " flat formwork ".
When the preparation method of described porphyrin two dimension covalency organic frame conjugated polymers is by 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin and Isosorbide-5-Nitrae-diiodo-benzene, Isosorbide-5-Nitrae-two iodo-1, when 3-diacetylene or Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene generation copolyreaction, described 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin and 1,4-diiodo-benzene, 1, the mol ratio of iodo-1, the 3-diacetylene of 4-bis-or Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene is 1:2.
More particularly, step 1) in, described Copper Foil or copper sheet process with hydrochloric acid soln, intermediate water, ethanol and acetone successively; Step 2) in, described organic solution is toluene, triethylamine and/or pyridine, the mixing solutions of preferred toluene and triethylamine or pyridine solution; Described catalyzer is bi triphenyl phosphorus palladium chloride and cuprous iodide, and the time of described back flow reaction is 40 ~ 55 hours.
In the present invention, the reactant 1 adopted, 4-diiodo-benzene is commercially available bulk drug, and the reactant 5,10 adopted, 15,20-tetra-(4-ethynyl phenyl) porphyrin, iodo-1, the 3-diacetylene of Isosorbide-5-Nitrae-two and 1, these three kinds of compounds of 4-bis-(2-iodoacetylene base) benzene obtain according to the method synthesis of document, specific as follows:
In the present invention, for the preparation of the reactant compound 5,10 of two-dimentional covalency organic frame conjugated polymers, 15,20-tetra-(4-ethynyl phenyl) porphyrin, be the method that provides according to following document with 4-bromobenzaldehyde for initial feed is obtained: Zhang, L.; Wang, K.; Qian, X.M.; Liu, H.B.; Shi, Z.Q.; PorousConjugatedpolymernanotiparraysforhighlystablefield emitter, ACSAppl.Mater.Interfaces, 5,2761-2766 (2013), method is see embodiment part, and the chemical equation of this reaction is shown below:
In the present invention, for the preparation of the reactant compound Isosorbide-5-Nitrae-two iodo-1 of two-dimentional covalency organic frame conjugated polymers, 3-diacetylene is that the method that provides according to following document is with 1,4-two (trimethylsilyl)-1,3-diacetylene is that initial feed is obtained: Gao, K.; Goroff, N.S., TwoNewIodine-CappedCarbonRods, J.Am.Chem.Soc., 122,9320 – 9321 (2000).Method is see embodiment part.
In the present invention, for the preparation of the reactant compound 1 of two-dimentional covalency organic frame conjugated polymers, 4-bis-(2-iodoacetylene base) benzene is that the method that provides according to following document is with 1,4-diacetylene-benzene is that initial feed is obtained: Li, M.R, Li, Y.J, Zhao, B.Z, Liang, F.S, Jin, L.Y, Facileandefficientsynthesisof1-haloalkynesviaDBU-mediate dreactionofterminalalkynesandN-haloimidesundermildcondit ions, RSCAdv., 2014,4,30046 – 30049.Method is see embodiment part.
For realizing the third object of the present invention, the present invention adopts following technical scheme:
The application of the porphyrin two dimension covalency organic frame conjugated polymers that a kind of porphyrin of the present invention two dimension covalency organic frame conjugated polymers or above-mentioned preparation method obtain in the negative material of metal ion battery or ultracapacitor.
Described porphyrin two dimension covalency organic frame conjugated polymers is film or powder.
The BET surface-area of described porphyrin two dimension covalency organic frame conjugated polymers is respectively 264 ~ 566m
2/ g, specific conductivity is 0.28 × 10
-6~ 3.21 × 10
-6s/m.
Described metal ion battery is metal-lithium ion, sodium Metal 99.5 ion, potassium metal ion, metallic zinc ion or metallic nickel ions, cadmium metal ion or cobalt metal ionization cell.
Porphyrin two dimension covalency organic frame conjugated polymers provided by the present invention preferably uses as the negative material of metal-lithium ion battery.
Compared with prior art, tool of the present invention has the following advantages:
Porphyrin two dimension covalency organic frame conjugated polymers provided by the invention, shows excellent performance as lithium ion battery negative material, comprises high specific storage, excellent high rate performance and longer cycle life.
Accompanying drawing explanation
Fig. 1 a, Fig. 1 b, Fig. 1 c, Fig. 1 d are respectively the synthesis schematic diagram of porphyrin two dimension covalency organic frame conjugated polymers of embodiment 1, embodiment 2, embodiment 3, embodiment 4;
The scanning electron microscope (SEM) photograph of two-dimentional covalency organic frame conjugated polymer thin films that Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d are respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 prepare on copper sheet surface; The two-dimentional covalency organic frame conjugated polymer thin films thickness that Fig. 2 e, Fig. 2 f, Fig. 2 g, Fig. 2 h are embodiment 1 respectively, embodiment 2, embodiment 3, embodiment 4 prepare;
The Raman spectrum of the two-dimentional covalency organic frame conjugated polymer thin films that Fig. 3 is embodiment 1, embodiment 2, embodiment 3 and embodiment 4 prepare;
The infrared spectra of the two-dimentional covalency organic frame conjugated polymer thin films that Fig. 4 is embodiment 1, embodiment 2, embodiment 3 and embodiment 4 prepare;
The x-ray photoelectron energy spectrogram of the two-dimentional covalency organic frame conjugated polymer thin films that Fig. 5 a, Fig. 5 b, Fig. 5 c, Fig. 5 d are respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 prepare;
The x-ray photoelectron energy spectrogram of the C1s of the two-dimentional covalency organic frame conjugated polymer thin films that Fig. 6 a, Fig. 6 b, Fig. 6 c, Fig. 6 d are respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 prepare;
The BET graphic representation of the two-dimentional covalency organic frame conjugated polymers powder that Fig. 7 is embodiment 1, embodiment 2, embodiment 3 and embodiment 4 prepare;
The I-V graphic representation of the two-dimentional covalency organic frame conjugated polymer thin films that Fig. 8 is embodiment 1, embodiment 2, embodiment 3 and embodiment 4 prepare;
The cycle performance curve of 2032 type button half-cells under 500mA/g current density that the two-dimentional covalency organic frame conjugated polymer thin films that Fig. 9 is embodiment 1, embodiment 2, embodiment 3 and embodiment 4 prepare is assembled into as negative material;
The curve of double curvature of 2032 type button half-cells under different current density that the two-dimentional covalency organic frame conjugated polymer thin films that Figure 10 is embodiment 1, embodiment 2, embodiment 3 and embodiment 4 prepare is assembled into as lithium ion battery negative material;
Specific storage-the voltage curve of 2032 type button half-cells within the scope of 5mV ~ 3V that the two-dimentional covalency organic frame conjugated polymer thin films that Figure 11 a, Figure 11 b, Figure 11 c, Figure 11 d are respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 prepare is assembled into as negative material.
The cyclic voltammetry curve of 2032 type button half-cells under 0.1mV/s sweep velocity that the two-dimentional covalency organic frame conjugated polymer thin films that Figure 12 a, Figure 12 b, Figure 12 c, Figure 12 d are respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 prepare is assembled into as negative material.
Embodiment
Be below the specific embodiment of the present invention, described embodiment is to further describe the present invention, instead of restriction the present invention.
The preparation of reactant 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin monomer
4.63g (5mmol) p-bromobenzaldehyde is joined (3:1 in the mixing solutions of tetrahydrofuran (THF) and triethylamine; v/v); vigorous stirring 30 minutes under the protection of nitrogen, adds 190mg (1.0mmol) cuprous iodide and 350mg bi triphenyl phosphorus palladium chloride (0.5mmol) afterwards.After 10 minutes, in 1 hour, be slowly added dropwise to 3.7mL (26.3mmol) trimethylsilyl acetylene, react 3 hours.After reaction terminates, with diluted ethyl acetate, saturated common salt water washing three times, uses anhydrous magnesium sulfate drying afterwards.Being spin-dried for the product after solvent is oily, and then purify through silicagel column, eluent used is sherwood oil: ethyl acetate=20:1, obtains pure compound 4-trimethylsilyl acetylene benzaldehyde.752mg4-trimethylsilyl acetylene benzaldehyde is dissolved in 100mL trichloromethane; under nitrogen protection, uniform stirring is after 30 minutes; 275mg pyrroles is added with liquid-transfering gun; add 116 μ L boron trifluoride diethyl etherate again; react 1.5 ~ 2 hours under room temperature, until 4-trimethylsilyl acetylene benzaldehyde reacts completely.Add 0.64g2, after chloro-5, the 6-dicyanos of 3-bis--Isosorbide-5-Nitrae-benzoquinones reacts 0.5 hour, then add 126 μ L triethylamines and react 10 minutes.Reaction solution directly joins in silicagel column, and with trichloromethane as eluent, until redfree liquid flows out, be spin-dried for afterwards, rinse with dissolve with methanol, suction filtration obtains violet solid four (trimethylsilyl acetylene base) porphyrin.-78 DEG C time; to containing 43.6 milligrams (mg) (0.066 mmole (mmol)) 5; 10; 15; 0.4ml tetrabutyl ammonium fluoride (TBAF) (1 mol/L (M) tetrahydrofuran solution is added in tetrahydrofuran (THF) (THF) solution of 20-tetra-(trimethylsilyl acetylene base) porphyrin; 0.4mmol), stirring reaction 1.5 hours under nitrogen protection, some plate tracks to and reacts completely.Reaction solution crosses silica column purification, obtains 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin monomer of trimethylsilyl acetylene group.
1HNMR(400MHz，CDCl
3):8.84(s,8H),8.18(d,J＝8.0Hz,8H),7.91(d,J＝8.0Hz,8H),3.33(s,4H),-2.83(s,2H)。
The preparation of iodo-1, the 3-diacetylene of reactant Isosorbide-5-Nitrae-two
1; two (trimethylsilyl)-1 of 4-; 3-diacetylene (194.6mg; 1mmol) be dissolved in 30mL acetone; nitrogen protection is after 30 minutes; add Silver Nitrate 130.5mg (0.76mmol) and N-N-iodosuccinimide (NIS) 550.6mg (2.37mmol), reaction system stirring at room temperature 4 hours under nitrogen protection, reaction lucifuge.Point plate tracks to and reacts completely.After reaction terminates, with normal hexane/water extraction, anhydrous magnesium sulfate drying, underpressure distillation is gone out after organic solvent, obtains iodo-1, the 3-diacetylene of light yellow solid Isosorbide-5-Nitrae-two (215.3mg, 80%).
13CNMR(CDCl
3)δ79.97,-2,70。
The preparation of reactant Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene
1; 4-diacetylene-benzene (126mg; 1.0mmol) be dissolved in 2.0mL acetonitrile; nitrogen protection is after 30 minutes; add N-N-iodosuccinimide (NIS) 247.5mg (1.1mmol) and 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU) 0.159mL (1.1mmol).Stirred at ambient temperature is after 1 minute, reaction system is poured into water, with dichloromethane extraction (3 × 10mL), anhydrous magnesium sulfate drying, underpressure distillation is gone out after organic solvent, white solid Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene (340mg, 90%) is obtained through silica column purification.
