CN113512164A - Novel snowflake-shaped bionic covalent organic framework COFs photocatalyst and preparation method thereof - Google Patents
Novel snowflake-shaped bionic covalent organic framework COFs photocatalyst and preparation method thereof Download PDFInfo
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- CN113512164A CN113512164A CN202110447620.XA CN202110447620A CN113512164A CN 113512164 A CN113512164 A CN 113512164A CN 202110447620 A CN202110447620 A CN 202110447620A CN 113512164 A CN113512164 A CN 113512164A
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- photocatalyst
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 66
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000000468 ketone group Chemical group 0.000 claims abstract description 18
- 150000001413 amino acids Chemical class 0.000 claims abstract description 10
- 238000007337 electrophilic addition reaction Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 16
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 7
- 229940024606 amino acid Drugs 0.000 claims description 7
- 235000001014 amino acid Nutrition 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 6
- 229960001553 phloroglucinol Drugs 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 4
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002274 desiccant Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 3
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 claims description 3
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims description 3
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 3
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012346 acetyl chloride Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229960001230 asparagine Drugs 0.000 claims description 3
- 235000009582 asparagine Nutrition 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 230000003592 biomimetic effect Effects 0.000 claims 1
- 239000012039 electrophile Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 238000006303 photolysis reaction Methods 0.000 abstract description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 4
- 241000533950 Leucojum Species 0.000 abstract description 3
- 150000002085 enols Chemical class 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 125000003172 aldehyde group Chemical group 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 238000011161 development Methods 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000013384 organic framework Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a novel snowflake-shaped bionic Covalent Organic Framework (COFs) photocatalyst and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, a three-dimensional COFs structure is formed by utilizing the reaction between an amino group and an aldehyde group in raw materials, and a ketone group is formed by enol interconversion to provide a basis for subsequent electrophilic addition. Secondly, a dihydroxyl structure is formed by electrophilic addition reaction of water molecules to ketone groups, a novel snowflake-shaped bionic COFs material is formed by dehydration reaction of the dihydroxyl structure and carboxyl groups in amino acid, aperture regulation and control can be further carried out subsequently by changing the types of reactant molecules and amino acid, and uniform dispersion of the cocatalyst is realized by utilizing the covalent action of amino lone pair electrons on the snowflake shape and an empty orbit of the cocatalyst Pt. The COFs material of the invention introduces amino acid, is cheap and easy to obtain, is environment-friendly, and the hydrophilic property of the snowflake material is beneficial to accelerating the hydrogen production by photolysis. The porosity, crystallinity and pi-pi conjugated system of the COFs material jointly endow the material with excellent physicochemical properties.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a novel snowflake-shaped bionic Covalent Organic Framework (COFs) photocatalyst and a preparation method thereof.
Background
With the rapid development of economy, the sustainable development problem of human society comes with the problem of excessive consumption of fossil energy, and the problem of energy shortage and environmental problem have become the restricting factors of sustainable development of human society, so that the development of some clean energy substitutes for fossil fuels is required. Hydrogen energy has received wide attention as a clean renewable energy source, and a photocatalytic hydrogen production technology can provide abundant clean energy sources for the future so as to alleviate the environmental crisis. Currently, many inorganic semiconductors including cadmium sulfide, zinc oxide, and other inorganic semiconductor materials have been studied for the photolysis of water to produce hydrogen. However, these photocatalysts still have some limitations, such as poor stability, poor visible light response and the like. The currently more popular photocatalytic material of research is graphite phase carbon nitride. However, the graphite-phase carbon nitride also has the traditional defects of high recombination rate of photo-generated electron-hole pairs, narrow visible light absorption and the like. Therefore, the search for a novel photocatalyst having high visible light adsorption and stability is the focus of current research.
