CN113717382B - Porphyrin and pyrimidine based high-density metallized covalent triazine polymer and preparation method and application thereof - Google Patents
Porphyrin and pyrimidine based high-density metallized covalent triazine polymer and preparation method and application thereof Download PDFInfo
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- CN113717382B CN113717382B CN202111005664.3A CN202111005664A CN113717382B CN 113717382 B CN113717382 B CN 113717382B CN 202111005664 A CN202111005664 A CN 202111005664A CN 113717382 B CN113717382 B CN 113717382B
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- covalent triazine
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229920000642 polymer Polymers 0.000 title claims abstract description 91
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 30
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- IIHQNAXFIODVDU-UHFFFAOYSA-N pyrimidine-2-carbonitrile Chemical compound N#CC1=NC=CC=N1 IIHQNAXFIODVDU-UHFFFAOYSA-N 0.000 claims abstract description 14
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229960001701 chloroform Drugs 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 13
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- AQIFPEIUSQBFJF-UHFFFAOYSA-N 4-[10,15,20-tris(4-cyanophenyl)-21,23-dihydroporphyrin-5-yl]benzonitrile Chemical compound N#Cc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C#N)c2ccc([nH]2)c(-c2ccc(cc2)C#N)c2ccc(n2)c(-c2ccc(cc2)C#N)c2ccc1[nH]2 AQIFPEIUSQBFJF-UHFFFAOYSA-N 0.000 claims description 4
- SSOJRFBFNLQGCL-UHFFFAOYSA-N C(#N)C=1C=C(C=CC=1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 Chemical compound C(#N)C=1C=C(C=CC=1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 SSOJRFBFNLQGCL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- GZCITSSHGGYVFC-UHFFFAOYSA-N 2-cyanopyrimidine-5-carboxylic acid Chemical compound OC(=O)C1=CN=C(C#N)N=C1 GZCITSSHGGYVFC-UHFFFAOYSA-N 0.000 claims description 2
- NOMODHWDBMCWFQ-UHFFFAOYSA-N 5-aminopyrimidine-2-carbonitrile Chemical compound NC1=CN=C(C#N)N=C1 NOMODHWDBMCWFQ-UHFFFAOYSA-N 0.000 claims description 2
- VPQICCOHFSGBMA-UHFFFAOYSA-N 5-bromopyrimidine-2-carbonitrile Chemical compound BrC1=CN=C(C#N)N=C1 VPQICCOHFSGBMA-UHFFFAOYSA-N 0.000 claims description 2
- BRBMDABLYHFXRX-UHFFFAOYSA-N 5-methylpyrimidine-2-carbonitrile Chemical compound CC1=CN=C(C#N)N=C1 BRBMDABLYHFXRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- WHGQAKJTBXKRSB-UHFFFAOYSA-N [N]1C2=CC=C1C=C(N1)C=C(C#N)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 Chemical compound [N]1C2=CC=C1C=C(N1)C=C(C#N)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 WHGQAKJTBXKRSB-UHFFFAOYSA-N 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 25
- 239000001569 carbon dioxide Substances 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 16
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000031700 light absorption Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000009849 vacuum degassing Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 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
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 porphyrin compound Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B01J35/39—
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/82—Metals of the platinum group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
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- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention relates to the technical field of catalytic materials, and particularly discloses a porphyrin and pyrimidine-based high-density catalystMetallized covalent triazine polymers and their preparation and use. The polymer takes porphyrin containing cyano group and 2-cyanopyrimidine or derivatives thereof as raw materials, trifluoromethanesulfonic acid as a catalyst, chloroform as a solvent, and under the protection of nitrogen, the polymer is subjected to a cyano cyclization reaction at a certain temperature to generate a triazine ring, so as to obtain a covalent triazine polymer; the obtained covalent triazine polymer and metal salt are heated in a solvent, metal ions are coordinated with the polymer to obtain the catalyst with high metal density, the metal ions are reaction active centers for catalyzing and converting carbon dioxide, and the high-density metal enriches the number of the active centers. Compared with the prior art, the covalent triazine polymer prepared by the invention has rich nitrogen content and high-density metal distribution, thereby having good light absorption performance and CO 2 Good adsorption and conversion performance, etc., in photocatalysis of CO 2 The method is well applied to the reaction.
