CN112159517B - 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 - Google Patents
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 Download PDFInfo
- Publication number
- CN112159517B CN112159517B CN202010883151.1A CN202010883151A CN112159517B CN 112159517 B CN112159517 B CN 112159517B CN 202010883151 A CN202010883151 A CN 202010883151A CN 112159517 B CN112159517 B CN 112159517B
- Authority
- CN
- China
- Prior art keywords
- microporous polymer
- conjugated microporous
- base
- troger
- reaction
- 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
- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011941 photocatalyst Substances 0.000 title description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 13
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 7
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005691 oxidative coupling reaction Methods 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000002585 base Substances 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000000944 Soxhlet extraction Methods 0.000 description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- SXPSZIHEWFTLEQ-UHFFFAOYSA-N tröger's base Chemical compound C12=CC=C(C)C=C2CN2C3=CC=C(C)C=C3CN1C2 SXPSZIHEWFTLEQ-UHFFFAOYSA-N 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZDRMMTYSQSIGRY-UHFFFAOYSA-N 1,3,5-triethynylbenzene Chemical compound C#CC1=CC(C#C)=CC(C#C)=C1 ZDRMMTYSQSIGRY-UHFFFAOYSA-N 0.000 description 1
- MVLGANVFCMOJHR-UHFFFAOYSA-N 1,4-diethynylbenzene Chemical compound C#CC1=CC=C(C#C)C=C1 MVLGANVFCMOJHR-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/132—Morphological aspects branched or hyperbranched
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3328—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms alkyne-based
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
- C08G2261/354—Macromonomers, i.e. comprising more than 10 repeat units containing hetero atoms
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/415—Sonogashira / Hagihara reactions
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/43—Chemical oxidative coupling reactions, e.g. with FeCl3
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/59—Stability
