CN113502505B - Azide porphyrin ligand, metalloporphyrin/carbon composite material and application of water electrolysis - Google Patents
Azide porphyrin ligand, metalloporphyrin/carbon composite material and application of water electrolysis Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000003446 ligand Substances 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 title claims description 9
- DPTHHDDKJUMMFO-UHFFFAOYSA-O [N-]=[N+]=[N-].C1=C(C=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=[NH+]C2=C2)NC2=C1 Chemical compound [N-]=[N+]=[N-].C1=C(C=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=[NH+]C2=C2)NC2=C1 DPTHHDDKJUMMFO-UHFFFAOYSA-O 0.000 title description 2
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 50
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- PFYDPKNQWFLWMM-UHFFFAOYSA-N [N]1C2=CC=C1C=C(N1)C=C(N=[N+]=[N-])C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 Chemical compound [N]1C2=CC=C1C=C(N1)C=C(N=[N+]=[N-])C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 PFYDPKNQWFLWMM-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 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 claims description 12
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical compound NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- -1 nitrine porphyrin Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 5
- DZQBLSOLVRLASG-UHFFFAOYSA-N iridium;methane Chemical compound C.[Ir] DZQBLSOLVRLASG-UHFFFAOYSA-N 0.000 abstract description 5
- 125000000304 alkynyl group Chemical group 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- 238000002360 preparation method Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000011572 manganese Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 description 5
- RNGSTWPRDROEIW-UHFFFAOYSA-N [Ni].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Ni].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RNGSTWPRDROEIW-UHFFFAOYSA-N 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 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 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- XJJWWOUJWDTXJC-UHFFFAOYSA-N [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 XJJWWOUJWDTXJC-UHFFFAOYSA-N 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 150000001540 azides Chemical class 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- QJXCFMJTJYCLFG-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzaldehyde Chemical compound FC1=C(F)C(F)=C(C=O)C(F)=C1F QJXCFMJTJYCLFG-UHFFFAOYSA-N 0.000 description 2
- SDJOUGYEUFYPLL-UHFFFAOYSA-N 4-azidobenzaldehyde Chemical compound [N-]=[N+]=NC1=CC=C(C=O)C=C1 SDJOUGYEUFYPLL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OGZSUORSSIIDJK-UHFFFAOYSA-N FC1=C(F)C(F)=C(F)C(F)=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 OGZSUORSSIIDJK-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 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 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an azinyl porphyrin ligand, a metal porphyrin complex/carbon composite material and an application of electrolytic water, wherein the structural formula of the ligand is as follows:
the ligand can be coordinated with various metal ions to obtain a stable metalloporphyrin complex, and an azide group on the molecule of the ligand can be covalently connected with an alkynyl group modified on the carbon nano tube in an azide-alkynyl cycloaddition mode, so that various metalloporphyrin complexes are immobilized on the carbon nano material. The invention firstly applies different metalloporphyrin complexes/carbon composite materials as a catalyst for cathodic hydrogen evolution and a catalyst for anodic oxygen evolution to electrocatalytic water decomposition respectively, the stability of the catalyst in the electrocatalytic water decomposition process is good, and the catalytic current density reaches 10mA/cm 2 The required voltage is less than that of commercial platinum carbon and iridium carbon catalysts with equal loading.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by electrocatalysis decomposition, and particularly relates to A 3 B-type azidoporphyrin ligand and metal porphyrin complex based on the ligand are immobilized on a carbon nano material through azide-alkynyl cycloaddition reaction and are used for electrocatalytic water decomposition hydrogen production and oxygen production.
Background
The energy problem is one of three major problems in the world at present, and hydrogen energy is taken as an ideal new energy in the future, and the development problem becomes a hot spot concerned by people. Electrocatalytic water splitting hydrogen production is an ideal process for converting electric energy into chemical energy, but the two half reactions of water splitting (hydrogen-evolution reaction and oxygen-evolution reaction) are limited by kinetics, and the reactions are slow, so that a high-efficiency catalyst is required to promote the reactions.