Description
Technical Field
The invention relates to the technical field of catalytic materials, relates to preparation and application of a covalent triazine polymer material, and particularly relates to a porphyrin and pyrimidine based high-density metallized covalent triazine polymer, a preparation method thereof and application thereof in the field of photocatalytic carbon dioxide reduction.
Background
Carbon dioxide is a potential carbon resource, and the photocatalytic carbon dioxide is converted into a high-value-added product, which is not only a key reaction with great industrial application prospects, but also one of important means for solving a series of serious environmental problems caused by excessive emission of carbon dioxide. Currently, much research is being conducted on photocatalytic reduction of CO 2 The catalyst mainly comprises inorganic semiconductor materials, organic framework compounds, organic-inorganic hybrid materials and the like, and the existing problems are mainly focused on: the catalyst has poor carbon dioxide adsorption capacity, poor light absorption performance, few catalytic active sites and low carbon dioxide concentration on the surface of the material. Therefore, how to design and construct a catalyst with strong carbon dioxide adsorption capacity, strong light absorption capacity and rich active sites is one of the important research points for realizing the efficient reduction of carbon dioxide.
The porphyrin compound is a special macrocyclic compound, has a conjugated ring structure of pi electrons, the mobility of electrons in the molecular ring is good, and most porphyrins and derivatives thereof have better propertiesOptical properties. Therefore, porphyrins have attracted attention in recent years to researchers in the field of photocatalytic carbon dioxide reduction. However, porphyrin monomer is conjugated to CO 2 The adsorption capacity is weak, and the application of the photocatalyst in the field of photocatalysis is greatly limited.
The covalent triazine polymer material is a novel solid porous organic polymer, has the advantages of high chemical stability, large specific surface area, good semiconductor performance, simple synthesis process and the like, has proven visible light response and a proper energy band structure, and is an organic polymer semiconductor with a good application prospect. The triazine ring has rich nitrogen element content and excellent carbon dioxide adsorption capacity, and in addition, the triazine structure can be used as a good electron acceptor to receive photo-generated electrons and reduce carbon dioxide. However, CO of covalent triazine polymers 2 The insufficient reduction active sites limit the application of the catalyst in the field.
Disclosure of Invention
Aiming at the problem that the prior art can not simultaneously consider the number of catalytic active sites and CO 2 The invention aims to provide a high-density metallized covalent triazine polymer based on porphyrin and pyrimidine, and a preparation method and application thereof.
The invention discloses a covalent triazine polymer or metallized covalent triazine polymer, the structure of the covalent triazine polymer contains porphyrin, pyrimidine and triazine ring, and the covalent triazine polymer is characterized in that the structure of the covalent triazine polymer contains porphyrin, pyrimidine and triazine ring
One or two of (a) and (b); wherein R is 1 Is composed of
R 2 Is composed of
R 3 Is H, Br, NH 2 、 CH 3 Or COOH, structure
Represents a repeating triazine ring or pyrimidine structural unit;
the metallized covalent triazine polymer is a covalent triazine polymer in which metal ions M are anchored among porphyrin molecules, triazine rings and pyrimidine, and the metal ions are Cu 2+ 、Co 2+ 、Fe 2+ 、 Pt 2+ 、Pd 2+ Or Ni 2+ 。
Further, the present invention defines a metallized covalent triazine polymer comprising repeating structural units of one or more of the following four structural formulas:
furthermore, the invention also defines a preparation method of the covalent triazine polymer or the metallized covalent triazine polymer, which comprises the steps of taking porphyrin containing cyano groups and 2-cyanopyrimidine or derivatives thereof as raw materials, taking trifluoromethanesulfonic acid as a catalyst, taking trichloromethane as a solvent, and carrying out a cyanocyclization reaction at a certain temperature under the protection of nitrogen to generate triazine rings so as to obtain the covalent triazine polymer; the obtained covalent triazine polymer and metal salt are heated in a solvent, and metal ions are coordinated with the polymer to obtain the high-density metallized covalent triazine polymer.
Furthermore, the ratio of the cyano-containing porphyrin to the pyrimidine monomer is limited to be 1: 0.1-10.