- C08G2261/598—Chemical stability
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明公开了一种朝格尔碱基共轭微孔聚合物及其制备方法,该材料以二碘代朝格尔碱以及咔唑或芳香族二炔、三炔化合物为原料,通过氧化偶联或Sonogashira偶联共聚反应制备而成。该共轭微孔聚合物具有V型刚性骨架结构,物理、化学稳定性高,气体吸附能力强,比表面积大,可见光吸收能力强,可应用于光催化污染物降解、水分解和CO2还原领域。
Description
技术领域
本发明属于光电功能材料技术领域,具体涉及一种朝格尔碱基共轭微孔聚合物、制备方法及其光催化应用。
背景技术
共轭微孔聚合物的有机骨架完全由苯环、碳-碳三键以π电子共轭形式连接,为其在光电、储能和传感等领域的应用提供了基础。自2007年Cooper报道了第一个基于聚芳炔的共轭微孔聚合物至今,众多具有不同结构和性质的共轭微孔聚合物被不断地开发出来。虽然该类材料不具有长程序性,由于其合成的反应条件比较温和,非常适合使用功能化单体构建功能化的新型共轭微孔聚合物,通过改变共轭结构之间链接的长度或共轭单体的构型可以有效实现孔结构与比表面积的调节。专利CN110394187A公开了一种氮、铁掺杂共轭微孔碳材料的制备方法及其应用,该材料制备简单,便于控制,具有较好的氧还原催化活性。然而,该材料主要用作燃料电池正极,且以金属元素为催化活性位点。专利CN109942570A公开了一种基于吩噻嗪的共轭微孔聚合物,并将该材料用于吲哚的光催化有氧硒化,但该共轭微孔聚合物主要体现为紫外吸收,对可见光的吸收利用不足。
发明内容
本发明的目的是提供一种朝格尔碱基共轭微孔聚合物及其制备方法,该聚合物制备工艺简单,结构可控,具有较高的比表面积和良好的可见光响应性,可应用于光催化污染物降解、水分解、CO2还原转换等多个领域。
实现本发明目的的技术解决方案是:一种朝格尔碱基共轭微孔聚合物,具有式I或II结构:
较佳的,所述的朝格尔碱基共轭微孔聚合物,其特征在于,所述的聚合物是粉末状,孔径分布范围主要在0.5~2nm。
较佳的,具有式I结构的朝格尔碱基共轭微孔聚合物的制备方法:配置0.1~0.2mol/L的二碘代朝格尔碱的N,N-二甲基甲酰胺溶液,以二碘代朝格尔碱与咔唑的摩尔比为1:4,将咔唑加入上述二碘代朝格尔碱溶液,以二碘代朝格尔碱与碳酸钾,碘化亚铜和1,10-菲咯啉的摩尔比为100:400:10:1,将碳酸钾,碘化亚铜和1,10-菲咯啉分散入上述溶液,氮气保护,150℃反应24h,冷却至室温,除去溶剂,通过柱层析(乙酸乙酯/石油醚=1:3)纯化产物,得到咔唑基共轭微孔聚合物单体。配置0.009~0.01mol/L的咔唑基共轭微孔聚合物单体的氯仿溶液,以咔唑基共轭微孔聚合物单体与FeCl3的摩尔比为1:10,将FeCl3加入到上述咔唑基共轭微孔聚合物单体的氯仿溶液中,氮气保护,60℃反应24h,然后向反应混合物中加入50mL甲醇,所得混合物再搅拌1小时,过滤收集沉淀物,依次用甲醇,二氯甲烷和丙酮洗涤。将该沉淀物用盐酸处理2小时,过滤,并依次用水、甲醇,二氯甲烷和丙酮洗涤。采用甲醇和四氢呋喃的混合溶液进行索氏提取,纯化24h,干燥,得到共轭微孔聚合物。
较佳的,具有式I结构的朝格尔碱基共轭微孔聚合物的制备方法:以N,N-二甲基甲酰胺和三乙胺体积比1:1的混合溶剂为介质,配置0.1~0.15mol/L的二碘代朝格尔碱溶液,以二碘代朝格尔碱与1,3,5-三乙炔基苯的摩尔比为1.5:1,加入三炔基单体,以二碘代朝格尔碱与Pd(pph3)4和CuI的摩尔比为30:1:1,将Pd(pph3)4和CuI分散入上述溶液,氮气保护下,80℃反应24h,进行Sonogashira偶联反应,收集反应后的沉淀物,将沉淀物在盐酸中搅拌1h,水洗,再在丙酮,甲苯,甲醇的混合溶液中搅拌1h,干燥,用甲醇和四氢呋喃的混合溶液进行索氏提取,得到共轭微孔聚合物。
较佳的,具有式II结构的朝格尔碱基共轭微孔聚合物的制备方法:以N,N-二甲基甲酰胺和三乙胺体积比1:1的混合溶剂为介质,配置0.1~0.15mol/L的二碘代朝格尔碱溶液,以二碘代朝格尔碱与1,4-二乙炔基苯的摩尔比为1.5:1,加入二炔基单体,以二碘代朝格尔碱与Pd(pph3)4和CuI的摩尔比为30:1:1,将Pd(pph3)4和CuI分散入上述溶液,氮气保护下,80℃反应24h,进行Sonogashira偶联反应,收集反应后的沉淀物,将沉淀物在盐酸中搅拌1h,水洗,再在丙酮,甲苯,甲醇的混合溶液中搅拌1h,干燥,用甲醇和四氢呋喃的混合溶液进行索氏提取,得到共轭微孔聚合物。
本发明还提供了上述朝格尔碱基共轭微孔聚合物的应用,所述的共轭微孔聚合物应用于光催化CO2还原反应中。
与现有技术相比,本发明的有益效果是:
(1)本发明的共轭微孔聚合物基于具有V型骨架结构的朝格尔碱,具有较大的比表面积和良好的物理、化学稳定性。
(2)本发明的基于朝格尔碱的共轭微孔聚合物具有优异的CO2吸附能力,在光催化CO2还原转换中,具有较高的反应物吸附和活化能力。
(3)本发明的基于朝格尔碱的共轭微孔聚合物具有较窄带隙,可见光吸收能力强,因此具有较大的应用潜力。
