CN116284633A - Porphyrin-containing covalent organic framework material and preparation method and application thereof - Google Patents
Porphyrin-containing covalent organic framework material and preparation method and application thereof Download PDFInfo
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- CN116284633A CN116284633A CN202310117913.0A CN202310117913A CN116284633A CN 116284633 A CN116284633 A CN 116284633A CN 202310117913 A CN202310117913 A CN 202310117913A CN 116284633 A CN116284633 A CN 116284633A
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- porphyrin
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- framework material
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- benzothiadiazole
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 53
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 claims abstract description 38
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 23
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- JDMIEZMXBAUTSW-UHFFFAOYSA-N 4-[4-(4-formylphenyl)-2,1,3-benzothiadiazol-7-yl]benzaldehyde Chemical compound O=Cc1ccc(cc1)-c1ccc(-c2ccc(C=O)cc2)c2nsnc12 JDMIEZMXBAUTSW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- REPFNYFEIOZRLM-UHFFFAOYSA-N chembl376444 Chemical compound C1=CC(N)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(N)=CC=1)=C1C=CC(=N1)C(C=1C=CC(N)=CC=1)=C1C=CC(N1)=C1C=2C=CC(N)=CC=2)=C2N=C1C=C2 REPFNYFEIOZRLM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical class [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- UIGXGNUMMVHJKX-UHFFFAOYSA-N (4-formylphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(C=O)C=C1 UIGXGNUMMVHJKX-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000004298 light response Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- SOZFIIXUNAKEJP-UHFFFAOYSA-N 1,2,3,4-tetrafluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1F SOZFIIXUNAKEJP-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YGHMZQVOFVDADV-UHFFFAOYSA-N 4-[4-(4-formylphenyl)phenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=C(C=2C=CC(C=O)=CC=2)C=C1 YGHMZQVOFVDADV-UHFFFAOYSA-N 0.000 description 1
- -1 4-formylphenyl Chemical group 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 238000007626 photothermal therapy Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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Abstract
The invention discloses a covalent organic framework material containing porphyrin, and a preparation method and application thereof, and belongs to the technical field of photocatalytic materials. The covalent organic framework material is prepared by taking 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4, 7-di (4-formylphenyl) -2,1, 3-benzothiadiazole as monomers for reaction and carrying out one-step vacuum thermal polymerization. The covalent organic framework material containing porphyrin prepared by the invention can be well dispersed in various common organic solvents and kept stable, has good visible light response capability, and can show good activity of photocatalytic rapid selective oxidation of 5-Hydroxymethylfurfural (HMF) to generate 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) under visible light irradiation.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a covalent organic framework material containing porphyrin, a preparation method thereof and application thereof in photocatalysis of 5-hydroxymethyl furfural (HMF) for selective oxidation to generate 5-hydroxymethyl-2-furancarboxylic acid (HMFCA).
Background
The 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) can be used as a precursor of synthetic fibers and plastics, has potential anti-tumor activity, and is a compound with wide application value. Currently, 5-hydroxymethyl-2-furancarboxylic acid can be prepared in a variety of ways. For example, the oxidation of 5-hydroxymethylfurfural is catalyzed in a mixed system of butanol and ethyl acetate using a lipase (sus. Chem. 2013, 6, 826); au@CeO was used at 130℃and 10 bar pressure 2 Catalytic oxidation for a long time (Green Chemistry, 2017, 19:1075). Since the known processes generally require relatively high cost enzymes, metal catalysis or require alkaline reaction environments and severe high temperature and high pressure oxidation conditions, it is particularly important to develop a process that can efficiently and environmentally synthesize 5-hydroxymethyl-2-furancarboxylic acid under mild reaction conditions.
The covalent organic framework material (Covanlent Organic Frameworks, COFs) is an ordered and large specific surface area functional porous material (Science, 2005,310 (5751):1166) with light atoms such as carbon, nitrogen, oxygen and boron covalently linked. Among them, COFs synthesized from porphyrin as a structural unit have both physicochemical properties of porphyrin and a porous structure of COFs, and have been receiving extensive attention from researchers. Covalent organic framework materials have broad application prospects in heterogeneous catalysis (Chemical Reviews, 2020, 120 (16), 8814), gas adsorption and storage (Science, 2015,349, 1208), photodynamic and photothermal therapy (Monatshefte Fur Chemie, 2012, 143, 153), and the like. According to the invention, 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4, 7-di (4-formylphenyl) -2,1, 3-benzothiadiazole are used as monomers, and a covalent organic framework material containing porphyrin is obtained through vacuum thermal polymerization. Under the condition of taking oxygen as an oxidant, the covalent organic framework material can realize the selective oxidation of 5-hydroxymethylfurfural at room temperature under the irradiation of visible light to efficiently generate 5-hydroxymethyl-2-furancarboxylic acid.
Disclosure of Invention
The invention aims to provide a covalent organic framework material containing porphyrin, a preparation method thereof and an application thereof in photocatalytic selective oxidation of 5-hydroxymethyl furfural (HMF) to generate 5-hydroxymethyl-2-furancarboxylic acid (HMFCA),
in order to achieve the above purpose, the invention adopts the following technical scheme:
a covalent organic framework material containing porphyrin is synthesized by using 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole and 5,10,15, 20-tetra (4-aminophenyl) porphyrin as reaction monomers through one-step vacuum thermal polymerization reaction. The reaction formula is as follows:
(1) Mixing 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4, 7-di (4-formylphenyl) -2,1, 3-benzothiadiazole, adding a mixed solution containing mesitylene and absolute ethyl alcohol and an aqueous solution of acetic acid, carrying out ultrasonic treatment for 30 minutes, vacuumizing and sealing, heating for 72 hours at 120 ℃, cooling to room temperature, filtering and collecting a solid sample, and washing with water, absolute methanol, tetrahydrofuran and dimethyl sulfoxide three times in sequence;
(2) Respectively Soxhlet extracting the solid sample washed in the step (1) with acetone and tetrahydrofuran for 24 hours, and collecting the obtained solid substance;
(3) And (3) heating and vacuum drying the solid matter treated in the step (2) to obtain the covalent organic framework material containing porphyrin.
Further, the preparation of the 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole comprises the steps of mixing 8.3mmol of 4-formylphenylboronic acid and 3.3mmol of 4, 7-dibromo-2, 1, 3-benzothiadiazole, sequentially adding 9mL of saturated potassium carbonate aqueous solution, 25mL of tetrahydrofuran and 17mL of absolute ethyl alcohol, degassing for 3 times, adding 0.16mmol of triphenylphosphine palladium in a nitrogen atmosphere, heating, stirring and refluxing for 12 hours, pouring the reaction mixture into water after the reaction mixture is cooled to room temperature, extracting for 3 times by chloroform, collecting an organic layer, drying by using anhydrous sodium sulfate, removing an organic solvent by rotary evaporation, and performing silica gel column chromatography purification by using dichloromethane as a mobile phase to obtain a light green solid.
Further, the molar ratio of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin to 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole used in step (1) is 1:2; the volume ratio of mesitylene to absolute ethyl alcohol in the mixed solution is 1:1, and the concentration of the acetic acid aqueous solution is 12 mol/L; the ratio of the amount of the reaction monomer to the amount of the mixed solution was about 10mg/mL.
Further, the volume of acetone or tetrahydrofuran used in step (2) for soxhlet extraction is 1000 times the mass of the solid sample.
Further, the temperature of the drying in the step (3) is 80 ℃ and the time is 12 hours.
The obtained covalent organic framework material containing porphyrin shows good activity of photocatalytic rapid selective oxidation of 5-hydroxymethyl furfural (HMF) to generate 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) under visible light irradiation, so that the covalent organic framework material can be used for efficiently catalyzing rapid selective oxidation of HMF to generate HMFCA under visible light. The method specifically comprises the steps of taking HMF as a reaction raw material, taking oxygen as an oxidant, taking N, N-dimethylformamide as a reaction solvent, taking the covalent organic framework material containing porphyrin as a photocatalyst, and irradiating under a 50W blue (420 nm) LED lamp for 10 minutes to generate HMFCA.
The invention has the remarkable advantages that:
(1) The covalent organic framework material containing porphyrin prepared by the invention has good visible light response, and simultaneously has higher reaction activity of catalyzing 5-hydroxymethyl furfural to be selectively oxidized and synthesized into 5-hydroxymethyl-2-furancarboxylic acid (complete conversion of 5-hydroxymethyl furfural can be realized in 10 minutes under oxygen conditions), so that the covalent organic framework material containing porphyrin is an efficient photocatalyst.
(2) The covalent organic framework material containing porphyrin prepared by the invention has good chemical stability and can be recycled for multiple times.
(3) The whole production process is simple, easy to control, low in energy consumption and low in cost, meets the actual production requirements, and is beneficial to large-scale popularization.
Drawings
FIG. 1 is a schematic illustration of 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole obtained in example 1 1 H-NMR chart.
FIG. 2 is a Fourier transform infrared spectrum of the 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole obtained in example 1 and a porphyrin-containing covalent organic framework material.
FIG. 3 is an X-ray powder diffraction pattern of the porphyrin-containing covalent organic framework material obtained in example 1.
FIG. 4 is a scanning electron microscope image of the porphyrin-containing covalent organic framework material obtained in example 1.
FIG. 5 is a UV-visible diffuse reflectance graph of the porphyrin-containing covalent organic framework material obtained in example 1.
FIG. 6 is a graph showing the comparative performance of the different structure covalent organic framework materials of example 2 in photocatalytic oxidation of 5-hydroxymethylfurfural.
FIG. 7 is a graph showing the composition analysis of a product synthesized by photocatalytic selective oxidation of 5-hydroxymethylfurfural using the porphyrin-containing covalent organic framework material obtained in example 1.
FIG. 8 is a graph showing the reactivity of the porphyrin-containing covalent organic framework material of example 3 over multiple cycles.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
Synthesis of 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole: 4-formylphenylboronic acid (1.25 g,8.3 mmol) and 4, 7-dibromo-2, 1, 3-benzothiadiazole (1 g,3.3 mmol) were added to a three-necked flask, 9mL of a saturated aqueous potassium carbonate solution, 25mL of tetrahydrofuran and 17mL of absolute ethyl alcohol were further added in this order, after degassing for 3 times, palladium tetraphenylphosphine (200 mg,0.16 mmol) was added under nitrogen atmosphere, heated and stirred under reflux for 12 hours, after the reaction mixture was cooled to room temperature, poured into water and extracted 3 times with chloroform, the organic layer was collected, dried with anhydrous sodium sulfate and then the organic solvent was removed by rotary evaporation. And then using dichloromethane as a mobile phase, purifying the obtained solid by silica gel column chromatography, and evaporating to dryness to obtain a light green solid which is 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole.
13.5 mg (0.02 mmol) of 5,10,15, 20-tetrakis (4-aminophenyl) -porphyrin (TAPP) and 15 mg (0.05 mmol) of 4, 7-bis (4-formylphenyl) -2,1, 3-Benzothiadiazole (BT) are weighed into 10 ml ampoules, 1 ml of mesitylene and 1 ml of absolute ethyl alcohol are added in sequence, after 30 minutes of ultrasound, 100. Mu.l of 12 mol/L aqueous acetic acid solution are added, after 30 minutes of ultrasound degassing, vacuum is drawn and the tube is sealed with a flame gun, and the reaction is carried out for 72 hours at 120 ℃. And after the reaction is finished, filtering and collecting a solid sample, washing the solid sample with water, absolute methanol, tetrahydrofuran and dimethyl sulfoxide for three times in sequence, respectively extracting the solid sample with tetrahydrofuran and acetone with the mass of 1000 times of the volume for 24 hours, and finally, placing the product at 80 ℃ for vacuum drying overnight to obtain the covalent organic framework material containing porphyrin.
FIG. 1 shows the obtained 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole 1 H-NMR chart. From the figure, it can be seen that the two double peaks of 10.09ppm corresponding to protons on aldehyde groups at two ends of the molecule, 8.24 ppm-8.25 ppm and 8.07 ppm-8.08 ppm correspond to protons on benzene rings connected with the aldehyde groups, the single peak of 8.11ppm corresponds to proton signals on benzene rings where benzothiadiazole is located, and the peak area ratio of the four signals is 1:2:2:1.
FIG. 2 is a Fourier transform infrared spectrum of the resulting 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole and porphyrin-containing covalent organic framework material. As can be seen from the figure, the 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole was found to be present at 1697cm -1 Characteristic peaks at the positions correspond to aldehyde groups at two ends of the molecule, 1601cm -1 Corresponding to c=n on benzothiadiazole; and the covalent organic framework material containing porphyrin has C=N bond and C=O bond and is 3200 cm to 3400cm -1 The N-H bonds of (c) are all changed.
Fig. 3 is an XRD pattern of the resulting porphyrin-containing covalent organic framework material. From the figure, it can be seen that the material shows a broad peak at 21.5 °, indicating that the synthesized organic covalent polymer has a partially stacked structure, and that peaks at 2.6 °,5.2 °,7.8 ° and 10.4 ° are characteristic peaks of the covalent organic framework containing porphyrin.
Fig. 4 is an SEM image of the resulting porphyrin-containing covalent organic framework material. As can be seen from the figure, the covalent organic framework material containing porphyrin has a porous structure, and through BET test, the covalent organic framework material is specifically a mesoporous material, and the specific surface area of the covalent organic framework material is 106.9308m 2 And/g, pore diameter of 6.6326nm.
FIG. 5 is a UV visible diffuse reflectance graph of the resulting porphyrin-containing covalent organic framework material.
Example 2
The procedure of example 1 was followed using [1,1':4',1 "-terphenyl ] -4, 4" -dicarboxaldehyde (3B), 4, 7-bis (4-formylphenyl) -1,2,4,5-s tetrafluorobenzene (3 BF 4) in place of 4, 7-bis (4-formylphenyl) -2,1, 3-Benzothiadiazole (BT) in example 1, and 5,10,15, 20-tetrakis (4-aminophenyl) -porphyrin to give a covalent organic framework material of different structure.
5 mg of the prepared covalent organic framework material is placed in a 10 ml glass reactor, 2 ml of N, N-dimethylformamide and 25.2 mg of HMF are added, oxygen is introduced, the reaction is carried out for 10 minutes under the illumination condition of an LED at 25 ℃ and 420 nm, and a high performance liquid chromatograph is used for analyzing the reaction product.
FIG. 6 is a comparison of the photocatalytic oxidation of 5-hydroxymethylfurfural by a covalent organic framework of different structures. From the figure, it can be seen that the covalent organic framework prepared using 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole as linker has the best effect of catalyzing the conversion of 5-hydroxymethylfurfural (conversion 99.6%).
FIG. 7 is a graph of the composition analysis of the product of photocatalytic oxidation of 5-hydroxymethylfurfural with porphyrin-containing covalent organic framework material prepared in example 1. As can be seen from the figure, the covalent organic framework material containing porphyrin catalyzes 5-hydroxymethylfurfural, the main product of which is 5-hydroxymethyl-2-furancarboxylic acid (selectivity 94.7%).
Example 3
The reaction solution after the reaction of example 2 was centrifuged at 10000 rpm for 5 minutes, and after the catalyst was collected and washed three times with ethanol (5 ml each time), it was dried in an oven at 75℃for 12 hours, and then the reaction was repeated as in example 2.
FIG. 8 is a graph showing the activity of the catalyst after five cycles. The graph shows that the recycling yield of the catalyst is basically stable, and the heterogeneous catalyst is fully proved to have better stability and the advantage of recycling.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A porphyrin-containing covalent organic framework material characterized in that: the unit structural formula is as follows:
2. a method of preparing the porphyrin-containing covalent organic framework material of claim 1, wherein: the porphyrin-containing covalent organic framework material is synthesized by one-step vacuum thermal polymerization using 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole and 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin as reaction monomers.
3. The method of preparing a porphyrin-containing covalent organic framework material according to claim 2, characterized in that: the preparation method of the 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole comprises the steps of mixing 8.3mmol of 4-formylphenylboric acid and 3.3mmol of 4, 7-dibromo-2, 1, 3-benzothiadiazole, sequentially adding 9mL of saturated potassium carbonate aqueous solution, 25mL of tetrahydrofuran and 17mL of absolute ethyl alcohol, degassing for 3 times, adding 0.16mmol of triphenylphosphine palladium in a nitrogen atmosphere, heating, stirring and refluxing for 12 hours, pouring the reaction mixture into water after the reaction mixture is cooled to room temperature, extracting for 3 times by chloroform, collecting an organic layer, drying by anhydrous sodium sulfate, removing the organic solvent by rotary evaporation, and purifying by silica gel column chromatography by using dichloromethane as a mobile phase to obtain pale green solid.
4. The method of preparing a porphyrin-containing covalent organic framework material according to claim 2, characterized in that: the method comprises the following steps:
(1) Mixing 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4, 7-di (4-formylphenyl) -2,1, 3-benzothiadiazole, adding a mixed solution containing mesitylene and absolute ethyl alcohol and an aqueous solution of acetic acid, carrying out ultrasonic treatment for 30 minutes, vacuumizing and sealing, heating for 72 hours at 120 ℃, cooling to room temperature, filtering and collecting a solid sample, and washing with water, absolute methanol, tetrahydrofuran and dimethyl sulfoxide three times in sequence;
(2) Respectively Soxhlet extracting the solid sample washed in the step (1) with acetone and tetrahydrofuran for 24 hours, and collecting the obtained solid substance;
(3) And (3) heating and vacuum drying the solid matter treated in the step (2) to obtain the covalent organic framework material containing porphyrin.
5. The method of preparing a porphyrin-containing covalent organic framework material according to claim 4, wherein: the molar ratio of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin to 4, 7-bis (4-formylphenyl) -2,1, 3-benzothiadiazole used in step (1) is 1:2; the volume ratio of mesitylene to absolute ethyl alcohol in the mixed solution is 1:1, and the concentration of the acetic acid aqueous solution is 12 mol/L; the dosage ratio of the reaction monomer to the mixed solution was 10mg/mL.
6. The method of preparing a porphyrin-containing covalent organic framework material according to claim 4, wherein: the volume of acetone or tetrahydrofuran used in step (2) for soxhlet extraction is 1000 times the mass of the solid sample.
7. The method of preparing a porphyrin-containing covalent organic framework material according to claim 4, wherein: the temperature of the drying in the step (3) is 80 ℃ and the time is 12 hours.
8. Use of the porphyrin-containing covalent organic framework material of claim 1 in the photocatalytic selective oxidation of 5-hydroxymethylfurfural to 5-hydroxymethyl-2-furancarboxylic acid.
9. The use according to claim 8, characterized in that: taking 5-hydroxymethylfurfural as a reaction raw material, taking oxygen as an oxidant, taking N, N-dimethylformamide as a reaction solvent, and irradiating under a 50W blue LED lamp for 10 minutes by taking the covalent organic framework material containing porphyrin as a photocatalyst to generate 5-hydroxymethyl-2-furancarboxylic acid;
wherein the dosage of the covalent organic framework material containing porphyrin is 2% -5% of the mass of the reaction raw material.
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| WO2015123781A1 (en) * | 2014-02-20 | 2015-08-27 | The University Of Western Ontario | Formaldehyde-free phenolic resins, downstream products, their synthesis and use |
| CN109134830A (en) * | 2018-09-26 | 2019-01-04 | 台州学院 | A kind of covalent organic framework material and its preparation method and application that porphyrin-benzothiazole is difunctional |
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| CN114671990A (en) * | 2022-05-27 | 2022-06-28 | 农业农村部环境保护科研监测所 | Porphyrin covalent organic framework material and preparation method and application thereof |
| CN115417960A (en) * | 2022-08-16 | 2022-12-02 | 西北师范大学 | Method for stripping porphyrin-based covalent organic framework material driven by ligand |
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| WO2015123781A1 (en) * | 2014-02-20 | 2015-08-27 | The University Of Western Ontario | Formaldehyde-free phenolic resins, downstream products, their synthesis and use |
| CN109134830A (en) * | 2018-09-26 | 2019-01-04 | 台州学院 | A kind of covalent organic framework material and its preparation method and application that porphyrin-benzothiazole is difunctional |
| CN112111070A (en) * | 2020-10-20 | 2020-12-22 | 苏州大学 | Metal coordination porphyrin-based conjugated polymer, preparation method thereof and application thereof in photocatalytic degradation of organic pollutants |
| CN114671990A (en) * | 2022-05-27 | 2022-06-28 | 农业农村部环境保护科研监测所 | Porphyrin covalent organic framework material and preparation method and application thereof |
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