In the field of organic small molecule catalysis, porphyrin ligands can be coordinated with various metal ions to form various metalloporphyrin complexes due to the rigid and stable coordination environment, so that the redox property of the metalloporphyrin complexes is enriched, and the porphyrin ligands can be used for the research of electrocatalytic hydrogen generation half reaction or oxygen generation half reaction (chem. Rev.2017,117, 3717-3797). However, considering that the metal complex has low solubility in aqueous solution and greatly reduces catalytic conductivity, molecules are usually loaded on carbon nanomaterials to realize the carbon nanocomposite material with functionalized metalloporphyrin complex (ACS cat.2017, 7, 8033-8041).
Disclosure of Invention
The invention aims to provide an azido porphyrin ligand capable of coordinating with various transition metal ions, a metalloporphyrin complex/carbon composite material which is based on the azido porphyrin ligand and covalently connected with a carbon nano material modified with alkynyl through azido-alkynyl cycloaddition reaction, and an application of the composite material.
Aiming at the purposes, the structural formula of the azidoporphyrin ligand adopted by the invention is as follows:
the preparation method of the azidoporphyrin ligand comprises the following steps: taking dichloromethane as a solvent, stirring 4-azidobenzaldehyde, pentafluorobenzaldehyde, pyrrole, boron trifluoride diethyl etherate, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) in a molar ratio of 1:3:4:1.6:3 in a dark place for reaction, and separating and purifying after the reaction is finished to obtain the azido porphyrin ligand.
The metalloporphyrin complex/carbon composite material is formed by covalently connecting a metalloporphyrin complex formed by coordination of any one metal of manganese, iron, cobalt, nickel and copper and the azidoporphyrin ligand with a carbon nano tube modified with alkynyl in an azido-alkynyl cycloaddition mode, and the preparation method comprises the following steps:
Adding a nitrine porphyrin ligand, a metal precursor and 2, 6-dimethyl pyridine into N, N-dimethylformamide, reacting for 0.5-12 h at 50-160 ℃ in a dark place under the condition of argon, and separating and purifying after the reaction is finished to obtain a metalloporphyrin complex with the following structural formula;
in the formula, M represents any one of Mn, Fe, Co, Ni and Cu, and the corresponding metal precursors are manganese acetate, ferrous chloride, cobalt acetate, nickel acetate and copper acetate in sequence.
Step 2, preparing alkynyl-modified carbon nano tube
Adding a carbon nano tube and 4-ethynylaniline into hydrochloric acid, performing ultrasonic dispersion uniformly, then adding a sodium nitrite aqueous solution at 0-5 ℃ and performing ultrasonic dispersion uniformly, then adding iron powder, and performing ultrasonic treatment for 1-1.5 h; and removing residual iron powder by using excessive dilute sulfuric acid, filtering, washing and drying to obtain the alkynyl-modified carbon nano tube.
Step 3, preparing the metalloporphyrin complex/carbon composite material
Adding the alkynyl-modified carbon nano tube and the metalloporphyrin complex into N, N-dimethylformamide, ultrasonically dispersing uniformly, stirring for 10-12 h at 70-90 ℃, and obtaining the metalloporphyrin/carbon composite material by agreeing to obtain the manganese porphyrin complex/carbon composite material or the iron porphyrin complex/carbon composite material or the cobalt porphyrin complex/carbon composite material or the nickel porphyrin complex/carbon composite material or the copper porphyrin complex/carbon composite material.
In the step 1, the molar ratio of the azidoporphyrin ligand to the metal precursor to the 2, 6-dimethylpyridine is preferably 1:10 to 12:0.15 to 0.20.
In the step 2, the molar ratio of the 4-ethynylaniline to the sodium nitrite is preferably 1:1 to 1.2, and the mass ratio of the carbon nanotube to the 4-ethynylaniline is preferably 1:8 to 12.
In the step 3, the mass ratio of the alkynyl-modified carbon nanotube to the metalloporphyrin complex is preferably 1:1 to 1.2.