Furthermore, the invention also limits the temperature of the cyano cyclization reaction to be-5-10 ℃.
Further, the invention also defines a process for the preparation of a covalent triazine polymer or a metallized covalent triazine polymer, comprising the steps of:
1) under the protection of nitrogen, dissolving porphyrin containing cyano group and 2-cyanopyrimidine or derivatives thereof in trichloromethane to form a solution A;
2) dissolving trifluoromethanesulfonic acid in chloroform at 0 ℃ in a nitrogen atmosphere to form a solution B;
3) keeping stirring in a nitrogen atmosphere, dropwise adding the solution A into the solution B by using an injector, stirring and reacting for 2-4 h at the temperature of-5-10 ℃, then heating the reaction mixture to room temperature, and continuously reacting for 10-13 h at the room temperature;
4) after the reaction in the step 3), adding ammonia water to neutralize the mixture to be neutral, stirring for 1.5-2.5 h, filtering to obtain a purple glossy crude product, washing and filtering with dichloromethane and acetone in sequence until the filtrate is colorless, and finally drying at 75-85 ℃ for 11-13 h to obtain the covalent triazine polymer;
5) adding the covalent triazine polymer and the metal salt obtained in the step 4) into a three-neck flask, adding a proper solvent by using an injector under the protection of nitrogen, stirring, heating, and carrying out reflux reaction for 8-30 h;
6) after the reaction is finished, cooling to room temperature, filtering to remove the solvent to obtain a crude product, washing with the solvent, filtering until the filtrate is colorless, and finally, drying in vacuum at 75-85 ℃ for 11-13 h to obtain the high-density metallized covalent triazine polymer.
Further, the present invention also defines derivatives of 2-cyanopyrimidines including 2-cyanopyrimidine, 2-cyano-5-bromopyrimidine, 2-cyano-5-aminopyrimidine, 2-cyano-5-methylpyrimidine or 2-cyano-5-carboxypyrimidine; the cyano-containing porphyrin is 5,10,15, 20-tetra (4-cyanophenyl) porphyrin or 5,10,15, 20-tetra (3-cyanophenyl) porphyrin.
Further, the invention also defines the solvent in the step 5) as N, N-dimethylformamide, acetonitrile or benzonitrile, the solvent input ratio is 15-25 mL/g solid, preferably 20 mL/g solid, and the solid amount refers to the total amount of the covalent triazine polymer and the metal salt.
Further, the invention also limits the metal salt in the step 5) to CuCl 2 、CoCl 2 、 FeCl 2 、PtCl 2 、PdCl 2 Or NiCl 2 。
The invention also defines a high-density metallized covalent triazine polymer in photocatalysis CO 2 Application in reduction.
The invention provides a porphyrin and pyrimidine based high-density metallized covalent triazine polymer, which takes four groups of compounds as examples, and the preparation process is as follows:
by adopting the technology, the invention takes cyanoporphyrin and 2-cyanopyrimidine or derivatives thereof as raw materials, a covalent triazine polymer is synthesized through polymerization reaction, the covalent triazine polymer is further metallized, and the high-density metallized covalent triazine polymer is prepared, the mobility of electrons in a porphyrin ring is good, photoproduction electrons excited by illumination can be efficiently transmitted in the ring, the triazine ring structure not only has excellent performance of adsorbing carbon dioxide molecules, but also can be used as a good electron acceptor, pyrimidine is another nitrogen-rich structure, on one hand, nitrogen content is increased by introducing the pyrimidine ring, the adsorption performance of carbon dioxide is increased therewith, on the other hand, nitrogen atoms adjacent to the space on the pyrimidine ring and the triazine ring can anchor metal ions to prepare a high-metal-density catalyst, the metal ions are reaction active centers for catalytically converting carbon dioxide, and the number of the active centers is enriched by high-density metals, therefore, the invention obtains high-density metallized covalent triazine polymer with good light absorption performance and CO 2 Good adsorption and conversion performance, etc., in photocatalysis of CO 2 The method is well applied to the reaction.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of the covalent triazine polymers obtained in examples 1-4;
FIG. 2a is an electron micrograph of the covalent triazine polymer obtained in examples 1-4;
FIG. 2b is the elemental distribution diagram of the covalent triazine polymer obtained in examples 1-4;
FIG. 3 is a graph of the carbon dioxide adsorption performance of the covalent triazine polymers obtained in examples 1-4;
FIG. 4 is a graph of the photocatalytic carbon dioxide reduction performance of the covalent triazine polymers obtained in examples 1-4.
Detailed Description
In order to make the synthesis and application of the present invention clearer, the present invention is further illustrated in detail with reference to the following examples. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
Example 1:
5,10,15, 20-tetrakis (4-cyanophenyl) porphyrin (0.71g, 1mmol) and 2-cyanopyrimidine (0.05g, 0.5mmol) were mixed in a molar ratio of 2: 1, adding the mixture into trichloromethane (anhydrous sodium sulfate is dried in advance), and keeping the mixture for 30min under the nitrogen atmosphere; trifluoromethanesulfonic acid (1mL) was added to chloroform (4mL) (anhydrous sodium sulfate pre-dried) at 0 deg.C and held under nitrogen for 30 min; then dropwise adding the dissolved mixture of porphyrin and pyrimidine into the mixture of trifluoromethanesulfonic acid and trichloromethane by using a syringe, reacting for 3h at 0 ℃, and then reacting for 12h at normal temperature; after the reaction is finished, 30mL of ammonia water and 70mL of deionized water are uniformly mixed and then added into a reaction bottle, stirring is continued for 2h, then filtering is carried out to obtain a purple glossy solid, namely a crude product, dichloromethane and acetone are sequentially used for washing and filtering until filtrate is colorless, and then the filtrate is transferred to a vacuum oven to be dried for 12h at 80 ℃ to obtain the clean covalent triazine polymer CTF-MD.
Adding the covalent triazine polymer (0.43g, 0.3mmol) obtained above and platinum dichloride (0.38 g, 1.44mmol) into a reaction bottle, vacuum degassing to replace nitrogen, adding benzonitrile (20mL) by using a syringe, vacuumizing again to replace nitrogen, stirring, heating to 180 ℃, and carrying out reflux reaction for 30 hours; and after the reaction is finished, cooling to room temperature, filtering to remove the solvent to obtain a crude product, washing and filtering with benzonitrile, methanol and acetone in sequence until the filtrate is colorless, and then transferring to a vacuum oven for drying at 80 ℃ for 12 hours to obtain the clean high-density metal platinum-loaded covalent triazine polymer Pt-CTF-MD.
Example 2:
mixing 5,10,15, 20-tetrakis (4-cyanophenyl) porphyrin (0.71g, 1mmol) and 2-cyanopyrimidine (0.2g, 2mmol) in a molar ratio of 1: 2 adding into chloroform (anhydrous sodium sulfate is dried in advance), and keeping for 30min under nitrogen atmosphere; trifluoromethanesulfonic acid (1mL) was added to chloroform (4mL) (anhydrous sodium sulfate pre-dried) at 0 deg.C and held under nitrogen for 30 min; then dropwise adding the dissolved mixture of porphyrin and pyrimidine into the mixture of trifluoromethanesulfonic acid and chloroform by using an injector, reacting for 3h at 0 ℃, and then transferring to normal temperature to react for 12 h; after the reaction is finished, 40mL of ammonia water and 60mL of deionized water are uniformly mixed and then added into a reaction bottle, the mixture is continuously stirred for 2 hours, then the mixture is filtered to obtain purple glossy solid, namely a crude product, the crude product is washed and filtered by dichloromethane and acetone in sequence until the filtrate is colorless, and then the filtrate is transferred to a vacuum oven to be dried for 12 hours at the temperature of 80 ℃ to obtain a clean covalent triazine polymer.
Adding the covalent triazine polymer (0.43g, 0.3mmol) obtained in the step (a) and palladium dichloride (0.26 g, 1.44mmol) into a reaction bottle, vacuum degassing to replace nitrogen, then adding acetonitrile (30mL) by using a syringe, vacuumizing to replace nitrogen again, stirring, heating to 65 ℃, and carrying out reflux reaction for 24 hours; and after the reaction is finished, cooling to room temperature, filtering to remove the solvent to obtain a crude product, washing and filtering with acetonitrile, methanol and acetone in sequence until the filtrate is colorless, and then transferring to a vacuum oven for drying at 80 ℃ for 12 hours to obtain the clean high-density metal palladium-supported covalent triazine polymer Pd-CTF-MD.
