CN113717382B - 一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物及其制备方法和应用 - Google Patents
一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物及其制备方法和应用 Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- covalent triazine
- polymer
- triazine polymer
- metallized
- covalent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/1815—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
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G73/065—Preparatory processes
-
- 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
- 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
-
- 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
- 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
-
- 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
- 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
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
-
- 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
- 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
- B01J2531/845—Cobalt
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
本发明涉及催化材料技术领域,具体公开了一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物及其制备与应用。该聚合物是以含氰基卟啉与2‑氰基嘧啶或其衍生物为原料,以三氟甲磺酸为催化剂,以三氯甲烷为溶剂,氮气保护下,于一定温度下进行氰基环化反应生成三嗪环,得到共价三嗪聚合物;所得共价三嗪聚合物与金属盐在溶剂中加热,金属离子与聚合物配位得到,高金属密度的催化剂,金属离子是催化转化二氧化碳的反应活性中心,高密度的金属丰富了活性中心数量。与现有技术相比,本发明制备的共价三嗪聚合物有丰富的氮含量和高密度的金属分布,因而具有光吸收性能良好,CO2吸附和转化性能良好等优点,在光催化CO2反应中得到良好应用。
Description
技术领域
本发明涉及催化材料技术领域,涉及一种共价三嗪聚合物材料的制备及其应用,具体涉及一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物及其制备方法和在光催化二氧化碳还原领域中的应用。
背景技术
二氧化碳是一种潜在的碳资源,光催化二氧化碳转化至高附加值产品,其不仅是极具工业应用前景的关键反应,而且是解决二氧化碳过量排放导致的一系列严重环境问题的重要手段之一。当前,研究较多的光催化还原CO2催化剂主要有无机半导体材料、有机框架化合物、有机-无机杂化材料等,存在的问题主要集中在:催化剂吸附二氧化碳能力差,光吸收性能差,催化活性位点少,材料表面二氧化碳浓度低。因此,如何设计构造出一种对二氧化碳吸附能力强、光吸收能力强,活性位点丰富的催化剂,是实现二氧化碳高效还原的研究重点之一。
卟啉化合物是一类特殊的大环化合物,具有π电子的共轭环状结构,分子环内电子的流动性良好,大多数卟啉及其衍生物均有较好的光学性质。因此,近年来,卟啉在光催化二氧化碳还原领域引起了研究者们的关注。然而,卟啉单体对CO2吸附能力较弱,极大地限制了其在光催化领域的应用。