The metalloporphyrin complex/carbon composite material can be used for catalyzing electrolyzed water to produce hydrogen and oxygen, and the specific use mode is as follows: the iron porphyrin complex/carbon composite material and the cobalt porphyrin complex/carbon composite material are respectively used as catalysts to be loaded on an electrode, the electrode loaded with the iron porphyrin complex/carbon composite material is used as a cathode, the electrode loaded with the cobalt porphyrin complex/carbon composite material is used as an anode, and water electrolysis is carried out in a KOH solution of 1.0 mol/L.
The invention has the following beneficial effects:
1. the azidoporphyrin ligand can be coordinated with different transition metal ions to form a metalloporphyrin complex. The metalloporphyrin complex can be covalently connected and immobilized on a carbon nano material through azide-alkynyl cycloaddition reaction with the alkynyl-modified carbon nano material to form the metalloporphyrin complex/carbon composite material. The construction of the immobilization mode not only realizes heterogeneous catalysis of various metalloporphyrin complexes, but also has excellent high conductivity, large specific surface area and good chemical stability of the carbon nano material.
2. The invention firstly forms the metalloporphyrin complex/carbon composite material into a double-electrode system to carry out electrocatalytic water decomposition and simultaneously produce hydrogen and oxygen, and the catalytic current density reaches 10mA/cm in the electrocatalytic water decomposition process 2 The required voltage is less than that of commercial platinum carbon and iridium carbon catalysts with the same loading.
3. The azido porphyrin ligand and the metal porphyrin complex/carbon composite material have the characteristics of simple and easily obtained raw materials, mild reaction conditions, simple operation and the like in the synthesis; in the aspect of catalyzing electrolysis water, the catalyst has low dosage, easily regulated and controlled catalysis conditions and good catalyst stability.
Drawings
FIG. 1 is a schematic synthesis scheme of a metalloporphyrin/carbon composite.
FIG. 2 is an infrared spectrum of 1-Mn @ CNT.
FIG. 3 is an infrared spectrum of 1-Fe @ CNT.
FIG. 4 is an infrared spectrum of 1-Co @ CNT.
FIG. 5 is an infrared spectrum of 1-Ni @ CNT.
FIG. 6 is an infrared spectrum of 1-Cu @ CNT.
FIG. 7 is an electrocatalytic water exploded view of 1-Fe @ CNT | |1-Co @ CNT with equal loading of platinum carbon and iridium carbon.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
Preparation of azidoporphyrin ligands
Into a 500mL round bottom flask equipped with a magnetic stir bar was added 300mL of methylene chloride, then 181.2mg (1.2mmol) of 4-azidobenzaldehyde, 444. mu.L (3.6mmol) of pentafluorobenzaldehyde, and 333. mu.L (4.8 mmol) of pyrrole were added in this order, and after stirring for 5min, 200. mu.L (1.6mmol) of boron trifluoride diethyl ether was added dropwise, and stirring was carried out for 45 min with exclusion of light, then 0.817g (3.6mmol) of DDQ was added, and stirring was continued for 1 h. Separating by thin-layer chromatography (using a mixed solution of petroleum ether and dichloromethane in a volume ratio of 2:1 as a developing agent), and then performing reduced pressure rotary evaporation to remove a solvent to obtain a purple solid, namely azido porphyrin ligand, namely porphyrin ligand 1, chemically named as 5- (4-azidophenyl) -10,15, 20-tris (perfluorophenyl) porphyrin, wherein the yield is 14.8%, and the structural characterization data are as follows:
1 H NMR(400MHz,CDCl 3 ):δ[ppm]＝9.01-8.78(m,8H),8.20(d,J＝8.2Hz,2H), 7.47(d,J＝8.0Hz,2H),-2.85(s,2H).
HRMS(ESI)m/z:C 44 H 15 F 15 N 7 ,[M+H] + theoretical value 926.1144; found 926.1143.