Example 3:
5,10,15, 20-tetrakis (3-cyanophenyl) porphyrin (0.71g, 1mmol) and 2-cyanopyrimidine (0.05g, 0.5mmol) were mixed in a molar ratio of 2: 1, adding the mixture into trichloromethane (anhydrous sodium sulfate is dried in advance), and keeping the mixture for 30min under the nitrogen atmosphere; trifluoromethanesulfonic acid (1mL) was added to chloroform (4mL) (anhydrous sodium sulfate pre-dried) at 10 deg.C and held under nitrogen for 30 min; then dropwise adding the dissolved mixture of porphyrin and pyrimidine into the mixture of trifluoromethanesulfonic acid and chloroform by using an injector, reacting for 3h at 10 ℃, and then transferring to normal temperature for reacting for 12 h; after the reaction is finished, 40mL of ammonia water and 60mL of deionized water are uniformly mixed and then added into a reaction bottle, the mixture is continuously stirred for 2 hours, then the mixture is filtered to obtain purple glossy solid, namely a crude product, the crude product is washed and filtered by dichloromethane and acetone in sequence until the filtrate is colorless, and then the filtrate is transferred to a vacuum oven to be dried for 12 hours at the temperature of 80 ℃ to obtain a clean covalent triazine polymer.
Adding the covalent triazine polymer (0.43g, 0.3mmol) obtained above and cobalt chloride hexahydrate (0.34g, 1.44mmol) into a reaction bottle, vacuum degassing to replace nitrogen, adding N, N-dimethylformamide (30mL) by using a syringe, vacuumizing again to replace nitrogen, stirring, heating to 120 ℃, and carrying out reflux reaction for 8 hours; and after the reaction is finished, cooling to room temperature, filtering to remove the solvent to obtain a crude product, washing and filtering by using N, N-dimethylformamide, methanol and acetone in sequence until the filtrate is colorless, and then transferring to a vacuum oven for drying at 80 ℃ for 12h to obtain the clean high-density metal cobalt-loaded covalent triazine polymer Co-CTF-MD.
As can be seen from the Fourier transform infrared spectrum of FIG. 1, all materials are at 1300cm -1 And 1500cm -1 Characteristic peaks of triazine ring appear at all parts, which proves that the covalent triazine polymer is successfully synthesized; and after metallization, at 1050cm -1 There appears a peak characteristic of coordination of metal to nitrogen, indicating that the material has been metallized, which is consistent with the expected results.
Example 4:
mixing 5,10,15, 20-tetrakis (3-cyanophenyl) porphyrin (0.71g, 1mmol) and 2-cyanopyrimidine (0.2g, 2mmol) in a molar ratio of 1: 2 adding into chloroform (anhydrous sodium sulfate is dried in advance), and keeping for 30min under nitrogen atmosphere; trifluoromethanesulfonic acid (1mL) was added to chloroform (4mL) (anhydrous sodium sulfate pre-dried) at 0 deg.C and held under nitrogen for 30 min; then dropwise adding the dissolved mixture of porphyrin and pyrimidine into the mixture of trifluoromethanesulfonic acid and chloroform by using an injector, reacting for 3h at-5 ℃, and then transferring to normal temperature to react for 12 h; after the reaction is finished, 30mL of ammonia water and 70mL of deionized water are uniformly mixed and then added into a reaction bottle, the mixture is continuously stirred for 2h, then the mixture is filtered to obtain purple glossy solid, namely a crude product, the crude product is washed and filtered by dichloromethane and acetone in sequence until the filtrate is colorless, and then the filtrate is transferred to a vacuum oven to be dried for 12h at the temperature of 80 ℃ to obtain the clean covalent triazine polymer.
