CN111013656A - Synthetic method of tetrazine hypercrosslinked porous photocatalyst - Google Patents
Synthetic method of tetrazine hypercrosslinked porous photocatalyst Download PDFInfo
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- CN111013656A CN111013656A CN201911378182.5A CN201911378182A CN111013656A CN 111013656 A CN111013656 A CN 111013656A CN 201911378182 A CN201911378182 A CN 201911378182A CN 111013656 A CN111013656 A CN 111013656A
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- tetrazine
- porous photocatalyst
- hypercrosslinked porous
- hypercrosslinked
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- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000013315 hypercross-linked polymer Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 14
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 10
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 239000012039 electrophile Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 25
- 239000007787 solid Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- -1 nitrogen-nitrogen heterocyclic compound Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 1
- HTJMXYRLEDBSLT-UHFFFAOYSA-N 1,2,4,5-tetrazine Chemical group C1=NN=CN=N1 HTJMXYRLEDBSLT-UHFFFAOYSA-N 0.000 description 1
- DMSHUVBQFSNBBL-UHFFFAOYSA-N 5-bromopyridine-2-carbonitrile Chemical compound BrC1=CC=C(C#N)N=C1 DMSHUVBQFSNBBL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- RCYFOPUXRMOLQM-UHFFFAOYSA-N pyrene-1-carbaldehyde Chemical compound C1=C2C(C=O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 RCYFOPUXRMOLQM-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- 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
-
- B01J35/60—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
-
- 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
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
Abstract
The invention discloses a synthetic method of a tetrazine type hypercrosslinked porous photocatalyst, which comprises the following steps: putting a precursor methoxy-substituted bipyridine tetrazine monomer, an aromatic block and a catalyst ferric trichloride into a dry two-neck flask, adding a solvent 1, 2-dichloroethane and a crosslinking agent dimethoxymethane under the protection of nitrogen, stirring at a low temperature of 45 ℃ for 5-24h, heating to 90 ℃, continuing to react for 19-48 h, and after the reaction is finished, treating with methanol and concentrated hydrochloric acid, carrying out vacuum filtration, Soxhlet extraction and drying to obtain the tetrazine type hypercrosslinked porous photocatalyst TZ-HCPs. The TZ-HCPs catalyst obtained by the method has small density, larger specific surface area and wide visible light absorption range, can efficiently catalyze the coupling reaction between o-phenylenediamine and electrophilic reagents such as p-chlorobenzaldehyde and the like under the conditions of room temperature, air atmosphere and visible light illumination, and has good reusability.
Description
Technical Field
The invention relates to the technical field of organic synthesis and functional materials, in particular to synthesis of a tetrazine super-crosslinked porous photocatalyst and application thereof in the field of photocatalysis.
Background
In the face of the current energy and environmental crisis challenges, photocatalysis is receiving increasing attention with its mild and efficient reaction rates and greening of the reaction. Since the last 70 s, scientists have developed various inorganic semiconductor materials (photosensitizers or photocatalysts) based on elements such as titanium, gallium, cadmium, zinc, tungsten, etc. However, due to the structural limitation of inorganic substances, such substances have high toxicity, narrow absorption range of visible light, wide forbidden band gap, low utilization efficiency of sunlight, and poor selectivity in catalyzing the synthesis of organic substances. In contrast, organic dyes such as porphyrins are widely available, and have more excellent optical activity, suitable forbidden band width, and easily adjustable structural properties. Scientists have realized the simple synthesis of a series of homogeneous catalysts according to the important effect that organic dyes play in the processes such as breaking, recombining, weaving of chemical bond. Thus, the discovery and application of organic dyes has greatly driven the development of photocatalysis. However, it is noted that these homogeneous catalysts are difficult to separate from the product, difficult to recycle, and some are very expensive. Therefore, it is necessary to develop a heterogeneous catalyst which is cheap in price, easy to prepare and adjust, recyclable, excellent in performance, capable of fully utilizing visible light and appropriate in forbidden band gap, and thus it is possible to widely realize industrialization of photocatalysis.