It is well known that Covalent Organic Frameworks (COFs) are one of the emerging next-generation two-dimensional (2D) or three-dimensional (3D) polymeric materials connected by covalent bonds. As the covalent organic framework has the advantages of adjustable pore diameter, large specific surface area, high crystallinity, light weight, chemical functional regulation and control according to requirements and the like, the COFs become a material with development prospects in the fields of gas storage and separation, catalysis, energy storage, photoelectricity, sensing, drug delivery and the like. Patent CN 111569942A provides a covalent triazine organic framework composite photocatalyst with surface-limited monodisperse Pt nanoparticles, and a preparation method and application thereof. Covalent triazine organic framework is used as a carrier, residual cyano groups are converted into stent carboxyl through alkaline hydrolysis, and Pt nano particles are anchored on the stent carboxyl by a method of photo-deposition to prepare the covalent triazine organic framework composite photocatalyst Pt-CTF-COOH with the surface domain-limited monodisperse Pt nano particles. The photocatalyst has long service life, but has the defects that the reaction process needs super acid trifluoromethanesulfonic acid, the requirements on equipment and operation safety are high, the existing photocatalyst generally has the problem of poor chemical stability, and the preparation process is difficult to realize green environmental protection.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a novel snowflake-shaped bionic Covalent Organic Frameworks (COFs) photocatalyst which is high in stability, low in price, easy to obtain and friendly to environment and a preparation method thereof.
The technical scheme is as follows: the preparation method of the novel snowflake-shaped bionic covalent organic framework COFs photocatalyst comprises the following steps:
(1) adding a COFs precursor and trialdehyde phloroglucinol into a mixed solution of 1,3, 5-trimethylbenzene and 1, 4-dioxane, dropwise adding weak acid, performing ultrasonic treatment until the weak acid is completely dissolved, and performing high-temperature reaction under a vacuum condition;
(2) adding N, N-dimethylformamide into the system in the step (1), washing with an organic solvent after reaction, and drying to obtain a three-dimensional COFs structural material with a ketone group;
(3) adding the three-dimensional COFs structural material obtained in the step (2) into water, dropwise adding an electrophilic reagent, reacting to perform ketone group addition, cooling the reaction to room temperature, washing, and drying to obtain a dihydroxy structural material after electrophilic addition reaction;
(4) sequentially adding amino acid, the dihydroxy structural material obtained in the step (3) and acyl chloride into a flask under a reflux state, performing ultrasonic treatment, and adding 1-methylimidazole for reaction;
(5) and (3) cooling the reaction mixture obtained in the step (4) to room temperature, pouring the cooled reaction mixture into water for quenching reaction, extracting the product from the water phase into the organic phase by using an extracting agent, washing the organic phase by using saturated salt solution to collect the organic phase, and drying the organic phase by using a drying agent.
(6) The solvent was concentrated and the crude product was purified by column chromatography on neutral alumina eluted with n-hexane to give the final product.
Further, in the step (1), the COFs precursor includes any one of 1,3, 5-tris (4-aminophenyl) benzene, tris (4-aminophenyl) amine, and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine; the weak acid is any one or combination of more of glacial acetic acid, phosphoric acid and sulfurous acid.
Further, in the step (1), the volume ratio of the 1,3, 5-trimethylbenzene to the 1, 4-dioxane is 1:1-3: 1; the ultrasonic time is 10-30 min; the high-temperature reaction is carried out at the temperature of 120-160 ℃ for 48-72 h.
Further, in the step (2), the amount of N, N-dimethylformamide is 4-7 mL, and the reaction time is 22-26 h.
Further, in the step (2), the organic solvent is any one or a combination of several of 1, 4-dioxane, dichloromethane and acetone; the washing times are 3-6 times, the drying temperature is 50-80 ℃, and the drying time is 6-10 hours.
Further, in the step (3), the electrophilic reagent is any one or a combination of more of glacial acetic acid, acetic anhydride and aluminum metaaluminate; the temperature for ketone group addition in the reaction is 70-90 ℃ and the time is 20-30 h.
Further, in the step (4), the amino acid is any one of glycine, tyrosine, asparagine and serine;
further, in the step (4), the acyl chloride is any one or a combination of several of 4-tosyl chloride, acetyl chloride, benzoyl chloride and thionyl chloride.
Further, the ultrasonic treatment is carried out for 10-20 min, and then 1-methylimidazole is added to react for 40-60 min at 50-80 ℃. Then, the reaction mixture is cooled to room temperature, and then poured into 20-30 mL of water for quenching reaction.
Further, in the step (5), the extractant is any one of carbon tetrachloride, chloroform and N, N-dimethylformamide; the saturated salt solution is any one of sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate and sodium chloride; the drying agent is any one of anhydrous calcium chloride, anhydrous copper sulfate and anhydrous magnesium sulfate.
The novel snowflake-shaped bionic Covalent Organic Frameworks (COFs) photocatalyst can be prepared by the preparation method. The invention firstly utilizes the reaction of amino and aldehyde group in the raw materials to form a three-dimensional COFs structure, and provides a foundation for subsequent electrophilic addition by means of enol interconversion to form a ketone group. Secondly, a dihydroxyl structure is formed by electrophilic addition reaction of water molecules to ketone groups, and then the dihydroxyl structure and the carboxyl dehydration reaction in amino acid are adopted to form a novel snowflake-shaped bionic COFs material, the pore diameter can be further regulated and controlled by changing the types of reactant molecules and amino acid subsequently, and the uniform dispersion of the cocatalyst is realized by utilizing the covalent action of amino lone pair electrons on the snowflake shape and the empty orbit of the cocatalyst Pt.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) the COFs materials with different pore sizes are synthesized by changing the species and the proportion of the COFs precursors, enol tautomerization is perfectly realized by regulating and controlling reaction conditions in the step, and a foundation is provided for subsequent electrophilic addition.
(2) Cheap and easily-obtained and environment-friendly biomass material amino acid is introduced to serve as a snowflake-shaped bionic structure, and the bionic hydrophilic group (long carbon chain) can increase the contact area with water, so that the hydrogen production activity of the catalyst through photolysis is improved.
(3) The snowflake-shaped bionic material is provided with rich amino groups, and the catalyst promoter Pt is uniformly dispersed on the snowflake-shaped amino groups by virtue of lone pair electrons on the amino groups and the empty orbit covalent action of the Pt. Thereby improving the performance of photolysis water hydrogen production.
Detailed Description
The technical solution of the present invention is further explained below.
Example 1:
0.351g of 1,3, 5-tri (4-aminophenyl) benzene and 0.210g of trialdehyde phloroglucinol were added to a mixed solution of 7mL of 1,3, 5-trimethylbenzene and 7mL of 1, 4-dioxane, 1mL of 3mol/L glacial acetic acid was added dropwise, and sonication was carried out for 30min until complete dissolution. The reaction is carried out for 60h at 150 ℃ under vacuum, 6mL of N, N-dimethylformamide is added into the reaction solution, and the reaction is continued for 24 h. Washing with 1, 4-dioxane for 3 times, and drying at 80 deg.C for 7 hr to obtain a three-dimensional COFs structural material with ketone group.
Adding 50mg of three-dimensional COFs structural material into 20mL of water, dropwise adding 0.5mL of 3mol/L acetic anhydride solution into the reaction solution, stirring at 75 ℃ for 26h to perform ketone group addition, cooling the reaction to room temperature, washing for 3 times, and drying to obtain the dihydroxy structural material.
0.076g of glycine, 0.088g of dihydroxy structure material and 0.191g of 4-toluenesulfonyl chloride were added to a 10mL flask in this order under reflux, and after sonication for 15min, 0.246g of 1-methylimidazole was added and the reaction was carried out at 70 ℃ for 45 min. Then, the reaction mixture was cooled to room temperature, and poured into 30mL of water to quench the reaction. The product was extracted from the aqueous phase into the organic phase with 2X 25mL chloroform, followed by 2X 25mL NaHCO3The organic phase was collected by washing and dried over 0.05g of anhydrous magnesium sulfate. The solvent was concentrated and the crude product was purified by column chromatography on neutral alumina eluted with n-hexane to give the final product.
Evaluation conditions were as follows: to investigate its performance in photolyzing water to produce hydrogen, 50mg of catalyst was dispersed in 90mL of water, 10mL of triethanolamine and 0.2mL of 3 wt% H were added2PtCl6The method comprises the following steps of carrying out ultrasonic treatment for 30min under a dark condition, adding the ultrasonic treatment into a reactor, connecting the reactor with a gas circuit circulating system, vacuumizing the reaction system by using a vacuum pump for 1h to remove air in the system, irradiating under a 300W xenon lamp with a 420nm cutoff wavelength filter, carrying out on-line monitoring on generated gas by using a gas chromatograph, wherein the sampling interval is 30min, the detector is a TCD thermal conductivity detector, and the carrier gas uses high-purity argon.
The results show that: the hydrogen production rate of the covalent organic framework photocatalyst is 1339 mu mol/g.h, and the stability reaches 92% after 16h circulation stability test.
Example 2:
adding 0.290g of tri (4 aminophenyl) amine and 0.210g of trialdehyde phloroglucinol into a mixed solution of 12mL of 1,3, 5-trimethylbenzene and 6mL of 1, 4-dioxane, dropwise adding a mixture of 0.5mL of 3mol/L glacial acetic acid and 0.5mL of 3mol/L phosphoric acid, carrying out ultrasonic treatment for 20min till complete dissolution, reacting at 140 ℃ for 48h under vacuum, adding 5mL of N, N-dimethylformamide into the reaction solution, continuing the reaction for 24h, washing 3 times with 1, 4-dioxane, washing 3 times with dichloromethane, and drying at 60 ℃ for 8h to obtain the three-dimensional COFs structural material with ketone groups.
Adding 50mg of three-dimensional COFs structural material into 15mL of water, adding 0.5mL of 3mol/L glacial acetic acid solution into the reaction solution, stirring for 24h at 80 ℃ to perform ketone group addition, cooling the reaction to room temperature, washing for 3 times by using deionized water, and drying to obtain the dihydroxy structural material.
0.181g of tyrosine, 0.079g of a bishydroxy structure material and 0.079g of acetyl chloride were sequentially added under reflux to a 10mL flask, and after sonication for 15min, 0.197g of 1-methylimidazole was added and reacted at 60 ℃ for 50 min. Then, the reaction mixture was cooled to room temperature and poured into 25mL of water to quench the reaction. The product was extracted from the aqueous phase into the organic phase with 2X 25mL of carbon tetrachloride, followed by 2X 25mL of Na2CO3The organic phase was collected by washing and dried with 0.06g of anhydrous calcium chloride. The solvent was concentrated and the crude product was purified by column chromatography on neutral alumina eluted with n-hexane to give the final product.
Evaluation conditions were as follows: the same as in example 1.
The results show that: the hydrogen production rate of the covalent organic framework photocatalyst is 1442 mu mol/g.h, and the stability reaches 90% after 16h circulation stability test.
Example 3:
adding 0.354g of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 0.210g of trialdehyde phloroglucinol into a mixed solution of 8mL of 1,3, 5-trimethylbenzene and 8mL of 1, 4-dioxane, dropwise adding 1mL of 3mol/L sulfurous acid, carrying out ultrasonic treatment for 25min until the mixture is completely dissolved, reacting for 48h at 135 ℃ in vacuum, adding 7mL of N, N-dimethylformamide into the reaction solution, continuing to react for 24h, washing for 3 times with 1, 4-dioxane, washing for 3 times with acetone, and drying for 8h at 55 ℃ to obtain the three-dimensional COFs structural material with ketone groups.
Adding 50mg of three-dimensional COFs structural material into 18mL of water, adding a mixture of 0.25mL of 3mol/L glacial acetic acid solution and 0.25mL of 3mol/L acetic anhydride solution into the reaction solution, stirring at 65 ℃ for 22h for ketone group addition, cooling the reaction to room temperature, washing with deionized water for 3 times, and drying to obtain the dihydroxy structural material.
0.763g of asparagine, 0.089g of dihydroxy structure material and 0.141g of benzoyl chloride were added to a 10mL flask in this order under reflux, and after sonication for 20min, 0.246g of 1-methylimidazole was added and the reaction was carried out at 65 ℃ for 60 min. Then, the reaction mixture was cooled to room temperature and poured into 18mL of water to quench the reaction. The product was extracted from the aqueous phase into the organic phase with 2X 25mL of N, N-dimethylformamide, followed by 2X 25mL of KHCO3The organic phase was collected by washing and dried over 0.08g of anhydrous copper sulfate. The solvent was concentrated and the crude product was purified by column chromatography on neutral alumina eluted with n-hexane to give the final product.
Evaluation conditions were as follows: the same as in example 1.
The results show that: the hydrogen production rate of the covalent organic framework photocatalyst is 1123 mu mol/g.h, and the stability reaches 88 percent after 16h circulation stability test.
Example 4:
adding 0.351g of 1,3, 5-tri (4-aminophenyl) benzene and 0.210g of trialdehyde phloroglucinol into a mixed solution of 7mL of 1,3, 5-trimethylbenzene and 7mL of 1, 4-dioxane, dropwise adding 0.5mL of 6mol/L glacial acetic acid and 0.5mL of 6mol/L sulfurous acid, carrying out ultrasonic treatment for 30min till complete dissolution, reacting at 160 ℃ for 48h under vacuum, adding 4mL of N, N-dimethylformamide into the reaction solution, continuing to react for 24h, washing with dichloromethane for 3 times, washing with acetone for 3 times, and drying at 80 ℃ for 6h to obtain the three-dimensional COFs structural material with ketone groups.
Adding 50mg of three-dimensional COFs structural material into 12mL of water, adding 0.5mL of 3mol/L metaaluminate solution into the reaction solution, heating the reaction to 85 ℃, stirring for 26 hours at 85 ℃ to perform ketone group addition, cooling the reaction to room temperature, washing with deionized water for 3 times, and drying to obtain the dihydroxy structural material.
0.105g of serine, 0.088g of dihydroxy structure material, 0.071g of benzoyl chloride and 0.060g of thionyl chloride were sequentially added to a 10mL flask under reflux, sonicated for 12min, then 0.369g of 1-methylimidazole was added, and the reaction was carried out at 70 ℃ for 45 min. Then, the reaction mixture was cooled toThe reaction was quenched at room temperature by pouring into 22mL of water, the product was extracted from the aqueous phase into the organic phase with 2X 25mL of chloroform, and then with 2X 25mL of K2CO3The organic phase was collected by washing and dried over 0.06g of anhydrous magnesium sulfate. The solvent was concentrated and the crude product was purified by column chromatography on neutral alumina eluted with n-hexane to give the final product.
Evaluation conditions were as follows: the same as in example 1.
The results show that: the hydrogen production rate of the covalent organic framework photocatalyst is 1526 mu mol/g.h, and the stability reaches 92% after 16h circulation stability test.
Claims (10)
1. A preparation method of a novel snowflake-shaped bionic Covalent Organic Framework (COFs) photocatalyst is characterized by comprising the following steps:
(1) adding a COFs precursor and trialdehyde phloroglucinol into a mixed solution of 1,3, 5-trimethylbenzene and 1, 4-dioxane, dropwise adding weak acid, performing ultrasonic treatment until the weak acid is completely dissolved, and performing high-temperature reaction under a vacuum condition;
(2) adding N, N-dimethylformamide into the system in the step (1), washing with an organic solvent after reaction, and drying to obtain a three-dimensional COFs structural material with a ketone group;
(3) adding the three-dimensional COFs structural material obtained in the step (2) into water, dropwise adding an electrophilic reagent, reacting to perform ketone group addition, cooling the reaction to room temperature, washing, and drying to obtain a dihydroxy structural material after electrophilic addition reaction;
(4) sequentially adding amino acid, the dihydroxy structural material obtained in the step (3) and acyl chloride into a flask under a reflux state, performing ultrasonic treatment, and adding 1-methylimidazole for reaction;
(5) and (3) cooling the reaction mixture obtained in the step (4) to room temperature, pouring the cooled reaction mixture into water for quenching reaction, extracting the product from the water phase into the organic phase by using an extracting agent, washing the organic phase by using saturated salt solution to collect the organic phase, and drying the organic phase by using a drying agent.
(6) The solvent was concentrated and the crude product was purified by column chromatography on neutral alumina eluted with n-hexane to give the final product.
2. The method for preparing a novel snowflake-shaped bionic Covalent Organic Frameworks (COFs) photocatalyst according to claim 1, wherein in the step (1), the COFs precursor comprises any one of 1,3, 5-tris (4-aminophenyl) benzene, tris (4-aminophenyl) amine and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine; the weak acid is any one or combination of more of glacial acetic acid, phosphoric acid and sulfurous acid.
3. The method for preparing the novel snowflake-shaped bionic Covalent Organic Frameworks (COFs) photocatalyst according to claim 1, wherein in the step (1), the volume ratio of the 1,3, 5-trimethylbenzene to the 1, 4-dioxane is 1:1-3: 1; the ultrasonic time is 10-30 min; the high-temperature reaction is carried out at the temperature of 120-160 ℃ for 48-72 h.
4. The preparation method of the novel snowflake-shaped bionic Covalent Organic Frameworks (COFs) photocatalyst according to claim 1, wherein in the step (2), the amount of N, N-dimethylformamide is 4-7 mL, and the reaction time is 22-26 h.
5. The preparation method of the novel snowflake-shaped bionic Covalent Organic Frameworks (COFs) photocatalyst according to claim 1, wherein in the step (2), the organic solvent is any one or a combination of 1, 4-dioxane, dichloromethane and acetone; the washing times are 3-6 times, the drying temperature is 50-80 ℃, and the drying time is 6-10 hours.
6. The method for preparing the novel snowflake-shaped bionic Covalent Organic Frameworks (COFs) photocatalyst according to claim 1, wherein in the step (3), the electrophile is any one or a combination of more of glacial acetic acid, acetic anhydride and aluminum meta-aluminate; the temperature for ketone group addition in the reaction is 70-90 ℃ and the time is 20-30 h.
7. The method for preparing novel snowflake-shaped bionic Covalent Organic Frameworks (COFs) photocatalyst according to claim 1, wherein in the step (4), the amino acid is any one of glycine, tyrosine, asparagine and serine.
8. The method for preparing novel snowflake-shaped bionic Covalent Organic Frameworks (COFs) photocatalyst according to claim 1, wherein in the step (4), the acyl chloride is any one or a combination of 4-tosyl chloride, acetyl chloride, benzoyl chloride and thionyl chloride.
9. The method for preparing a novel snowflake-shaped bionic Covalent Organic Frameworks (COFs) photocatalyst according to claim 1, wherein in the step (5), the extracting agent is any one of carbon tetrachloride, chloroform and N, N-dimethylformamide; the saturated salt solution is any one of sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate and sodium chloride; the drying agent is any one of anhydrous calcium chloride, anhydrous copper sulfate and anhydrous magnesium sulfate.
10. A novel snowflake-shaped biomimetic Covalent Organic Frameworks (COFs) photocatalyst prepared according to the preparation method of one of claims 1 to 9.
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