13CNMR(CDCl
3，125MHz):9.13,93.5,123.7,132.1。
The synthesis of embodiment 1, COF-1
Be that the Copper Foil of 1.5cm × 8cm is placed into and fills toluene (15 milliliters) with the there-necked flask of triethylamine (15 milliliters) mixing solutions by area.Copper Foil processed successively with 0.5M hydrochloric acid soln, intermediate water, ethanol, acetone before the use.Nitrogen protection, after 30 minutes, adds catalyzer bi triphenyl phosphorus palladium chloride (8.4mg, 0.012mmol) and cuprous iodide (2.2mg, 0.012mmol) in there-necked flask, and at room temperature logical nitrogen protection, stirs 1 hour.Add 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin (1.2mg, 0.0017mmol), Isosorbide-5-Nitrae-diiodo-benzene (1.1mg, 0.0034mmol), reaction system refluxes 48 hours under nitrogen protection.On copper sheet, generate the film of one deck mulberry after reaction terminates, with acetone, methyl alcohol, methylene dichloride, diethyl ether successively washing 3 copper sheets, namely obtain two-dimentional covalency organic frame conjugated polymers COF-1 film.Synthesis schematic diagram as shown in Figure 1a.
(Fig. 2 a) shows scanning electron microscope (SEM) test result, and prepare the growth of the two-dimentional covalency organic frame conjugated polymers COF-1 film continuous uniform of gained by the method on copper sheet, thickness is 0.71 micron (Fig. 2 e).
In Raman spectrum (Fig. 3), 1566cm
-1by all sp of aromatic nucleus
2stretching vibration (the E of atom pairs
2gpattern) produce, 1363cm
-1by sp in aromatic nucleus
2atom breathing vibration pattern produces.2215cm
-1produced by single acetylene bond.2214cm in infrared spectra (Fig. 4)
-1place's vibration also belongs to single acetylene bond.
X-ray photoelectron power spectrum (XPS) (Fig. 5 a) show two-dimentional covalency organic frame conjugated polymers COF-1 film by carbon and nitrogen elementary composition, wherein C1s is sp
2(Fig. 6 a), can be divided into 4 secondary peaks, be respectively 284.7eV (C-Csp with sp hydridization
2hybridized orbital), 285.2eV (C-Csp hybridized orbital), 286.9eV (C-O), 288.6eV (C=O), C-C (sp
2) and the peak area ratio of C-C (sp) be 14:2, conform to object construction.N1s can break up 2 secondary peaks, and be respectively 398.0eV (C=N-) and 399.3eV (C-NH), peak area ratio is 1:1.
BET graphic representation (Fig. 7) shows that the specific surface area of two-dimentional covalency organic frame conjugated polymers COF-1 powder is 374m
2/ g.
I-V graphic representation (Fig. 8) shows that the I-V curve of two-dimentional covalency organic frame conjugated polymers COF-1 film is straight line, and follow ohm property, specific conductivity is 0.82 × 10
-6s/m, has good characteristic of semiconductor.
The synthesis of embodiment 2, COF-2
Be that the Copper Foil of 1.5cm × 8cm is placed in the there-necked flask filling pyridine (30 milliliters) solution by area.Copper Foil processed successively with 0.5M hydrochloric acid soln, intermediate water, ethanol, acetone before the use.Nitrogen protection is after 30 minutes, and add 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin (1.2mg, 0.0017mmol), reaction system refluxes 48 hours under nitrogen protection.On copper sheet, generate the film of one deck purple after reaction terminates, with acetone, N, N '-dimethyl methane amide is washing 3 copper sheets successively, namely obtain two-dimentional covalency organic frame conjugated polymers COF-2 film.Synthesis schematic diagram as shown in Figure 1 b.
Scanning electron microscope (SEM) test result (Fig. 2 b) shows, prepare the growth of the two-dimentional covalency organic frame conjugated polymers COF-2 film continuous uniform of gained by the method on copper sheet, thickness is 0.72 micron (Fig. 2 f).
In Raman spectrum (Fig. 3), 1566cm
-1by all sp of aromatic nucleus
2stretching vibration (the E of atom pairs
2gpattern) produce, 1363cm
-1by sp in aromatic nucleus
2atom breathing vibration pattern produces.2206cm
-1produced by the two acetylene bond of conjugation.2194cm in infrared spectra (Fig. 4)
-1place's vibration also belongs to the two acetylene bond of conjugation.