Ultra-high cross-linked polymers (HCPs) are an emerging class of organic porous materials connected by covalent bonds. Compared with traditional inorganic materials (such as molecular sieve and activated carbon) and other porous materials, the HCPs have multiple connection modes and functional monomers, stronger designability, simpler synthesis, larger specific surface area and small density (generally only C, H, O, N and other elements). HCPs have a rigid structure and a large pi-conjugated system, which provides a structural basis for pore formation, catalytic site exposure, light absorption, and electron transfer. In addition, HCPs also have better stability than some organic-inorganic hybrid materials (such as ordered mesoporous silicones and metal organic frameworks) due to their formation by strong covalent bonds. In addition, the ultraviolet-visible light absorption range of the material is generally wider than that of an inorganic semiconductor, the forbidden band gap is narrower, and the visible light utilization rate is higher. Thus, HCPs have unique advantages as photocatalysts, combining their optoelectronic properties with their heterogeneous catalytic properties.
The 1,2,4, 5-tetrazine unit can be regarded as a heterocyclic compound in which 4 methine groups (-CH ═ on a benzene ring are substituted by 4 tertiary amino groups (-N ═) and the molecular formula is C2H2N4The nitrogen element accounts for 68.3 percent by mass, the hydrocarbon element accounts for 29.3 percent by mass and 2.5 percent by mass respectively, and the nitrogen-nitrogen heterocyclic compound is a typical high nitrogen heterocyclic compound. The electronegativity of nitrogen is larger, the electron cloud on the ring is biased towards the nitrogen, under the action of an induction effect, the electron deficiency degree on the ring is larger, and carbon atoms have more positive charges, so that the nucleophilic substitution reaction is facilitated. Meanwhile, the tetrazine unit has good rigidity and a large pi conjugated system, and is beneficial to constructing an organic porous material. By combining the characteristics, the tetrazine unit is introduced into the HCPs to synthesize the HCPs material taking the tetrazine unit as a precursor, and the method has important significance in the aspect of functionalizing the HCPs material.
In conclusion, the invention provides a synthesis method of a tetrazine hypercrosslinked porous photocatalyst, which realizes that tetrazine units are introduced into HCPs materials, and the obtained materials are used for synthesizing benzimidazole compounds.
Disclosure of Invention
In order to overcome the difficulty of the application of HCPs in functionalization, the invention aims to provide a synthetic method of a tetrazine type hypercrosslinked porous photocatalyst. The adopted specific technical scheme is as follows:
a synthetic method of a tetrazine hypercrosslinked porous photocatalyst comprises the following steps: putting a precursor methoxy-substituted bipyridine tetrazine monomer, an aromatic block and a catalyst ferric trichloride into a dry two-neck flask, adding a solvent 1, 2-dichloroethane and a crosslinking agent dimethoxymethane under the protection of nitrogen, stirring at a low temperature of 45 ℃ for 5-24h, heating to 90 ℃, continuing to react for 19-48 h, and after the reaction is finished, treating with methanol and concentrated hydrochloric acid, carrying out vacuum filtration, Soxhlet extraction and drying to obtain the tetrazine type hypercrosslinked porous photocatalyst TZ-HCPs.
Further, the molar ratio of the methoxy substituted bipyridine tetrazine monomer to the aromatic building block is 1:0-50, and the molar ratio of the methoxy substituted bipyridine tetrazine monomer to the aromatic building block is preferably 1: 20.
Further, the precursor concentration: the concentration of the methoxyl substituted bipyridine tetrazine monomer is 0.02-0.40 mmol/mL, and the concentration of the aromatic building block is 0.0-1.00 mmol/mL.
Further, the aromatic building blocks include, but are not limited to, benzene, fluorene.
Further, the volume ratio of the dimethoxymethane to the 1, 2-dichloroethane is 1:0-20, and the volume ratio of the dimethoxymethane to the 1, 2-dichloroethane is preferably 1: 6.
Further, the reaction temperature is 30-150 ℃, and preferably 45-90 ℃; the reaction time is 1-5 days, preferably 1-3 days.
Preferably, the heating operation is specifically that after stirring for 5h at the low temperature of 45 ℃, the temperature is increased to 90 ℃ again, and the reaction is continued for 19 h.
The new node unit of the TZ-HCP catalyst synthesized based on the methoxyl substituted bipyridine tetrazine monomer comprises but not limited to benzene, fluorene and other aromatic hydrocarbons.
The invention also aims to provide the tetrazine super-crosslinked porous photocatalyst prepared by the synthesis method.
The invention also provides application of the tetrazine hypercrosslinked porous photocatalyst in the aspect of catalytic photoreaction.
Further, the invention provides application of the tetrazine hypercrosslinked porous photocatalyst in catalyzing the coupling reaction between o-phenylenediamine and aldehyde electrophiles.
The tetrazine hypercrosslinked porous photocatalyst obtained by the synthesis method can be used for photocatalysis of coupling reaction between o-phenylenediamine and electrophiles such as p-chlorobenzaldehyde (such as benzaldehyde, propionaldehyde, 1-pyrene formaldehyde and the like), and synthesis of benzimidazole compounds is realized.
Compared with the prior art, the synthetic method of the oxazine super-crosslinked porous photocatalyst provided by the invention has the following beneficial effects:
1. the TZ-HCPs catalyst obtained by the synthesis method provided by the invention has small density (only containing carbon, hydrogen, oxygen and nitrogen elements), larger specific surface area and wide visible light absorption range;
2. the TZ-HCPs catalyst prepared by the invention can efficiently catalyze the coupling reaction between o-phenylenediamine and electrophiles such as p-chlorobenzaldehyde (such as benzaldehyde, propionaldehyde, 1-pyrene formaldehyde and the like) at room temperature, in an air atmosphere and under the illumination of visible light, realizes the synthesis of benzimidazole compounds, has good reusability, and can be used for at least 20 times.
Drawings
FIG. 1 shows the BET specific surface area test results of TZ-HCP1, TZ-HCP2@ A, TZ-HCP2@ B, TZ-HCP2@ C and TZ-HCP2@ D synthesized in the present invention.
FIG. 2 shows the nitrogen adsorption and desorption curves of TZ-HCP2@ B, TZ-HCP2@ C, TZ-HCP2@ D and TZ-HCP3 synthesized by the present invention.
FIG. 3 is a plot of pore size distribution of synthesized TZ-HCP2@ B, TZ-HCP2@ C, TZ-HCP2@ D and TZ-HCP 3.
FIG. 4 shows the solid NMR spectra of TZ-HCP2@ D and TZ-HCP3 synthesized by the present invention.
FIG. 5 is a Fourier infrared spectrum of TZ-HCP2@ C, TZ-HCP2@ D, TZ-HCP3 synthesized in accordance with the present invention, and starting material (III) which is a methoxy substituted bipyridyltetrazine.
FIG. 6 shows the thermograms of TZ-HCP2@ B, TZ-HCP2@ C, TZ-HCP2@ D and TZ-HCP3 synthesized by the present invention.
FIG. 7 is a catalytic test of the synthesized TZ-HCP2@ D of the present invention.
FIG. 8 is a cycle test of synthesized TZ-HCP2@ D of the present invention.
Detailed Description
To further illustrate the technical means adopted by the present invention and the effects thereof, the following detailed description is given with reference to the accompanying drawings and preferred embodiments of the present invention.
(1) Synthesis of Material precursors
The synthetic route is shown as formula (i):
the substrates benzene or fluorene and dimethoxymethane used in the invention are all products available in the market. The methoxy-substituted bipyridine tetrazine monomer can be prepared from 5- (4-methoxybenzene) -2-cyanopyridine, and the 5- (4-methoxybenzene) -2-cyanopyridine (ACSOmega2017,2,5666-5683.) can be obtained relatively easily by simple transformation according to a method reported in the literature. The synthesis method specifically comprises the following steps:
the first step is as follows: p-methoxyphenylboronic acid (996mg,6.55mmol), 5-bromo-2-cyanopyridine (1g,5.46mmol), potassium carbonate (2.26g,16.38mmol) and tetrakis (triphenylphosphine) palladium (500mg,0.43mmol) were placed in a dry flask, then 40mL of tetrahydrofuran and 20mL of aqueous solution were added to the flask, stirred at 80 ℃ for 5-24h under nitrogen, after which the tetrahydrofuran was removed in vacuo, extracted with dichloromethane (100mL), and column chromatographed to give a light yellow solid (I) in 98% yield.
The second step is that: 5- (4-methoxybenzene) -2-cyanopyridine (371.4mg,1.76mmol) and sulfur powder (28mg,0.88mmol) were placed in a dry flask and 2mL of ethanol were added, heated with stirring at 90 deg.C, 1mL of hydrazine hydrate was added under reflux, and then heating under reflux was continued for 5-24 h. Finally, the reaction system was cooled to 0 ℃ and filtered with suction, while washing with-30 ℃ glacial ethanol (20mL) to give a tan solid (II).
The third step: dispersing the solid (II) into 4mL of glacial acetic acid, adding sodium nitrite (0.40g,5.79mmol) in batches under stirring at room temperature, wherein a brownish red gas is generated during the addition of the sodium nitrite, and continuing stirring for 5-24h at room temperature after the addition is finished. And pouring the reaction system into saturated potassium carbonate solution (100mL), standing, filtering, washing with a large amount of water, and drying in an oven at 50 ℃ to obtain a mauve solid (III) with the yield of 34%.
(2) Synthesis of tetrazine hypercrosslinked porous photocatalyst (TZ-HCP)
The reaction formula is shown as the following formula (ii):
example 1
Methoxy-substituted bipyridine tetrazine monomer (165mg,0.37mmol) and ferric chloride (2.4g,14mmol) are placed in a dry two-neck flask, vacuum pumping is carried out for 3-5 times under the protection of nitrogen, then 7.4mL of 1, 2-dichloroethane is added into the flask through a needle tube, stirring is carried out for 0.5h at room temperature, 1.33mL of dimethoxymethane is added into the flask, stirring is carried out for 5h at the low temperature of 45 ℃, then the temperature is raised to 90 ℃ and reaction is continued for 19 h. And then adding 20mL of methanol into the flask, stirring for 0.5h at 90 ℃, carrying out vacuum filtration, washing with N, N-dimethylformamide and methanol, transferring the solid into the flask, adding 20mL of concentrated hydrochloric acid, stirring for 2h at room temperature, carrying out vacuum filtration, washing with N, N-dimethylformamide, methanol and dichloromethane in sequence, carrying out Soxhlet extraction on the residue for 48h (methanol: dichloromethane ═ 1:1), and drying in an oven to obtain 568mg of the tetrazine hypercrosslinked porous photocatalyst TZ-HCP1 (brown black solid powder).
Example 2
Putting a methoxy substituted bipyridine tetrazine monomer (179mg,0.4mmol) and ferric trichloride (520mg,3.2mmol) into a dry two-neck flask, vacuumizing for 3-5 times under the protection of nitrogen, then adding 1.6mL of 1, 2-dichloroethane and 0.11mL of benzene into the flask, stirring for 0.5h at room temperature, adding 0.29mL of dimethoxymethane into the flask, stirring for 5h at the low temperature of 45 ℃, heating to 90 ℃, and continuing to react for 19 h. The reaction system was vacuum filtered, washed sequentially with petroleum ether and acetone, the solid was transferred to a dry flask, 20mL of hydrochloric acid (6M) was added and stirred at room temperature for 2 h. Vacuum filtration, washing sequentially by N, N-dimethylformamide, methanol and dichloromethane, performing Soxhlet extraction on the crude product for 48h by using acetone as a solvent, and drying in an oven at 80 ℃ to obtain 241mg of the tetrazine hypercrosslinked porous photocatalyst TZ-HCP2@ A (black solid powder).
Example 3
Putting a methoxy-substituted bipyridine tetrazine monomer (103mg,0.23mmol) and ferric trichloride (464mg,2.86mmol) into a dry two-neck flask, vacuumizing for 3-5 times under the protection of nitrogen, then adding 1.43mL of 1, 2-dichloroethane and 0.11mL of benzene into the flask, stirring for 0.5h at room temperature, adding 0.26mL of dimethoxymethane into the flask, stirring for 5h at the low temperature of 45 ℃, heating to 90 ℃, and continuing to react for 19 h. The reaction system was vacuum filtered, washed sequentially with petroleum ether and acetone, the solid was transferred to a dry flask, 20mL of hydrochloric acid (6M) was added and stirred at room temperature for 2 h. Vacuum filtering, washing sequentially with N, N-dimethylformamide, methanol and dichloromethane, Soxhlet extracting the crude product with acetone as solvent for 48h, and drying in oven at 80 deg.C to obtain 214mg of tetrazine hypercrosslinked porous photocatalyst TZ-HCP2@ B (brown solid powder).
Example 4
Methoxy-substituted bipyridine tetrazine monomer (165mg,0.37mmol) and ferric chloride (2.40g,14mmol) were placed in a dry two-necked flask, evacuated 3-5 times under nitrogen, then 7.4mL of 1, 2-dichloroethane and 0.66mL of benzene were added to the flask, stirred at room temperature for 0.5h, then 1.33mL of dimethoxymethane was added to the flask, stirred at 45 ℃ for 24h, and then 7.4mL of 1, 2-dichloroethane was added. The temperature is increased to 90 ℃ and the reaction is continued for 48 h. The reaction system was vacuum filtered, washed sequentially with petroleum ether and acetone, the solid was transferred to a dry flask, 20mL of hydrochloric acid (6M) was added and stirred at room temperature for 2 h. Vacuum filtration, washing sequentially by N, N-dimethylformamide, methanol and dichloromethane, performing Soxhlet extraction on the crude product for 48h by using acetone as a solvent, and drying in an oven at 80 ℃ to obtain 977mg of the tetrazine hypercrosslinked porous photocatalyst TZ-HCP2@ C (reddish brown solid powder).
Example 5
Methoxy-substituted bipyridine tetrazine monomer (165mg,0.37mmol) and ferric chloride (2.4g,14mmol) are placed in a dry two-neck flask, vacuum is pulled for 3-5 times under the protection of nitrogen, then 7.4mL1, 2-dichloroethane and 0.66mL benzene are added into the flask through a needle tube, stirring is carried out for 0.5h at room temperature, 1.33mL dimethoxymethane is added into the flask, stirring is carried out for 5h at the low temperature of 45 ℃, then the temperature is raised to 90 ℃ and reaction is continued for 19 h. And then adding 20mL of methanol into the flask, stirring for 0.5h at 90 ℃, carrying out vacuum filtration, washing with N, N-dimethylformamide and methanol, transferring the solid into the flask, adding 20mL of concentrated hydrochloric acid, stirring for 2h at room temperature, carrying out vacuum filtration, washing with N, N-dimethylformamide, methanol and dichloromethane in sequence, carrying out Soxhlet extraction on the residue for 48h (methanol: dichloromethane ═ 1:1), and drying in an oven to obtain 880mg of the tetrazine hypercrosslinked porous photocatalyst TZ-HCP2@ D (red brown solid powder).
Example 6
Placing methoxy substituted bipyridine tetrazine monomer (82.50mg,0.18mmol), fluorene (612mg,3.68mmol) and ferric trichloride (1.20g,7.38mmol) in a dry two-neck flask, vacuumizing for 3-5 times under the protection of nitrogen, adding 3.7mL of 1, 2-dichloroethane into the flask through a needle tube, stirring for 0.5h at room temperature, adding 0.67mL of dimethoxymethane into the flask, stirring for 5h at the low temperature of 45 ℃, heating to 90 ℃, and continuing to react for 19 h. Then 20mL of methanol was added to the flask, stirred at 90 ℃ for 0.5h, vacuum filtered, washed with water, saturated sodium bicarbonate solution, N-dimethylformamide and methanol in that order, and the solid was transferred to the flask. Adding 20mL of concentrated hydrochloric acid, stirring at room temperature for 2h, carrying out vacuum filtration, washing sequentially with N, N-dimethylformamide, methanol and dichloromethane, carrying out Soxhlet extraction on the residue for 24h (methanol: dichloromethane ═ 1:1), and drying in an oven to obtain 798mg of the tetrazine hypercrosslinked porous photocatalyst TZ-HCP3 (solid powder in earthy yellow).
As shown in FIG. 1, the BET specific surface areas of the TZ-HCP1 and TZ-HCP2 materials obtained by the different methods were different. The specific surface areas of TZ-HCP1, TZ-HCP2@ A, TZ-HCP2@ B, TZ-HCP2@ C and TZ-HCP2@ D were 3.0m2/g、73.1m2/g、217.6m2/g、733.0m2/g、741.0m2The more the content of the monomer (III), the smaller the BET specific surface area. Among them, TZ-HCP2@ D has the largest specific surface area and the shortest synthesis time.
As shown in figure 2, the nitrogen adsorption and desorption curves show that the adsorption amounts of TZ-HCP2@ B, TZ-HCP2@ C, TZ-HCP2@ D and TZ-HCP3 to nitrogen are different. TZ-HCP2@ C, TZ-HCP2@ D and TZ-HCP3 showed better adsorption effect.
As shown in figure 3, the pore size distribution of TZ-HCP2@ B, TZ-HCP2@ C, TZ-HCP2@ D and TZ-HCP3 is calculated by the NLDFT method, wherein the pore size distribution of TZ-HCP2@ B is mainly about 4.1nm, the pore size distribution of TZ-HCP2@ C is mainly about 4.2nm, the pore size distribution of TZ-HCP2@ D is mainly about 4.2nm, and the pore size distribution of TZ-HCP3 is mainly about 4.1 nm.
Referring to FIG. 4, signals of 55ppm, 158ppm, 36(37) ppm, etc. can be seen through solid nuclear magnetic carbon spectrum, and they can be respectively assigned to methoxy, imine bond and methylene formed after cross-linking in the material. This shows that the bipyridine tetrazine monomer is successfully embedded into the organic porous material by Friedel-crafts alkylation reaction and methylene linkage.
As shown in fig. 5, by comparing the fourier ir spectra of TZ-HCP and the starting material, it can be seen that the ir spectrum of TZ-HCP is similar to that of starting material (III), and both have distinct C ═ N bond oscillation peaks, indicating that the tetrazine units were successfully incorporated into the HCP material.
As shown in FIG. 6, it was found by thermal analysis that TZ-HCP2@ B was stable to 295 ℃ without significant decomposition under a nitrogen atmosphere, TZ-HCP2@ C was stable to 318 ℃ without significant decomposition (decomposition below 100 ℃ is derived from volatile substances such as air, water vapor and the like in the material), TZ-HCP2@ D was stable to 319 ℃ without significant decomposition under a nitrogen atmosphere, and TZ-HCP3 was stable to 335 ℃ without significant decomposition under a nitrogen atmosphere.