Example 2
1. Preparation of manganese porphyrin complex
To a 50mL round-bottomed flask equipped with a magnetic stir bar, 15mL of N, N-dimethylformamide was added, and 29.6mg (0.032mmol) of porphyrin ligand 1, 78.4mg (0.32mmol) of manganese acetate tetrahydrate, and 20. mu.L of 2, 6-lutidine were sequentially added, and the mixture was refluxed at 110 ℃ under argon atmosphere with the exclusion of light for 12 hours. Performing reduced pressure rotary evaporation to remove N, N-dimethylformamide, repeatedly washing with dichloromethane and saturated sodium chloride aqueous solution for three times, collecting an organic phase, drying with anhydrous sodium sulfate, performing rotary evaporation to remove dichloromethane, and recrystallizing with tetrahydrofuran to obtain a dark brown yellow solid, namely a manganese porphyrin complex (marked as 1-Mn), storing at low temperature in a dark place, wherein the yield is 70%, and the structural characterization data is as follows:
HRMS(ESI)m/z:C 44 H 12 F 15 N 7 Mn,[M] + theoretical value 978.0290; found 978.0289.
2. Preparation of alkynyl-modified carbon nanotubes
70mL of 0.5M hydrochloric acid solution is added into a 200mL round bottom flask, 30mg of Carbon Nanotubes (CNTs) and 305mg (2.6mmol) of 4-ethynylaniline are added and ultrasonic treatment is carried out for 30min, 15mL (2.6mmol) of sodium nitrite aqueous solution is added at 0 ℃ and ultrasonic treatment is carried out for 30min, and then 500mg of iron powder is added and ultrasonic treatment is carried out for 1 h. And removing residual iron powder by using excessive dilute sulfuric acid, sequentially washing with water, ethanol and acetone until the filtrate is colorless, and finally drying at room temperature to obtain the alkynyl-modified CNTs.
3. Preparation of manganese porphyrin complex/carbon composite material
Adding 20mLN, N-dimethylformamide into a 50mL round-bottom flask, adding 10mg of alkynyl-modified CNTs and 10mg of 1-Mn into the round-bottom flask, performing ultrasonic treatment for 10min, stirring for 12h at 85 ℃, centrifuging and collecting, dispersing in dichloromethane again, centrifuging and collecting for multiple times, washing off unreacted 1-Mn, and drying at room temperature in a dark place to obtain the manganoporphyrin complex/carbon composite material (marked as 1-Mn @ CNT).
The resulting product was characterized by IR spectroscopy, as shown in FIG. 2, with 1-Mn at 2100cm -1 Has a characteristic peak of azide, when the azide reacts with the CNTs modified with alkynyl, the characteristic peak of the azide disappears, and an infrared spectrogram of 1-Mn @ CNT and an infrared spectrogram of 1-Mn are 1800cm -1 ～600cm -1 There is a one-to-one correspondence, demonstrating successful covalent attachment of 1-Mn to CNTs.
Example 3
1. Preparation of iron porphyrin complexes
To a 50mL round-bottomed flask equipped with a magnetic stir bar, 15mL of N, N-dimethylformamide was added, and 29.6mg (0.032mmol) of porphyrin ligand 1, 40.6mg (0.32mmol) of ferrous chloride, and 20. mu.L of 2, 6-lutidine were sequentially added, followed by reflux reaction under argon at 110 ℃ for 3 hours in the absence of light. Removing N, N-dimethylformamide by reduced pressure rotary evaporation, repeatedly washing with dichloromethane and saturated sodium chloride aqueous solution for three times, then washing with dichloromethane and dilute hydrochloric acid aqueous solution for three times, collecting an organic phase, drying with anhydrous sodium sulfate, removing dichloromethane by rotary evaporation, and recrystallizing with tetrahydrofuran to obtain a dark brown yellow solid, namely the ferriporphyrin complex (marked as 1-Fe), wherein the yield is 75% by storing in a dark place at low temperature, and the structural characterization data is as follows:
HRMS(ESI)m/z:C 44 H 12 F 15 N 7 Fe,[M] + theoretical value 979.0259; found 979.0247.
2. Preparation of alkynyl-modified carbon nanotubes
This step is the same as step 2 of example 2.
3. Preparation of iron porphyrin complex/carbon composite material
Adding 20mLN, N-dimethylformamide into a 50mL round-bottom flask, adding 10mg of alkynyl-modified CNTs and 10mg of 1-Fe into the round-bottom flask, performing ultrasonic treatment for 10min, stirring for 12h at 85 ℃, centrifuging and collecting, dispersing in dichloromethane again, centrifuging and collecting for multiple times, washing away unreacted 1-Fe, and drying at room temperature in a dark place to obtain the iron porphyrin complex/carbon composite material (marked as 1-Fe @ CNT). As can be seen in FIG. 3, 1-Fe was successfully covalently attached to CNTs.
Example 4
1. Preparation of cobalt porphyrin complexes
To a 50mL round-bottomed flask equipped with a magnetic stirrer bar, 15mL of N, N-dimethylformamide was added, and 29.6mg (0.032mmol) of porphyrin ligand 1, 79.7mg (0.32mmol) of cobalt acetate tetrahydrate, and 20. mu.L of 2, 6-lutidine were sequentially added, followed by reflux reaction at 110 ℃ under argon atmosphere with exclusion of light for 3 hours. Decompressing and rotary steaming to remove N, N-dimethylformamide, repeatedly washing with dichloromethane and saturated sodium chloride aqueous solution for three times, collecting an organic phase, drying with anhydrous sodium sulfate, rotary steaming to remove dichloromethane, and recrystallizing with tetrahydrofuran to obtain a reddish brown solid, namely a cobalt porphyrin complex (marked as 1-Co), storing at low temperature in a dark place, wherein the yield is 80%, and the structural characterization data is as follows:
HRMS(ESI)m/z:C 44 H 12 F 15 N 7 co, theoretical 982.0241; found 982.0227.
2. Preparation of alkynyl-modified carbon nanotubes
This step is the same as step 2 of example 2.
3. Preparation of cobalt porphyrin complex/carbon composite material
Adding 20mLN, N-dimethylformamide into a 50mL round-bottom flask, adding 10mg of alkynyl-modified CNTs and 10mg of 1-Co into the round-bottom flask, performing ultrasonic treatment for 10min, stirring for 12h at 85 ℃, centrifuging and collecting, dispersing into dichloromethane again, centrifuging and collecting for multiple times, washing away unreacted 1-Co, and drying at room temperature in a dark place to obtain the cobalt porphyrin complex/carbon composite material (marked as 1-Co @ CNT). As can be seen in FIG. 4, 1-Co was successfully covalently attached to CNTs.
Example 5
1. Preparation of Nickel porphyrin complexes
In a 50mL round-bottomed flask equipped with a magnetic stir bar, 15mL of N, N-dimethylformamide was added, and 29.6mg (0.032mmol) of porphyrin ligand 1, 79.6mg (0.32mmol) of nickel acetate tetrahydrate, and 20. mu.L of 2, 6-lutidine were sequentially added, and the mixture was refluxed at 160 ℃ for 1 hour under argon atmosphere and protected from light. Decompressing and rotary steaming to remove N, N-dimethylformamide, repeatedly washing with dichloromethane and saturated sodium chloride aqueous solution for three times, collecting an organic phase, drying with anhydrous sodium sulfate, rotary steaming to remove dichloromethane, and recrystallizing with tetrahydrofuran to obtain a reddish brown solid, namely a nickel porphyrin complex (marked as 1-Ni), storing at low temperature in a dark place, wherein the yield is 80%, and the structural characterization data is as follows:
1 H NMR(400MHz,CDCl 3 ):δ[ppm]＝8.82-8.69(m,8H),8.57(d,J＝8.1Hz,2H), 8.18(d,J＝8.2Hz,2H).
2. preparation of alkynyl-modified carbon nanotubes
This procedure was the same as in example 2, step 2.
3. Preparation of nickel porphyrin complex/carbon composite material
Adding 20mLN, N-dimethylformamide into a 50mL round-bottom flask, adding 10mg of alkynyl-modified CNTs and 10mg of 1-Ni into the round-bottom flask, performing ultrasonic treatment for 10min, stirring for 12h at 85 ℃, centrifuging and collecting, then re-dispersing the mixture in dichloromethane, centrifuging and collecting for multiple times, washing away unreacted 1-Ni, and drying the mixture at room temperature in a dark place to obtain the nickel porphyrin complex/carbon composite material (marked as 1-Ni @ CNT). As can be seen in FIG. 5, 1-Ni is successfully covalently attached to CNTs.
Example 6
1. Preparation of copper porphyrin complexes
In a 50mL round-bottom flask equipped with a magnetic stir bar, 15mL of N, N-dimethylformamide was added, and 29.6mg (0.032mmol) of porphyrin ligand 1, 63.9mg (0.32mmol) of copper acetate monohydrate, and 20. mu.L of 2, 6-lutidine were sequentially added, and the mixture was reacted under argon at 50 ℃ for 30min in the dark. Decompressing and rotary steaming to remove N, N-dimethylformamide, repeatedly washing with dichloromethane and saturated sodium chloride aqueous solution for three times, collecting an organic phase, drying with anhydrous sodium sulfate, rotary steaming to remove dichloromethane, and recrystallizing with tetrahydrofuran to obtain a reddish brown solid, namely a copper porphyrin complex (marked as 1-Cu), storing at low temperature in a dark place, wherein the yield is 95%, and the structural characterization data is as follows:
HRMS(ESI)m/z:C 44 H 13 F 15 N 7 Cu,[M+H] + theoretical value 987.0283; found 987.0301.
2. Preparation of alkynyl-modified carbon nanotubes
This procedure was the same as in example 2, step 2.
3. Preparation of copper porphyrin complex/carbon composite material
Adding 20mLN, N-dimethylformamide into a 50mL round-bottom flask, adding 10mg of alkynyl-modified CNTs and 10mg of 1-Cu into the round-bottom flask, performing ultrasonic treatment for 10min, stirring the mixture for 12h at 85 ℃, centrifuging and collecting the mixture, dispersing the mixture in dichloromethane again, centrifuging and collecting the mixture for multiple times, washing away unreacted 1-Cu, and drying the mixture at room temperature in a dark place to obtain the copper porphyrin complex/carbon composite material (marked as 1-Cu @ CNT). As can be seen in FIG. 6, 1-Cu was successfully covalently attached to CNTs.
Example 7
Application of metalloporphyrin complex/carbon composite material in hydrogen production and oxygen production by catalytic electrolysis of water
Adding 3mg of 1-Fe @ CNT and 20 mu L of 5% Nafion into 1mL of N, N-dimethylformamide, performing ultrasonic treatment until the mixture is uniformly dispersed, uniformly dripping 3 mu L of mixed suspension onto the surface of a clean glassy carbon electrode, and airing at room temperature to obtain the electrode loaded with the 1-Fe @ CNT. The same procedure was used to prepare 1-Co @ CNT-loaded electrodes.
A double-electrode system 1-Fe @ CNT | |1-Co @ CNT is formed by taking an electrode loaded with 1-Fe @ CNT as a cathode and an electrode loaded with 1-Co @ CNT as an anode, and a total hydrolysis experiment is carried out under the conditions of a 1.0M KOH solution and a sweep rate of 10 mV/s. Meanwhile, a double-electrode system Pt/C I Ir/C formed by taking platinum carbon with the same loading amount as a cathode and iridium carbon as an anode is subjected to a total hydrolysis experiment under the same conditions. The results of the experiment are shown in FIG. 7.
As can be seen from FIG. 7, the current density reached 10mA/cm 2 When the water is decomposed by electrocatalysis water, the voltage required by 1-Fe @ CNT | |1-Co @ CNT is 2.18V, the voltage required by Pt/C | | Ir/C is 2.39V, 1-Fe @ CNT | | |1-Co @ CNT is 210 mV less than Pt/C | | Ir/C, namely the catalytic current density of the 1-Fe @ CNT | |1-Co @ CNT in the electrocatalysis water decomposition reaches 10mA/cm 2 The required voltage is less than Pt/C I Ir/C with equal load capacity, which shows that the performance of hydrogen production and oxygen production of the double-electrode catalytic electrolyzed water prepared by using the metalloporphyrin complex/carbon composite material as the catalyst is better than that of a platinum carbon and iridium carbon double electrode.
Claims (5)
1. The application of the metalloporphyrin complex/carbon composite material in hydrogen production and oxygen production by catalyzing and electrolyzing water comprises the following specific application modes: respectively taking an iron porphyrin complex/carbon composite material and a cobalt porphyrin complex/carbon composite material as catalysts to be loaded on an electrode, taking the electrode loaded with the iron porphyrin complex/carbon composite material as a cathode, taking the electrode loaded with the cobalt porphyrin complex/carbon composite material as an anode, and electrolyzing water in a 1.0mol/L KOH solution;
the iron porphyrin complex/carbon composite material is formed by covalently connecting a metal porphyrin complex formed by coordination of iron metal and an azidoporphyrin ligand with an alkynyl-modified carbon nanotube in an azido-alkynyl cycloaddition mode;
the cobalt porphyrin complex/carbon composite material is formed by covalently connecting a metal porphyrin complex formed by coordination of cobalt metal and an azidoporphyrin ligand with an alkynyl-modified carbon nanotube in an azido-alkynyl cycloaddition mode;
the structural formula of the azidoporphyrin ligand is shown as follows:
2. the application of the metalloporphyrin complex/carbon composite material in hydrogen production and oxygen production by catalytic electrolysis of water according to claim 1, wherein the iron porphyrin complex/carbon composite material and the cobalt porphyrin complex/carbon composite material are prepared by the following steps:
step 1, preparing metalloporphyrin complex
Adding a nitrine porphyrin ligand, a metal precursor and 2, 6-dimethyl pyridine into N, N-dimethylformamide, reacting for 0.5-12 h at 50-160 ℃ in a dark place under the condition of argon, and separating and purifying after the reaction is finished to obtain a metalloporphyrin complex with the following structural formula;
in the formula, M represents any one of Fe and Co, and the corresponding metal precursors are ferrous chloride and cobalt acetate in sequence;
step 2, preparing alkynyl-modified carbon nano tube
Adding a carbon nano tube and 4-ethynylaniline into hydrochloric acid, performing ultrasonic dispersion uniformly, then adding a sodium nitrite aqueous solution at 0-5 ℃ and performing ultrasonic dispersion uniformly, then adding iron powder, and performing ultrasonic treatment for 1-1.5 h; removing residual iron powder by using excessive dilute sulfuric acid, filtering, washing and drying to obtain the alkynyl-modified carbon nano tube;
step 3, preparing the metalloporphyrin complex/carbon composite material
Adding the alkynyl-modified carbon nano tube and the metal porphyrin complex into N, N-dimethylformamide, ultrasonically dispersing uniformly, and stirring for 10-12 hours at 70-90 ℃ to obtain a metal porphyrin/carbon composite material, namely an iron porphyrin complex/carbon composite material or a cobalt porphyrin complex/carbon composite material.
3. The application of metalloporphyrin complex/carbon composite material in hydrogen production and oxygen production by catalytic electrolysis of water according to claim 2, wherein: in the step 1, the molar ratio of the azidoporphyrin ligand to the metal precursor to the 2, 6-dimethylpyridine is 1: 10-12: 0.15-0.20.
4. The application of metalloporphyrin complex/carbon composite material in hydrogen production and oxygen production by catalytic electrolysis of water according to claim 2, wherein: in the step 2, the molar ratio of the 4-ethynylaniline to the sodium nitrite is 1: 1-1.2, and the mass ratio of the carbon nano tube to the 4-ethynylaniline is 1: 8-12.
5. The application of metalloporphyrin complex/carbon composite material in hydrogen production and oxygen production by catalytic electrolysis of water according to claim 2, wherein: in the step 3, the mass ratio of the alkynyl-modified carbon nanotube to the metalloporphyrin complex is 1: 1-1.2.
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