下面结合附图对本发明作进一步详细描述。
附图说明
图1为实施例1所制备共轭微孔聚合物的红外光谱图。
图2为实施例1所制备共轭微孔聚合物的13C固体核磁谱图。
图3为实施例1所制备共轭微孔聚合物的光催化CO2还原性能。
图4为实施例1所制备共轭微孔聚合物的扫描电镜图。
图5为实施例2所制备共轭微孔聚合物的红外光谱图。
图6为实施例2所制备共轭微孔聚合物的13C固体核磁谱图。
图7为实施例2所制备共轭微孔聚合物的光催化CO2还原性能。
图8为实施例3所制备共轭微孔聚合物的红外光谱图。
图9为实施例3所制备共轭微孔聚合物的13C固体核磁谱图。
图10为实施例3所制备共轭微孔聚合物的光催化CO2还原性能。
图11为实施例3所制备共轭微孔聚合物的紫外-可见漫反射光谱。
具体实施方式
下面的实施例可以使本专业技术人员更全面地理解本发明。
朝格尔碱是一个有百年研究历史的化合物,其衍生物都具有类似的V型分子框架,分子中心为亚甲基二氮芳辛桥,芳香烃分别连接在二氮芳辛桥中心两侧。之前,人们对朝格尔碱的关注主要集中于分子识别,手性催化、主客体化学等方面。最近,朝格尔碱骨架在电子转移、推拉方面的效应被应用于新型固态荧光和非线性光学活性材料,其V型刚性结构被用于多孔有机聚合物的构建。此外,由于氮元素存在而带来的碱性特质,朝格尔碱基材料在CO2分离和储存方面显示出巨大优势。因此,将朝格尔碱结构引入聚合物骨架,协同共轭基元扩展构筑共轭微孔聚合物,将在光催化污染物降解、分解水产氢产氧、CO2还原转换等领域发挥巨大应用价值。
实施例1
本实施例的反应方程式如下:
将2.369g二碘代朝格尔碱(5.0mmol)溶于40mL无水N,N-二甲基甲酰胺,依次加入3.344g咔唑(20mmol),2.764g碳酸钾(20mmol),0.095g碘化亚铜(0.5mmol)和0.009g 1,10-菲咯啉(0.05mmol),氮气保护,150℃反应24h。冷却至室温,除去溶剂,通过柱层析(乙酸乙酯/石油醚=1:3)纯化产物,得到淡棕色咔唑基共轭微孔聚合物单体。
将0.203g(0.367mmol)咔唑基共轭微孔聚合物单体分散在25mL无水氯仿中,然后加入0.595g(3.67mmol)氯化铁,氮气保护下,60℃反应24h。然后向反应混合物中加入50mL甲醇,所得混合物再搅拌1小时,过滤收集沉淀物,依次用甲醇,二氯甲烷和丙酮洗涤。将该沉淀物用盐酸处理2小时,过滤,并依次用水、甲醇,二氯甲烷和丙酮洗涤。采用甲醇和四氢呋喃的混合溶液进行索氏提取,纯化24h。干燥,得到土黄色粉末状共轭微孔聚合物。
图1为实施例1所制备的共轭微孔聚合物的红外光谱图。其中在1318cm-1和1060cm-1处为环外C-N的伸缩振动吸收峰,此为朝格尔碱结构中桥联结构上的碳氮键,1400-1720cm-1为共轭微孔聚合物结构中苯环骨架的特征吸收峰。
图2为实施例1所制备共轭微孔聚合物的13C固体核磁谱图。在58ppm处为中间桥联骨架上C-N键的出峰位置,表明结构中朝格尔碱的存在,在128ppm处为咔唑上苯环结构的三取代基的位置,表明材料的成功聚合。
图3为实施例1所制备共轭微孔聚合物的光催化CO2还原性能。6h的产量为424μmolg-1h-1。
图4为实施例1所制备共轭微孔聚合物的扫描电镜图,可以看出微观结构为絮状结构。
实施例2
本实施例的反应方程式如下:
以20ml N,N-二甲基甲酰胺和20ml三乙胺混合溶液为反应介质,加入0.356g二碘代朝格尔碱(0.75mmol),0.075g 1,3,5-三乙炔基苯(0.5mmol),0.029g Pd(pph3)4(0.025mmol)和0.005g CuI(0.025mmol),氮气保护下,80℃反应24h。收集反应后的沉淀物,将沉淀物在盐酸溶液中搅拌1h后,水洗,再在丙酮,甲苯,甲醇的混合溶液中搅拌1h,干燥,用甲醇和四氢呋喃的混合溶液进行索氏提取,得到黄色粉末状共轭微孔聚合物。
图5为实施例2所制备共轭微孔聚合物的红外光谱图。其中在1316cm-1和1097cm-1处为环外C-N的伸缩振动吸收峰,此为朝格尔碱结构中桥联结构上的碳氮键,1400-1720cm-1为共轭微孔聚合物结构中苯环骨架的特征吸收峰,在2190cm-1处为结构中炔基的特征峰。
图6为实施例2所制备共轭微孔聚合物的13C固体核磁谱图。在57ppm与65ppm处为中间桥联骨架上C-N键的出峰位置,表明结构中朝格尔碱的存在,在87ppm处为咔唑上苯环结构的三取代基的位置。
图7为实施例2所制备共轭微孔聚合物的光催化CO2还原性能。6h的产量为761μmolg-1h-1。
实施例3
本实施例的反应方程式如下:
以20ml N,N-二甲基甲酰胺和20ml三乙胺混合溶液为反应介质,加入0.356g二碘代朝格尔碱(0.75mmol),0.063g 1,4-二乙炔基苯(0.5mmol),0.029g Pd(pph3)4(0.025mmol)和0.005g CuI(0.025mmol),氮气保护下,80℃反应24h。收集反应后的沉淀物,将沉淀物在盐酸溶液中搅拌1h后,水洗,再在丙酮,甲苯,甲醇的混合溶液中搅拌1h,干燥,用甲醇和四氢呋喃的混合溶液进行索氏提取,得到黄色粉末状共轭微孔聚合物。