(3) Catalytic testing of TZ-HCP2@ D
Example 7
The reaction formula is shown in the following formula (iii):
electrophiles such as p-chlorobenzaldehyde (0.20mmol), e.g., benzaldehyde, propionaldehyde, 1-pyrenecarboxaldehyde, etc., o-phenylenediamine (21.6mg,0.20mmol) and TZ-HCP2@ D (10mg) were added to a 10mL reaction tube, 2mL of ethanol was added, and then stirred at room temperature for 0.5 to 4 hours under 6W LED white light illumination. The reaction was washed centrifugally with acetone (5X 5mL), the organic phases were combined, the solvent was removed by rotary evaporation in vacuo, and the residue was isolated by column chromatography to give the product.
As shown in FIG. 7, the TZ-HCP2@ D catalyzes the coupling reaction between o-phenylenediamine and electrophiles such as p-chlorobenzaldehyde (e.g. benzaldehyde, propionaldehyde, 1-pyrene formaldehyde, etc.) with a yield of over 90%, and it can be seen that TZ-HCP2@ D has good photocatalytic activity.
(4) Cycling test of TZ-HCP2@ D:
example 8
The reaction formula is shown as the following formula (iv):
o-phenylenediamine (21.6mg,0.20mmol) and TZ-HCP2@ D (10mg) were added to a 10mL reaction tube, 2mL ethanol was added, 20.4. mu.L benzaldehyde (0.20mmol) was added, and the mixture was stirred under 6W LED white light at room temperature for 0.5-2 h. The reaction was washed centrifugally with acetone (5X 5mL), the organic phases were combined, the solvent was removed by rotary evaporation in vacuo, and the residue was isolated by column chromatography to give the product.
As shown in FIG. 8, TZ-HCP2@ D catalyzes the coupling reaction of o-phenylenediamine and benzaldehyde to repeat 20 times, each time the reaction time is 1.0-2.5h, and the yield of the coupling reaction product can be kept between 95% and 99%. Therefore, the repeated use has little influence on the catalytic effect of the TZ-HCP2@ D, which indicates that the TZ-HCP2@ D has good catalytic stability.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and other modifications or equivalent substitutions made by the technical solution of the present invention by the ordinary skilled in the art should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A synthetic method of a tetrazine hypercrosslinked porous photocatalyst is characterized by comprising the following steps: putting a precursor methoxy-substituted bipyridine tetrazine monomer, an aromatic block and a catalyst ferric trichloride into a dry two-neck flask, adding a solvent 1, 2-dichloroethane and a crosslinking agent dimethoxymethane under the protection of nitrogen, stirring at a low temperature of 45 ℃ for 5-24h, heating to 90 ℃, continuing to react for 19-48 h, and after the reaction is finished, treating with methanol and concentrated hydrochloric acid, carrying out vacuum filtration, Soxhlet extraction and drying to obtain the tetrazine type hypercrosslinked porous photocatalyst TZ-HCPs.
2. The method for synthesizing the tetrazine type hypercrosslinked porous photocatalyst as claimed in claim 1, wherein the molar ratio of the methoxy substituted bipyridine tetrazine monomer to the aromatic building block is 1: 0-50; the volume ratio of the dimethoxymethane to the 1, 2-dichloroethane is 1: 0-20.
3. The method for synthesizing the tetrazine type hypercrosslinked porous photocatalyst as claimed in claim 2, wherein the molar ratio of the methoxy substituted bipyridine tetrazine monomer to the aromatic building block is 1: 20; the volume ratio of dimethoxymethane to 1, 2-dichloroethane is 1: 6.
4. The method for synthesizing the tetrazine-based hypercrosslinked porous photocatalyst as claimed in claim 1, wherein the precursor concentration: the concentration of the methoxyl substituted bipyridine tetrazine monomer is 0.02-0.40 mmol/mL, and the concentration of the aromatic building block is 0.0-1.00 mmol/mL.
5. The method for synthesizing the tetrazine-based hypercrosslinked porous photocatalyst as claimed in claim 1, wherein the aromatic building blocks include but are not limited to benzene and fluorene.
6. The method for synthesizing the tetrazine type hypercrosslinked porous photocatalyst as claimed in claim 1, wherein the reaction temperature is 30-150 ℃; the reaction time is 1-5 days.
7. The method for synthesizing the tetrazine type hypercrosslinked porous photocatalyst as claimed in claim 6, wherein the reaction temperature is 45-90 ℃; the reaction time is 1-3 d.
8. A tetrazine type hypercrosslinked porous photocatalyst prepared by the method for synthesizing the tetrazine type hypercrosslinked porous photocatalyst according to any one of claims 1 to 7.
9. The application of the oxazine hypercrosslinked porous photocatalyst in catalyzing photoreaction according to claim 8.
10. The use of the porous catalyst according to claim 8 for catalyzing the coupling reaction between o-phenylenediamine and aldehyde electrophiles.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142958A (en) * | 2020-09-27 | 2020-12-29 | 中国科学院上海高等研究院 | Tetrazine aromatic skeleton polymer, functional derivative and synthetic method thereof |
| CN115386083A (en) * | 2022-09-16 | 2022-11-25 | 河南农业大学 | 3, 4-ethylenedioxythiophene covalent triazine framework and synthesis method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013158279A1 (en) * | 2012-04-20 | 2013-10-24 | Abbvie Inc. | Protein purification methods to reduce acidic species |
| CN104610486A (en) * | 2015-02-04 | 2015-05-13 | 杭州锐沃科技有限公司 | Ionic liquid functionalized ultra-crosslinking polymer as well preparation method and application thereof |
| CN107683305A (en) * | 2015-05-26 | 2018-02-09 | 联邦科学与工业研究组织 | Microporous polymer compositions |
| CN108767275A (en) * | 2018-05-16 | 2018-11-06 | 湘潭大学 | A kind of nitrogen-doped carbon oxygen reduction catalyst and its preparation method and application based on tetrazine ring polycarbazole |
| CN109485831A (en) * | 2018-11-29 | 2019-03-19 | 华东理工大学 | The preparation method of super cross-linked polymer |
-
2019
- 2019-12-27 CN CN201911378182.5A patent/CN111013656B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013158279A1 (en) * | 2012-04-20 | 2013-10-24 | Abbvie Inc. | Protein purification methods to reduce acidic species |
| CN104610486A (en) * | 2015-02-04 | 2015-05-13 | 杭州锐沃科技有限公司 | Ionic liquid functionalized ultra-crosslinking polymer as well preparation method and application thereof |
| CN107683305A (en) * | 2015-05-26 | 2018-02-09 | 联邦科学与工业研究组织 | Microporous polymer compositions |
| CN108767275A (en) * | 2018-05-16 | 2018-11-06 | 湘潭大学 | A kind of nitrogen-doped carbon oxygen reduction catalyst and its preparation method and application based on tetrazine ring polycarbazole |
| CN109485831A (en) * | 2018-11-29 | 2019-03-19 | 华东理工大学 | The preparation method of super cross-linked polymer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142958A (en) * | 2020-09-27 | 2020-12-29 | 中国科学院上海高等研究院 | Tetrazine aromatic skeleton polymer, functional derivative and synthetic method thereof |
| CN112142958B (en) * | 2020-09-27 | 2023-01-17 | 中国科学院上海高等研究院 | Tetrazine aromatic skeleton polymer, functional derivative and synthetic method thereof |
| CN115386083A (en) * | 2022-09-16 | 2022-11-25 | 河南农业大学 | 3, 4-ethylenedioxythiophene covalent triazine framework and synthesis method and application thereof |
| CN115386083B (en) * | 2022-09-16 | 2024-02-27 | 河南农业大学 | 3, 4-ethylenedioxythiophene covalent triazine framework and synthetic method and application thereof |
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