X-ray photoelectron power spectrum (XPS) (Fig. 5 b) show two-dimentional covalency organic frame conjugated polymers COF-2 film by carbon and nitrogen elementary composition, wherein C1s is sp
2with sp hydridization (Fig. 6 b), 4 secondary peaks can be divided into, be respectively 284.7eV (C-Csp
2hybridized orbital), 285.2eV (C-Csp hybridized orbital), 286.9eV (C-O), 288.6eV (C=O), C-C (sp
2) and the peak area ratio of C-C (sp) be 11:2, conform to object construction.N1s can break up 2 secondary peaks, and be respectively 398.0eV (C=N-) and 399.3eV (C-NH), peak area ratio is 1:1.
BET graphic representation (Fig. 7) shows that the specific surface area of two-dimentional covalency organic frame conjugated polymers COF-2 powder is 264m
2/ g.
I-V graphic representation (Fig. 8) shows that the I-V curve of COF-2 film is straight line, follows ohm property, and specific conductivity is 0.28 × 10
-6s/m, has good characteristic of semiconductor.
The synthesis of embodiment 3, COF-3
Be that the Copper Foil of 1.5cm × 8cm is placed into and fills toluene (15 milliliters) with the there-necked flask of triethylamine (15 milliliters) mixing solutions by area.Copper Foil processed successively with 0.5M hydrochloric acid soln, intermediate water, ethanol, acetone before the use.Nitrogen protection, after 30 minutes, adds catalyzer bi triphenyl phosphorus palladium chloride (8.4mg, 0.012mmol) and cuprous iodide (2.2mg, 0.012mmol) in there-necked flask, and at room temperature logical nitrogen protection stirs 1 hour.Add 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin (1.2mg, 0.0017mmol), after iodo-1, the 3-diacetylene (1.02mg, 0.0034mmol) of Isosorbide-5-Nitrae-two, reaction system refluxes 48 hours under nitrogen protection.On copper sheet, generate the film of one deck palm fibre purple after reaction terminates, with acetone, methyl alcohol, methylene dichloride, diethyl ether successively washing 3 copper sheets, namely obtain two-dimentional covalency organic frame conjugated polymers COF-3 film.Synthesis schematic diagram as illustrated in figure 1 c.
Scanning electron microscope (SEM) test result (Fig. 2 c) shows, prepare the growth of the two-dimentional covalency organic frame conjugated polymers COF-3 film continuous uniform of gained by the method on copper sheet, thickness is 0.59 micron (Fig. 2 g).
In Raman spectrum (Fig. 3), 1566cm
-1by all sp of aromatic nucleus
2stretching vibration (the E of atom pairs
2gpattern) produce, 1363cm-1 is by sp in aromatic nucleus
2atom breathing vibration pattern produces.2205cm
-1produced by conjugation four acetylene bond.2192cm in infrared spectra (Fig. 4)
-1place's vibration also belongs to conjugation four acetylene bond.
X-ray photoelectron power spectrum (XPS) (Fig. 5 c) show two-dimentional covalency organic frame conjugated polymers COF-3 film by carbon and nitrogen elementary composition, wherein C1s is sp
2with sp hydridization (Fig. 6 c), 4 secondary peaks can be divided into, be respectively 284.7eV (C-Csp
2hybridized orbital), 285.2eV (C-Csp hybridized orbital), 286.9eV (C-O), 288.6eV (C=O), C-C (sp
2) and the peak area ratio of C-C (sp) be 11:4, conform to object construction.N1s can break up 2 secondary peaks, and be respectively 398.0eV (C=N-) and 399.3eV (C-NH), peak area ratio is 1:1.
BET graphic representation (Fig. 7) shows that the specific surface area of two-dimentional covalency organic frame conjugated polymers COF-3 powder is 566m
2/ g.
I-V graphic representation (Fig. 8) shows that the I-V curve of two-dimentional covalency organic frame conjugated polymers COF-3 film is straight line, and follow ohm property, specific conductivity is 2.14 × 10
-6s/m, has good characteristic of semiconductor.