Adding the covalent triazine polymer (0.43g, 0.3mmol) and copper acetate (0.29 g, 1.44mmol) into a reaction bottle, adding N, N-dimethylformamide (20mL), stirring, heating to 120 ℃, and carrying out reflux reaction for 12 h; and after the reaction is finished, cooling to room temperature, filtering to remove the solvent to obtain a crude product, washing and filtering by using N, N-dimethylformamide, methanol and acetone in sequence until the filtrate is colorless, and then transferring to a vacuum oven for drying at 80 ℃ for 12h to obtain the clean high-density metallic copper-loaded covalent triazine polymer Cu-CTF-MD.
FIG. 2a is an electron micrograph of the synthesized covalent triazine polymer, the morphology of the material was bulk solid with no apparent change before and after metallization, indicating that the material was not damaged after metallization; fig. 2b is an element distribution diagram, and it can be seen that the metal ions are uniformly distributed on the surface of the material, which proves that the material has been successfully metallized.
Example 5:
the application of a porphyrin and pyrimidine based high-density metallized covalent triazine polymer in photocatalytic carbon dioxide reduction comprises the following specific steps:
the photocatalytic reaction is carried out in a special reactor, the reactor contains 50mg of the catalyst in the embodiment 1-4 and 15mL of pure water respectively, and the reactor is used for pure CO 2 Gas is inflated and deflated for three times, and CO is introduced into the reactor after the three times 2 Until the pressure in the reactor is 80kPa, then the reactor is irradiated under a xenon lamp with stirring at 600rpm, and the temperature of the circulating water control system is 20 ℃. The gas in the reactor was sampled every 1h to a gas chromatograph to determine the amount of product.
Example 6:
an application of a porphyrin and pyrimidine based high-density metallized covalent triazine polymer in photocatalytic carbon dioxide reduction comprises the following specific steps:
the photocatalytic reaction was carried out in a specially prepared reactor containing the catalysts of examples 1-4, respectively50mg of agent, 15mL of pure water and 5mL of triethylamine, and using pure CO for the reactor 2 Gas is inflated and deflated for three times, and CO is introduced into the reactor after the three times 2 Until the pressure in the reactor is 80kPa, then the reactor is irradiated under a xenon lamp under the stirring of 600rpm, and the temperature of the circulating water control system is 20 ℃. The gas in the reactor was sampled every 1h to a gas chromatograph to determine the amount of product.
Example 7:
the application of a porphyrin and pyrimidine based high-density metallized covalent triazine polymer in photocatalytic carbon dioxide reduction comprises the following specific steps:
the photocatalytic reaction is carried out in a special reactor, the reactor contains 50mg of the catalyst in the embodiment 1-4, 10mL of pure water, 20mL of triethanolamine and 30mL of acetonitrile, and the reactor is used with pure CO 2 Gas is inflated and deflated for three times, and CO is introduced into the reactor after the three times 2 Until the pressure in the reactor is 80kPa, then the reactor is irradiated under a xenon lamp under the stirring of 600rpm, and the temperature of the circulating water control system is 20 ℃. The gas in the reactor was sampled every 1h to a gas chromatograph to determine the amount of product.
First, the adsorption performance of the polymer materials obtained in examples 1-4 on carbon dioxide is evaluated, as shown in fig. 3, it can be seen from fig. 3 that the metallized covalent triazine polymer has good adsorption performance on carbon dioxide, which is beneficial to further activating the material on carbon dioxide, thereby promoting the smooth proceeding of the photocatalytic reaction. Examples 5 to 7 are tests on the photocatalytic carbon dioxide reduction performance of the material under different systems, and as can be seen by combining fig. 4, the material can maintain good and stable photocatalytic carbon dioxide reduction performance within 6 hours, and the high-density metallized covalent triazine material of the invention has better catalytic performance under the same conditions of the catalytic system as the same type of material in the literature.
The above description is only exemplary of the present invention, and all modifications and substitutions within the scope of the claims should be considered to be included in the present invention.