共价三嗪聚合物材料是一种新型固体多孔有机聚合物,具有化学稳定性高、比表面积大、半导体性能好、合成工艺简单等优点,且已被证明具有可见光响应及合适的能带结构,是一种很有应用前途的有机聚合物半导体。三嗪环上氮元素含量丰富,拥有优良的二氧化碳吸附能力,另外,三嗪结构可以作为良好的电子受体,接收光生电子,还原二氧化碳。然而,共价三嗪聚合物的CO2还原活性位点不足,使其在该领域的应用受到一定限制。
发明内容
针对现有技术不能同时兼顾催化活性位点数量、CO2吸附和光吸收能力的问题,本发明的目的在于提供一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物及其制备方法和应用。
本发明公开了一种共价三嗪聚合物或金属化的共价三嗪聚合物,所述共价三嗪聚合物结构中含有卟啉、嘧啶和三嗪环,其特征在于其结构为含有中的一种或两种;其中,R1为R2为R3为H、Br、NH2、 CH3或COOH,结构中的表示重复的三嗪环或嘧啶结构单元;
所述金属化的共价三嗪聚合物为共价三嗪聚合物中卟啉分子本身、三嗪环和嘧啶之间锚定金属离子M,金属离子为Cu2+、Co2+、Fe2+、 Pt2+、Pd2+或Ni2+。
进一步地,本发明限定了金属化的共价三嗪聚合物包括以下四种结构式的一种或多种的重复结构单元:
更进一步地,本发明还限定了所述的共价三嗪聚合物或金属化的共价三嗪聚合物的制备方法,以含氰基卟啉与2-氰基嘧啶或其衍生物为原料,以三氟甲磺酸为催化剂,以三氯甲烷为溶剂,氮气保护下,于一定温度下进行氰基环化反应生成三嗪环,得到共价三嗪聚合物;所得共价三嗪聚合物与金属盐在溶剂中加热,金属离子与聚合物配位,得到高密度金属化的共价三嗪聚合物。
进一步地,本发明还限定了含氰基卟啉和嘧啶单体比例为 1:0.1~10。
进一步地,本发明还限定了氰基环化反应的温度为-5~10℃。
进一步地,本发明还限定了共价三嗪聚合物或金属化的共价三嗪聚合物的制备方法,具体包括如下步骤:
1)在氮气保护下,将含氰基卟啉与2-氰基嘧啶或其衍生物溶解于三氯甲烷形成溶液A;
2)在氮气氛围下,0℃下将三氟甲磺酸溶解于三氯甲烷形成溶液 B;
3)在氮气氛围下,保持搅拌,利用注射器将溶液A逐滴滴加至溶液B,并在-5~10℃搅拌反应2~4h,再将反应混合物升温至室温,并在室温下继续反应10~13h;
4)步骤3)反应结束后,加氨水中和混合物至中性,并搅拌1.5~ 2.5h,过滤得到紫色有光泽的粗产物,依次用二氯甲烷、丙酮洗涤过滤,洗至滤液为无色,最后在75~85℃下干燥11~13h,得到共价三嗪聚合物;
5)步骤4)得到的共价三嗪聚合物和金属盐加至三颈烧瓶,在氮气保护下,用注射器加入合适的溶剂,搅拌升温回流反应8~30h;
6)反应结束后,冷却至室温,过滤除去溶剂得到粗产物,用溶剂洗涤过滤,直至滤液为无色,最后在75~85℃下真空干燥11~13h,得到高密度金属化的共价三嗪聚合物。
进一步地,本发明还限定了2-氰基嘧啶的衍生物包括2-氰基嘧啶、 2-氰基-5-溴基嘧啶、2-氰基-5-氨基嘧啶、2-氰基-5-甲基嘧啶或2-氰基 -5-羧基嘧啶;含氰基卟啉为5,10,15,20-四(4-氰基苯基)卟啉或 5,10,15,20-四(3-氰基苯基)卟啉。
进一步地,本发明还限定了步骤5)中的溶剂为N,N-二甲基甲酰胺、乙腈或苯甲腈,溶剂投入比为15-25mL/克固体,优选为20mL/ 克固体,固体量是指共价三嗪聚合物和金属盐的总量。
进一步地,本发明还限定了步骤5)中的金属盐为CuCl2、CoCl2、 FeCl2、PtCl2、PdCl2或NiCl2。
本发明还限定了一种高密度金属化的共价三嗪聚合物在光催化 CO2还原中的应用。
本发明提供的一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物,以下四组化合物为例,其制备过程如下:
通过采用上述技术,本发明以含氰基卟啉和2-氰基嘧啶或其衍生物为原料,通过聚合反应合成共价三嗪聚合物,共价三嗪聚合物进一步金属化,制备得到高密度金属化的共价三嗪聚合物,卟啉环内电子的流动性良好,光照激发的光生电子能够在环内高效传输,三嗪环结构既拥有吸附二氧化碳分子的优良性能,又可以作为良好的电子受体,嘧啶是另一种富氮结构,引入嘧啶环一方面增加了氮含量,二氧化碳的吸附性能随之增加,另一方面,嘧啶环与三嗪环上空间相邻的氮原子可以锚定金属离子,制备高金属密度的催化剂,金属离子是催化转化二氧化碳的反应活性中心,高密度的金属丰富了活性中心数量,因此,本发明得到高密度金属化的共价三嗪聚合物,具有光吸收性能良好,CO2吸附和转化性能良好等优点,在光催化CO2反应中得到良好应用。