The synthesis of embodiment 4, COF-4
Be that the Copper Foil of 1.5cm × 8cm is placed into toluene (15 milliliters) with the there-necked flask of triethylamine (15 milliliters) mixing solutions by area.Copper Foil processed successively with 0.5M hydrochloric acid soln, intermediate water, ethanol, acetone before the use.Nitrogen protection, after 30 minutes, adds catalyzer bi triphenyl phosphorus palladium chloride (8.4mg, 0.012mmol) and cuprous iodide (2.2mg, 0.012mmol) in there-necked flask, and at room temperature logical nitrogen protection stirs 1 hour.Add 5,10,15; 20-tetra-(4-ethynyl phenyl) porphyrin (1.2mg, 0.0017mmol), 1; after 4-bis-(2-iodoacetylene base) benzene (1.1mg, 0.0034mmol), reaction system refluxes 48 hours under nitrogen protection.On copper sheet, generate the film of one deck palm fibre purple after reaction terminates, with acetone, methyl alcohol, methylene dichloride, diethyl ether successively washing 3 copper sheets, namely obtain two-dimentional covalency organic frame conjugated polymers COF-4 film.Synthesis schematic diagram as shown in Figure 1 d.
Scanning electron microscope (SEM) test result (Fig. 2 d) shows, prepare the growth of the two-dimentional covalency organic frame conjugated polymers COF-4 film continuous uniform of gained by the method on copper sheet, thickness is 0.67 micron (Fig. 2 h).
In Raman spectrum (Fig. 3), 1566cm
-1by all sp of aromatic nucleus
2stretching vibration (the E of atom pairs
2gpattern) produce, 1363cm
-1by sp in aromatic nucleus
2atom breathing vibration pattern produces.2191cm
-1produced by the two acetylene bond of conjugation.2185cm in infrared spectra (Fig. 4)
-1place's vibration also belongs to the two acetylene bond of conjugation.
X-ray photoelectron power spectrum (XPS) (Fig. 5 d) show COF-4 film by carbon and nitrogen elementary composition, wherein C1s is sp
2with sp hydridization (Fig. 6 d), 4 secondary peaks can be divided into, be respectively 284.7eV (C-Csp
2hybridized orbital), 285.2eV (C-Csp hybridized orbital), 286.9eV (C-O), 288.6eV (C=O), C-C (sp
2) and the peak area ratio of C-C (sp) be 14:4, conform to object construction.N1s can break up 2 secondary peaks, and be respectively 398.0eV (C=N-) and 399.3eV (C-NH), peak area ratio is 1:1.
BET graphic representation (Fig. 7) shows that the specific surface area of two-dimentional covalency organic frame conjugated polymers COF-4 powder is 476m
2/ g.
I-V graphic representation (Fig. 8) shows that the I-V curve of two-dimentional covalency organic frame conjugated polymers COF-4 film is straight line, and follow ohm property, specific conductivity is 3.21 × 10
-6s/m, has good characteristic of semiconductor.
Embodiment 5
Toluene (150 milliliters) and triethylamine (150 milliliters) mixing solutions is added in there-necked flask; nitrogen protection is after 30 minutes; catalyzer bi triphenyl phosphorus palladium chloride (84mg is added in there-necked flask; 0.12mmol) with cuprous iodide (22mg; 0.12mmol); at room temperature logical nitrogen protection, stirs 1 hour.Add 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin (120mg, 0.17mmol), Isosorbide-5-Nitrae-diiodo-benzene (110mg, 0.34mmol), reaction system refluxes 45 hours under nitrogen protection.Reaction terminates rear suction filtration except desolventizing, with acetone, methyl alcohol, methylene dichloride, diethyl ether successively washing 3 powder, namely obtains two-dimentional covalency organic frame conjugated polymers COF-1 powder.
Embodiment 6
In there-necked flask, add pyridine (30 milliliters) solution, nitrogen protection, after 30 minutes, adds catalyzer cuprous iodide (22mg, 0.12mmol) in there-necked flask, and at room temperature logical nitrogen protection, stirs 1 hour.Add 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin (120mg, 0.17mmol), reaction system refluxes 50 hours under nitrogen protection.Reaction terminates rear suction filtration except desolventizing, and with acetone, N, N '-dimethyl methane amide is washing 3 powder successively, namely obtain two-dimentional covalency organic frame conjugated polymers COF-2 powder.
The preparation of test example 1, battery and electrochemical property test
Porphyrin alkynes on copper sheet is gathered two-dimentional covalency organic frame conjugated polymer thin films material to dry 12 hours under 120 DEG C of vacuum conditions, be cut into 1cm × 1cm (1cm
2) size.Porphyrin alkynes gathers two-dimentional covalency organic frame conjugated polymer thin films material as lithium ion battery negative material, and lithium sheet is assembled into 2032 type button half-cells as positive electrode material and carries out electrochemical property test.Electrolytic solution is 1mol/L lithium hexafluoro phosphate (LiPF6)/NSC 11801 (EC): methylcarbonate (DMC), vinyl acetate (EC): methylcarbonate (DMC) volume ratio is 1:1.
The test of chemical property is carried out on indigo plant electric CT2001A type cell tester.First battery is carried out to the test of cycle performance under the current density of 500mA/g, under 100mA/g, 200mA/g, 500mA/g, 1A/g, 2A/g, 4A/g current density, carry out the test of high rate performance.Cyclic voltammetry sweep velocity is 0.1mV/s, and voltage range is 5mV ~ 3V.
After Fig. 9 shows that circulation 100 is enclosed under the current density of 500mA/g, COF-1, COF-2, COF-3, COF-4 obtain the reversible capacity of 715mAh/g, 1068mAh/g, 2030mAh/g, 2608mAh/g respectively, show that these four kinds of porphyrin alkynes gather two-dimentional covalency organic frame conjugated polymer thin films negative material and have good cyclical stability.In the high rate performance curve of Figure 10, COF-4 can obtain 2860mAh/g respectively under 100mA/g, 200mA/g, 500mA/g, 1A/g, 2A/g, 4A/g current density, 2620mAh/g, 2350mAh/g, the reversible capacity of 1900mAh/g, 1480mAh/g, 970mAh/g; COF-3 can obtain 2820mAh/g respectively under 100mA/g, 200mA/g, 500mA/g, 1A/g, 2A/g, 4A/g current density, the reversible capacity of 2590mAh/g, 2280mAh/g, 1890mAh/g, 1480mAh/g, 980mAh/g; COF-2 can obtain the reversible capacity of 1335mAh/g, 1122mAh/g, 901mAh/g, 683mAh/g, 542mAh/g, 425mAh/g respectively under 100mA/g, 200mA/g, 500mA/g, 1A/g, 2A/g, 4A/g current density; COF-1 can obtain the reversible capacity of 973mAh/g, 852mAh/g, 695mAh/g, 592mAh/g, 468mAh/g, 357mAh/g respectively under 100mA/g, 200mA/g, 500mA/g, 1A/g, 2A/g, 4A/g current density.These four kinds two-dimentional covalency organic frame conjugated polymer thin films negative materials, especially COF-4, shows excellent high rate performance.Charging and discharging curve in Figure 11 a, Figure 11 b, Figure 11 c, Figure 11 d, there is flex point at 1.74V, 1.5V, 1.46V, 1.68V place respectively in COF-1, COF-2, COF-3, COF-4, this may be caused by copper substrate in first time charge and discharge cycles.The flex point appearing at about 0.9V in ensuing circulation is caused by being formed of SEI film.The cyclic voltammetry curve four kinds two-dimentional covalency organic frame conjugated polymer thin films negative material of Figure 12 a, Figure 12 b, Figure 12 c, Figure 12 d is consistent with charging and discharging curve in the reduction peak of about 1.4V, 0.75V.
Claims (10)
1. a porphyrin two dimension covalency organic frame conjugated polymers, is characterized in that, the structural formula of described porphyrin two dimension covalency organic frame conjugated polymers is:
Wherein
m=0 or 1, n=0 or 1.
2. porphyrin two dimension covalency organic frame conjugated polymers according to claim 1, it is characterized in that, described porphyrin two dimension covalency organic frame conjugated polymers is 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin and 1,4-diiodo-benzene, 1, the two-dimentional covalency organic frame conjugated polymers of iodo-1, the 3-diacetylene of 4-bis-or Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene copolymerization, or 5, the two-dimentional covalency organic frame conjugated polymers of 10,15,20-tetra-(4-ethynyl phenyl) porphyrin autohemagglutination.
3. a preparation method for the porphyrin two dimension covalency organic frame conjugated polymers described in claim 1 or 2, it is characterized in that, described preparation method is: by 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin is respectively with 1,4-diiodo-benzene, 1, iodo-1, the 3-diacetylene of 4-bis-or Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene carry out copolymerization, or by 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin carries out autohemagglutination.
4. preparation method according to claim 3, is characterized in that, described 5,10,15,20-tetra-(4-ethynyl phenyl) porphyrin and Isosorbide-5-Nitrae-diiodo-benzene, 1, the mol ratio of iodo-1, the 3-diacetylene of 4-bis-or Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene is 1:2.
5. preparation method according to claim 4, is characterized in that, described preparation method comprises the steps:
1) Copper Foil or copper sheet are processed;
2) Copper Foil processed or copper sheet are placed in the container filling organic solution, after nitrogen protection, 5 are added in container, 10,15,20-tetra-(4-ethynyl phenyl) porphyrin, carries out back flow reaction under nitrogen protection, reaction terminates rear washing Copper Foil or copper sheet, obtains porphyrin two dimension covalency organic frame conjugated polymers;
Or the Copper Foil processed or copper sheet are placed in the container filling organic solution, after nitrogen protection, in container, add catalyzer; logical nitrogen protection under room temperature, then in container, add 5,10; 15,20-tetra-(4-ethynyl phenyl) porphyrin and Isosorbide-5-Nitrae-diiodo-benzene, 1; 4-bis-iodo-1; 3-diacetylene or Isosorbide-5-Nitrae-two (2-iodoacetylene base) benzene, back flow reaction under nitrogen protection; reaction terminates rear washing metal, obtains porphyrin two dimension covalency organic frame conjugated polymers.
6. preparation method according to claim 5, is characterized in that, step 1) in, described Copper Foil or copper sheet process with hydrochloric acid soln, intermediate water, ethanol and acetone successively; Step 2) in, described organic solution is toluene, triethylamine and/or pyridine, the mixing solutions of preferred toluene and triethylamine or pyridine solution; Described catalyzer is bi triphenyl phosphorus palladium chloride and cuprous iodide, and the time of described back flow reaction is 40 ~ 55 hours.
7. the application of the porphyrin two dimension covalency organic frame conjugated polymers that the porphyrin two dimension covalency organic frame conjugated polymers described in a claim 1 or 2 or the preparation method described in claim 3-6 any one obtain in the negative material of metal ion battery or ultracapacitor.
8. application according to claim 7, is characterized in that, described porphyrin two dimension covalency organic frame conjugated polymers is film or powder.
9. application according to claim 8, is characterized in that, the BET surface-area of described porphyrin two dimension covalency organic frame conjugated polymers is respectively 264 ~ 566m
2/ g, specific conductivity is 0.28 × 10
-6~ 3.21 × 10
-6s/m.
10. the application according to claim 7-9 any one, is characterized in that, described metal ion battery is metal-lithium ion, sodium Metal 99.5 ion, potassium metal ion, metallic zinc ion, metallic nickel ions, cadmium metal ion or cobalt metal ionization cell.
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