图8为实施例3所制备共轭微孔聚合物的红外光谱图。其中在1316cm-1和1097cm-1处为环外C-N的伸缩振动吸收峰,此为朝格尔碱结构中桥联结构上的碳氮键,1400-1720cm-1为共轭微孔聚合物结构中苯环骨架的特征吸收峰,在2190cm-1处为结构中炔基的特征峰。
图9在57ppm与65ppm处为中间桥联骨架上C-N键的出峰位置,表明结构中朝格尔碱的存在,在89ppm处为咔唑上苯环结构的三取代基的位置。
图10为实施例3所制备共轭微孔聚合物的光催化CO2还原性能。6h的产量为346μmol g-1h-1。
图11为实施例3所制备共轭微孔聚合物的紫外-可见漫反射光谱,该材料在波长200-650nm之间都有良好的吸收,吸收范围延伸到可见光区域。
Claims (6)
2.一种如权利要求1所述的朝格尔碱基共轭微孔聚合物,其特征在于,所述的聚合物是粉末状,孔径分布范围主要在0.5~2nm。
4.如权利要求3所述的方法,其特征在于,步骤(1)中,二碘代朝格尔碱与咔唑的摩尔比为1:4;二碘代朝格尔碱与碘化亚铜的摩尔比为10:1;反应温度为150℃,反应在氮气保护下进行。
5.如权利要求3所述的方法,其特征在于,步骤(2)中,单体与FeCl3的摩尔比为1:10;
反应温度为60℃,反应在氮气保护下进行。
6.一种如权利要求1所述的朝格尔碱基共轭微孔聚合物在光催化还原CO2中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010883151.1A CN112159517B (zh) | 2020-08-28 | 2020-08-28 | 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 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010883151.1A CN112159517B (zh) | 2020-08-28 | 2020-08-28 | 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 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112159517A CN112159517A (zh) | 2021-01-01 |
CN112159517B true CN112159517B (zh) | 2022-09-27 |
Family
ID=73860342
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010883151.1A Active CN112159517B (zh) | 2020-08-28 | 2020-08-28 | 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 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112159517B (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109988306B (zh) * | 2019-04-23 | 2021-04-30 | 湘潭大学 | 苯并噁唑连接三苯基咪唑的聚合物及其制备方法和用途 |
CN113416299B (zh) * | 2021-07-02 | 2023-06-09 | 河南科技学院 | 侧链悬挂生物碱基的有机共轭聚合物光催化剂 |
CN114106296B (zh) * | 2021-11-29 | 2023-10-17 | 吉林大学 | 基于4-三苯代甲基苯胺的Troger′s base构筑的PAF-102s及其应用 |
CN115926118A (zh) * | 2022-11-22 | 2023-04-07 | 宁夏大学 | 一种钯/共轭微孔聚合物的制备方法及其应用 |
CN116284967B (zh) * | 2023-03-22 | 2024-07-23 | 四川大学 | Tröger’s Base连接的多孔有机聚合物凝胶及其制备和应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104926819A (zh) * | 2015-05-15 | 2015-09-23 | 江苏师范大学 | 2,8-二芳基(氨基)朝格尔碱衍生物的合成方法 |
-
2020
- 2020-08-28 CN CN202010883151.1A patent/CN112159517B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104926819A (zh) * | 2015-05-15 | 2015-09-23 | 江苏师范大学 | 2,8-二芳基(氨基)朝格尔碱衍生物的合成方法 |
Non-Patent Citations (3)
Title |
---|