附图说明
图1为实施例1-4所得的共价三嗪聚合物的傅里叶转换红外光谱图;
图2a为实施例1-4所得的共价三嗪聚合物的电镜图;
图2b为实施例1-4所得的共价三嗪聚合物的元素分布图;
图3为实施例1-4所得的共价三嗪聚合物的二氧化碳吸附性能图;
图4为实施例1-4所得的共价三嗪聚合物的光催化二氧化碳还原性能图。
具体实施方式
为了使本发明合成及应用更加清晰,以下结合实施例对本发明进行进一步详细说明。此处所描述的具体实施例仅仅用于解释本发明,但不用于限定本发明。
实施例1:
将5,10,15,20-四(4-氰基苯基)卟啉(0.71g,1mmol)和2-氰基嘧啶(0.05g,0.5mmol)按照摩尔比2:1加入到三氯甲烷中(无水硫酸钠提前干燥),在氮气氛围下保持30min;在0℃下,将三氟甲磺酸 (1mL)加入到三氯甲烷(4mL)中(无水硫酸钠提前干燥),在氮气氛围下保持30min;然后将溶解好的卟啉和嘧啶的混合物利用注射器逐滴滴加至三氟甲磺酸和三氯甲烷的混合物中,0℃下反应3h,接着转至常温反应12h;反应结束后,将30mL氨水和70mL去离子水混合均匀后加入反应瓶中,继续搅拌2h,然后过滤得到紫色有光泽的固体即为粗产物,依次用二氯甲烷、丙酮洗涤过滤,直至滤液无色,然后转移至真空烘箱80℃下干燥12h,得到干净的共价三嗪聚合物 CTF-MD。
将上述所得共价三嗪聚合物(0.43g,0.3mmol)和二氯化铂(0.38 g,1.44mmol)加入反应瓶中,真空脱气置换氮气,然后用注射器加入苯甲腈(20mL),再次抽真空置换氮气,搅拌加热升温至180℃,回流反应30h;反应结束后冷却至室温,过滤除去溶剂得到粗产物,依次用苯甲腈、甲醇、丙酮洗涤过滤,直至滤液无色,然后转移至真空烘箱80℃下干燥12h,得到干净的高密度金属铂负载的共价三嗪聚合物Pt-CTF-MD。
实施例2:
将5,10,15,20-四(4-氰基苯基)卟啉(0.71g,1mmol)和2-氰基嘧啶(0.2g,2mmol)按照摩尔比1:2加入到三氯甲烷中(无水硫酸钠提前干燥),在氮气氛围下保持30min;在0℃下,将三氟甲磺酸 (1mL)加入到三氯甲烷(4mL)中(无水硫酸钠提前干燥),在氮气氛围下保持30min;然后将溶解好的卟啉和嘧啶的混合物利用注射器逐滴滴加至三氟甲磺酸和三氯甲烷的混合物中,0℃下反应3h,接着转至常温反应12h;反应结束后,将40mL氨水和60mL去离子水混合均匀后加入反应瓶中,继续搅拌2h,然后过滤得到紫色有光泽的固体即为粗产物,依次用二氯甲烷、丙酮洗涤过滤,直至滤液无色,然后转移至真空烘箱80℃下干燥12h,得到干净的共价三嗪聚合物。
将上述所得共价三嗪聚合物(0.43g,0.3mmol)和二氯化钯(0.26 g,1.44mmol)加入反应瓶中,真空脱气置换氮气,然后用注射器加入乙腈(30mL),再次抽真空置换氮气,搅拌加热升温至65℃,回流反应24h;反应结束后冷却至室温,过滤除去溶剂得到粗产物,依次用乙腈、甲醇、丙酮洗涤过滤,直至滤液无色,然后转移至真空烘箱80℃下干燥12h,得到干净的高密度金属钯负载的共价三嗪聚合物Pd-CTF-MD。
实施例3:
将5,10,15,20-四(3-氰基苯基)卟啉(0.71g,1mmol)和2-氰基嘧啶(0.05g,0.5mmol)按照摩尔比2:1加入到三氯甲烷中(无水硫酸钠提前干燥),在氮气氛围下保持30min;在10℃下,将三氟甲磺酸(1mL)加入到三氯甲烷(4mL)中(无水硫酸钠提前干燥),在氮气氛围下保持30min;然后将溶解好的卟啉和嘧啶的混合物利用注射器逐滴滴加至三氟甲磺酸和三氯甲烷的混合物中,10℃下反应3h,接着转至常温反应12h;反应结束后,将40mL氨水和60mL去离子水混合均匀后加入反应瓶中,继续搅拌2h,然后过滤得到紫色有光泽的固体即为粗产物,依次用二氯甲烷、丙酮洗涤过滤,直至滤液无色,然后转移至真空烘箱80℃下干燥12h,得到干净的共价三嗪聚合物。
将上述所得共价三嗪聚合物(0.43g,0.3mmol)和六水合氯化钴 (0.34g,1.44mmol)加入反应瓶中,真空脱气置换氮气,然后用注射器加入N,N-二甲基甲酰胺(30mL),再次抽真空置换氮气,搅拌加热升温至120℃,回流反应8h;反应结束后冷却至室温,过滤除去溶剂得到粗产物,依次用N,N-二甲基甲酰胺、甲醇、丙酮洗涤过滤,直至滤液无色,然后转移至真空烘箱80℃下干燥12h,得到干净的高密度金属钴负载的共价三嗪聚合物Co-CTF-MD。