Claims (10)
1. A covalent triazine polymer or metallized covalent triazine polymer, the covalent triazine polymer structure contains porphyrin, pyrimidine and triazine ring, characterized in that the structure contains
One or two of them;
wherein R is 1 Is composed of
R 2 Is composed of
In the structure of
Represents a repeating structural unit;
R 3 is H, Br, NH 2 、CH 3 Or COOH, the metallized covalent triazine polymer is a covalent triazine polymer in which metal ions M are anchored among porphyrin molecules, triazine rings and pyrimidine, and the metal ions M are Cu 2+ 、Co 2+ 、Fe 2+ 、Pt 2+ 、Pd 2+ Or Ni 2+ ；
The metallized covalent triazine polymer specifically includes repeating structural units of one or more of the following four structural formulae:
2. a method for preparing a covalent triazine polymer or a metallized covalent triazine polymer according to claim 1, characterized in that cyano-containing porphyrin and 2-cyanopyrimidine or derivatives thereof are used as raw materials, trifluoromethanesulfonic acid is used as a catalyst, chloroform is used as a solvent, and a cyanocyclization reaction is performed at a certain temperature under the protection of nitrogen to generate a triazine ring, thereby obtaining the covalent triazine polymer; the resulting covalent triazine polymer is heated with a metal salt in a solvent, and the metal ions coordinate with the polymer to yield a high density metallized covalent triazine polymer.
3. The method of claim 2, wherein the monomer ratio of cyanoporphyrin-containing to 2-cyanopyrimidine or derivative thereof is 1:0.1 to 10.
4. The process for the preparation of a covalent triazine polymer or a metallized covalent triazine polymer of claim 2, wherein the temperature of the cyanocyclization reaction is from-5 to 10 ℃.
5. Process for the preparation of a covalent triazine polymer or of a metallized covalent triazine polymer according to claim 2, characterized in that it comprises in particular the following steps:
1) under the protection of nitrogen, dissolving porphyrin containing cyano group and 2-cyanopyrimidine or derivatives thereof in trichloromethane to form a solution A;
2) dissolving trifluoromethanesulfonic acid in chloroform at 0 ℃ under the atmosphere of nitrogen to form a solution B;
3) keeping stirring in a nitrogen atmosphere, dropwise adding the solution A into the solution B by using an injector, stirring and reacting for 2-4 h at-5-10 ℃, then heating the reaction mixture to room temperature, and continuously reacting for 10-13 h at the room temperature;
4) after the reaction in the step 3), adding ammonia water to neutralize the mixture to be neutral, stirring for 1.5-2.5 h, filtering to obtain a purple glossy crude product, washing and filtering with dichloromethane and acetone in sequence until the filtrate is colorless, and finally drying at 75-85 ℃ for 11-13 h to obtain the covalent triazine polymer;
5) adding the covalent triazine polymer and the metal salt obtained in the step 4) into a three-neck flask, adding a proper solvent by using an injector under the protection of nitrogen, stirring, heating, and carrying out reflux reaction for 8-30 h;
6) after the reaction is finished, cooling to room temperature, filtering to remove the solvent to obtain a crude product, washing with the solvent, filtering until the filtrate is colorless, and finally, drying in vacuum at 75-85 ℃ for 11-13 h to obtain the high-density metallized covalent triazine polymer.
6. A process for the preparation of a covalent triazine polymer or of a metallated covalent triazine polymer according to claim 2, characterized in that the derivative of 2-cyanopyrimidine comprises 2-cyano-5-bromopyrimidine, 2-cyano-5-aminopyrimidine, 2-cyano-5-methylpyrimidine or 2-cyano-5-carboxypyrimidine; the cyano-containing porphyrin is 5,10,15, 20-tetra (4-cyanophenyl) porphyrin or 5,10,15, 20-tetra (3-cyanophenyl) porphyrin.
7. The process for the preparation of covalent triazine polymers or metallized covalent triazine polymers of claim 5, wherein the solvent in step 5) is N, N-dimethylformamide, acetonitrile or benzonitrile, the solvent input ratio is 15-25 mL/g solid, and the amount of solid refers to the total amount of covalent triazine polymer and metal salt.
8. The process for the preparation of a covalent triazine polymer or a metallized covalent triazine polymer of claim 5, the solvent input ratio in step 5) being 20 mL/g solid.
9. Process for the preparation of covalent triazine polymers or metallized covalent triazine polymers according to claim 5, characterized in that the metal salt in step 5) is CuCl 2 、CoCl 2 、FeCl 2 、PtCl 2 、PdCl 2 Or NiCl 2 。
10. A covalent triazine polymer or metallized covalent triazine polymer of claim 1 in photocatalytic CO 2 Application in reduction.
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