"Novel 6FDA-based polyimides derived from sterically hindered Troger"s base diamines: Synthesis and gas permeation properties";Ghanem Bader;《Polymer》;20160430;第96卷;第13-19页 * |
"Synthesis of metalloporphyrin-based conjugated microporous polymer spheres directed by bipyridine-type ligands";Ji Guipeng et al.;《Chemical Communications》;20151231;第51卷(第34期);第7352-7355页 * |
"Tro¨ ger’s base-functionalised organic nanoporous polymer for heterogeneous catalysis";Xin Du et al.;《Chemical Communications》;20091214;第46卷(第6期);第970-972页 * |
Also Published As
Publication number | Publication date |
---|---|
CN112159517A (zh) | 2021-01-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
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 | |
CN109867770B (zh) | 基于卟啉官能团的共轭微孔聚合物及其制备方法与应用 | |
CN103406150B (zh) | 一种高分子负载金属钯配合物催化剂及其制备方法和应用 | |
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 | |
CN110452365B (zh) | 一种共轭多孔聚合物及其制备方法与在光催化伯胺氧化制备亚胺的应用 | |
CN110280306B (zh) | 一种基于共轭多孔有机光催化剂高效分解水制氢的方法 | |
CN112961327B (zh) | 共价七嗪聚合物、其制备方法及产生过氧化氢的催化方法 | |
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 | |
CN102558555B (zh) | 一种含芴聚***耐高温紫外吸收剂及其制备方法 | |
CN114736356B (zh) | 用于光催化分解水制氢的二苯并稠二萘基聚合物光催化剂及其制备方法 | |
CN110227544B (zh) | 蜂巢结构卟啉COP与g-C3N4复合材料的合成及在光催化降解染料方面的应用 | |
CN114392774B (zh) | 一种聚合物负载协同催化剂的制备方法及其在二氧化碳光还原催化中的应用 | |
CN115286757B (zh) | 基于多氮烯烃连接的共价有机框架材料及其制备方法和应用 | |
CN101613339A (zh) | 合成碳酸乙烯酯的方法及催化剂 | |
CN110156988A (zh) | 一种菲并咪唑基三嗪聚合物及其制备方法和用途 | |
CN111871462B (zh) | 一种铁钴有机催化剂和其制备方法及其转化co2合成苯并氮杂环的应用 | |
Sobarzo et al. | Effect of thiophene, furan moieties and zinc ions on melamine-based porous polyaminals properties and catalytic activity on CO2 cycloaddition reaction | |
CN109942570B (zh) | 一种基于吩噻嗪的共轭微孔聚合物、制备方法和高效催化应用 | |
CN110642745B (zh) | 一种光催化胺氧化偶联制备亚胺的方法 | |
WO2021186459A1 (en) | An improved process for photocatalytic hydrocarboxylation of methanol with co2 to produce acetic acid | |
CN113413900A (zh) | 基于聚氮化碳的共聚物及其制备方法和应用 | |
CN113355688A (zh) | 一种电催化还原CO2的Cu-MOF材料及其制备方法 | |
CN114805797B (zh) | 一种含氮杂环的共轭多孔有机聚合物及制备方法和应用 | |
CN113735746B (zh) | 一种2-硝基-4-甲砜基苯甲酸的制备方法 | |
CN116474826A (zh) | 一种聚苯胺负载钯纳米粒子催化剂的制备方法及应用 |
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 |