由图1的傅里叶转换红外光谱图可以看出,所有材料在1300cm-1和1500cm-1处均出现了三嗪环的特征峰,即证明共价三嗪聚合物已顺利合成;且金属化后,在1050cm-1处出现了金属与氮的配位特征峰,即说明材料已金属化完成,这与预期结果一致。
实施例4:
将5,10,15,20-四(3-氰基苯基)卟啉(0.71g,1mmol)和2-氰基嘧啶(0.2g,2mmol)按照摩尔比1:2加入到三氯甲烷中(无水硫酸钠提前干燥),在氮气氛围下保持30min;在0℃下,将三氟甲磺酸 (1mL)加入到三氯甲烷(4mL)中(无水硫酸钠提前干燥),在氮气氛围下保持30min;然后将溶解好的卟啉和嘧啶的混合物利用注射器逐滴滴加至三氟甲磺酸和三氯甲烷的混合物中,-5℃下反应3h,接着转至常温反应12h;反应结束后,将30mL氨水和70mL去离子水混合均匀后加入反应瓶中,继续搅拌2h,然后过滤得到紫色有光泽的固体即为粗产物,依次用二氯甲烷、丙酮洗涤过滤,直至滤液无色,然后转移至真空烘箱80℃下干燥12h,得到干净的共价三嗪聚合物。
将上述所得共价三嗪聚合物(0.43g,0.3mmol)和醋酸铜(0.29 g,1.44mmol)加入反应瓶中,然后加入N,N-二甲基甲酰胺(20mL),搅拌加热升温至120℃,回流反应12h;反应结束后冷却至室温,过滤除去溶剂得到粗产物,依次用N,N-二甲基甲酰胺、甲醇、丙酮洗涤过滤,直至滤液无色,然后转移至真空烘箱80℃下干燥12h,得到干净的高密度金属铜负载的共价三嗪聚合物Cu-CTF-MD。
图2a是所合成的共价三嗪聚合物的电镜图,金属化前后,材料的形貌均为块状固体,没有明显变化,说明材料在金属化之后没有被破坏;图2b是元素分布图,可以看出金属离子在材料表面分布均匀,证明材料已成功金属化。
实施例5:
一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物在光催化二氧化碳还原中的应用,具体步骤为:
光催化反应在特制反应器中进行,该反应器分别含有实施例1~4 中的催化剂50mg,纯水15mL,将反应器用纯CO2气体充气和放气三次,三次过后向反应器中通入CO2至反应器内压力为80kPa,然后反应器在氙灯下以600rpm的搅拌下照射,循环水控制体系温度为20℃。反应器中的气体每隔1h向气相色谱进一次样以测定产物的量。
实施例6:
一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物在光催化二氧化碳还原中的应用,具体步骤为:
光催化反应在特制反应器中进行,该反应器分别含有实施例1~4 中的催化剂50mg,纯水15mL,三乙胺5mL,将反应器用纯CO2气体充气和放气三次,三次过后向反应器中通入CO2至反应器内压力为 80kPa,然后反应器在氙灯下以600rpm的搅拌下照射,循环水控制体系温度为20℃。反应器中的气体每隔1h向气相色谱进一次样以测定产物的量。
实施例7:
一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物在光催化二氧化碳还原中的应用,具体步骤为:
光催化反应在特制反应器中进行,该反应器含有实施例1~4中的催化剂50mg,纯水10mL,三乙醇胺20mL,乙腈30mL,将反应器用纯CO2气体充气和放气三次,三次过后向反应器中通入CO2至反应器内压力为80kPa,然后反应器在氙灯下以600rpm的搅拌下照射,循环水控制体系温度为20℃。反应器中的气体每隔1h向气相色谱进一次样以测定产物的量。
首先将实施例1-4所得的聚合物材料对二氧化碳的吸附性能进行评估,如图3所示,从图3中可以看出,金属化后的共价三嗪聚合物对二氧化碳拥有良好的吸附性能,这将有利于材料对二氧化碳的进一步活化,进而促进光催化反应的顺利进行。实施例5-7是对材料在不同体系下光催化二氧化碳还原性能的测试,结合图4可以看出,材料在6h内能保持良好稳定的光催化二氧化碳还原性能,且本发明中的高密度金属化共价三嗪材料与文献中同类型的材料在催化体系相同的条件下,本发明的催化性能更优越。
以上所述仅为本发明的代表实施例,凡是依据本发明申请专利范围内所做的修改和替代,皆应属于本发明的涵盖范围。
Claims (10)
2.一种根据权利要求1所述的共价三嗪聚合物或金属化的共价三嗪聚合物的制备方法,其特征在于以含氰基卟啉与2-氰基嘧啶或其衍生物为原料,以三氟甲磺酸为催化剂,以三氯甲烷为溶剂,氮气保护下,于一定温度下进行氰基环化反应生成三嗪环,得到共价三嗪聚合物;所得共价三嗪聚合物与金属盐在溶剂中加热,金属离子与聚合物配位,得到高密度金属化的共价三嗪聚合物。
3.根据权利要求2所述的共价三嗪聚合物或金属化的共价三嗪聚合物的制备方法,其特征在于含氰基卟啉和2-氰基嘧啶或其衍生物单体比例为1:0.1~10。
4.根据权利要求2所述的共价三嗪聚合物或金属化的共价三嗪聚合物的制备方法,氰基环化反应的温度为-5~10℃。
5.根据权利要求2所述的共价三嗪聚合物或金属化的共价三嗪聚合物的制备方法,其特征在于具体包括如下步骤:
1)在氮气保护下,将含氰基卟啉与2-氰基嘧啶或其衍生物溶解于三氯甲烷形成溶液A;
2)在氮气氛围下,0℃下将三氟甲磺酸溶解于三氯甲烷形成溶液B;
3)在氮气氛围下,保持搅拌,利用注射器将溶液A逐滴滴加至溶液B,并在-5~10℃搅拌反应2~4h,再将反应混合物升温至室温,并在室温下继续反应10~13h;
4)步骤3)反应结束后,加氨水中和混合物至中性,并搅拌1.5~2.5h,过滤得到紫色有光泽的粗产物,依次用二氯甲烷、丙酮洗涤过滤,洗至滤液为无色,最后在75~85℃下干燥11~13h,得到共价三嗪聚合物;
5)步骤4)得到的共价三嗪聚合物和金属盐加至三颈烧瓶,在氮气保护下,用注射器加入合适的溶剂,搅拌升温回流反应8~30h;
6)反应结束后,冷却至室温,过滤除去溶剂得到粗产物,用溶剂洗涤过滤,直至滤液为无色,最后在75~85℃下真空干燥11~13h,得到高密度金属化的共价三嗪聚合物。
6.根据权利要求2所述的共价三嗪聚合物或金属化的共价三嗪聚合物的制备方法,其特征在于2-氰基嘧啶的衍生物包括2-氰基-5-溴基嘧啶、2-氰基-5-氨基嘧啶、2-氰基-5-甲基嘧啶或2-氰基-5-羧基嘧啶;含氰基卟啉为5,10,15,20-四(4-氰基苯基)卟啉或5,10,15,20-四(3-氰基苯基)卟啉。
7.根据权利要求5所述的共价三嗪聚合物或金属化的共价三嗪聚合物的制备方法,步骤5)中的溶剂为N,N-二甲基甲酰胺、乙腈或苯甲腈,溶剂投入比为15-25mL/克固体,固体量是指共价三嗪聚合物和金属盐的总量。
8.根据权利要求5所述的共价三嗪聚合物或金属化的共价三嗪聚合物的制备方法,步骤5)中的溶剂投入比为20mL/克固体。
9.根据权利要求5所述的共价三嗪聚合物或金属化的共价三嗪聚合物的制备方法,其特征在于步骤5)中的金属盐为CuCl2、CoCl2、FeCl2、PtCl2、PdCl2或NiCl2。
10.根据权利要求1所述的一种共价三嗪聚合物或金属化的共价三嗪聚合物在光催化CO2还原中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111005664.3A CN113717382B (zh) | 2021-08-30 | 2021-08-30 | 一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111005664.3A CN113717382B (zh) | 2021-08-30 | 2021-08-30 | 一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113717382A CN113717382A (zh) | 2021-11-30 |
CN113717382B true CN113717382B (zh) | 2022-08-19 |
Family
ID=78679315
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111005664.3A Active CN113717382B (zh) | 2021-08-30 | 2021-08-30 | 一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113717382B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114790286A (zh) * | 2022-03-30 | 2022-07-26 | 绍兴文理学院 | 一种共价三嗪框架聚合物微球的制备方法 |
CN117659432B (zh) * | 2024-02-01 | 2024-04-02 | 四川大学 | 一种多孔镍卟啉基氢键有机框架材料及其制备方法与应用 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014172825A (ja) * | 2013-03-06 | 2014-09-22 | Tokyo Univ Of Science | 環状ポルフィリン多量体及びその製造方法 |
CN103934026B (zh) * | 2014-04-30 | 2016-01-06 | 浙江大学 | 一种多孔金属卟啉有机共价聚合材料及其制备方法与用途 |
CN107335458B (zh) * | 2017-07-06 | 2019-10-01 | 华东师范大学 | 一种氮掺杂碳或铁氮磷共掺杂碳电催化材料的制备方法 |
CN110615793A (zh) * | 2019-10-04 | 2019-12-27 | 吉林工程技术师范学院 | 一种金属卟啉配合物及其有机电致发光器件 |
-
2021
- 2021-08-30 CN CN202111005664.3A patent/CN113717382B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN113717382A (zh) | 2021-11-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Photosensitizing single-site metal− organic framework enabling visible-light-driven CO2 reduction for syngas production | |
CN113717382B (zh) | 一种基于卟啉和嘧啶的高密度金属化的共价三嗪聚合物及其制备方法和应用 | |
CN112159517B (zh) | 朝格尔碱基共轭微孔聚合物光催化剂及其制备方法和应用 | |
CN110746601A (zh) | 一种卟啉基聚吡咯共轭微孔聚合物及其制备方法 | |
CN111151285B (zh) | 一种氮掺杂多孔碳负载ZnS纳米复合材料及其制备方法和应用 | |
CN112521263A (zh) | 一种MOF担载的Ir配合物催化CO2加氢还原制备甲酸盐/甲酸的方法 | |
CN111286024B (zh) | 一种咪唑功能化的共价三嗪框架材料及其制备方法和应用 | |
CN114797942A (zh) | 一种多孔金属(铁、镍、钴)掺杂石墨相氮化碳光催化剂及其制备方法和应用 | |
CN111171331B (zh) | 一种卟啉-蒽基共价有机框架材料及其制备方法和应用 | |
CN108080036B (zh) | 一种基于光敏性金属-有机配位纳米笼与二氧化钛的杂化材料及其制备方法和应用 | |
CN114308132A (zh) | 一种质子化的CdS-COF-366-M复合光催化剂及其制备方法 | |
CN114177940A (zh) | 一种单原子Cu锚定共价有机框架材料的制备及其应用 | |
CN107540660B (zh) | 一种以三联吡啶衍生物为配体的铁配合物及其合成方法和应用 | |
CN111330612A (zh) | 氮空位氧掺杂的空心多孔棱柱状氮化碳及其应用 | |
CN113231101A (zh) | 一种Cu-NM-101(Fe)光催化剂的制备及应用 | |
CN114573086B (zh) | 一种SEP@CTFs复合材料在可见光下催化降解水体中低浓度抗生素的方法 | |
CN114713264B (zh) | 氯酚和二氧化碳在氮化碳纳米管上的光催化羧基化转化 | |
CN114471727B (zh) | 一种Au@NH2-MIL-125(Cu/Ti)光催化剂及其制备方法和应用 | |
CN113751075B (zh) | 一种高效催化co2还原的m1m2-双齿配体/cof-5双原子催化剂及其制备方法 | |
CN116120505A (zh) | 一类含卤素芘基共价有机框架聚合物光催化剂及其制备方法和应用 | |
CN111153937A (zh) | 一种钴金属有机大环状化合物的制备方法及其应用 | |
CN113908873B (zh) | 一种利用氮化碳基光催化剂光催化选择性氧化葡萄糖的方法 | |
CN109701658A (zh) | 一种基于光敏性金属-有机配位纳米笼与类石墨相氮化碳的杂化材料及其制备方法和应用 | |
CN116284818B (zh) | 一种光敏Co-MOF材料及其制备方法和应用 | |
CN115926189B (zh) | 一种复合材料hkust-1@pq及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |