CN114085388A - 一种含恶二唑连接基元的共价有机框架材料 - Google Patents
一种含恶二唑连接基元的共价有机框架材料 Download PDFInfo
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- CN114085388A CN114085388A CN202111619981.4A CN202111619981A CN114085388A CN 114085388 A CN114085388 A CN 114085388A CN 202111619981 A CN202111619981 A CN 202111619981A CN 114085388 A CN114085388 A CN 114085388A
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- oxadiazole
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 83
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 7
- 238000000944 Soxhlet extraction Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- -1 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine tetrakis (4-formylphenyl) ethene Chemical compound 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 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
- 239000000203 mixture Substances 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ZCJZVMNBJKPQEV-UHFFFAOYSA-N 4-[3,5-bis(4-formylphenyl)phenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC(C=2C=CC(C=O)=CC=2)=CC(C=2C=CC(C=O)=CC=2)=C1 ZCJZVMNBJKPQEV-UHFFFAOYSA-N 0.000 claims description 3
- STUIYJQOYVPIKS-UHFFFAOYSA-N CCOC1(C=CC(OCC)=CC1C(NN)=O)C(NN)=O Chemical compound CCOC1(C=CC(OCC)=CC1C(NN)=O)C(NN)=O STUIYJQOYVPIKS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YOXHQRNDWBRUOL-UHFFFAOYSA-N 4-(4-formyl-n-(4-formylphenyl)anilino)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1N(C=1C=CC(C=O)=CC=1)C1=CC=C(C=O)C=C1 YOXHQRNDWBRUOL-UHFFFAOYSA-N 0.000 claims description 2
- ZGLHKEJAGHMUHR-UHFFFAOYSA-N 4-[3,6,8-tris(4-formylphenyl)pyren-1-yl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C(C1=CC=C23)=CC(C=4C=CC(C=O)=CC=4)=C(C=C4)C1=C2C4=C(C=1C=CC(C=O)=CC=1)C=C3C1=CC=C(C=O)C=C1 ZGLHKEJAGHMUHR-UHFFFAOYSA-N 0.000 claims description 2
- YNLBSRHGIHAPAE-UHFFFAOYSA-N 4-[[4,6-bis(4-formylphenoxy)-1,3,5-triazin-2-yl]oxy]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1OC1=NC(OC=2C=CC(C=O)=CC=2)=NC(OC=2C=CC(C=O)=CC=2)=N1 YNLBSRHGIHAPAE-UHFFFAOYSA-N 0.000 claims description 2
- SUQGULAGAKSTIB-UHFFFAOYSA-N 6-(5-formylpyridin-2-yl)pyridine-3-carbaldehyde Chemical compound N1=CC(C=O)=CC=C1C1=CC=C(C=O)C=N1 SUQGULAGAKSTIB-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- RSQZINMBNWLMKM-UHFFFAOYSA-N C(=O)C1=CC=C(C=C1)C#CC1=CC(=CC(=C1)C#CC1=CC=C(C=C1)C=O)C#CC1=CC=C(C=C1)C=O Chemical compound C(=O)C1=CC=C(C=C1)C#CC1=CC(=CC(=C1)C#CC1=CC=C(C=C1)C=O)C#CC1=CC=C(C=C1)C=O RSQZINMBNWLMKM-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 125000005647 linker group Chemical group 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007243 oxidative cyclization reaction Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005072 1,3,4-oxadiazoles Chemical class 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- RXFWPOMAJBVGRU-UHFFFAOYSA-N 4-[4,6-bis(4-formylphenyl)-1,3,5-triazin-2-yl]benzaldehyde Chemical compound N1=C(N=C(N=C1C1=CC=C(C=O)C=C1)C1=CC=C(C=O)C=C1)C1=CC=C(C=O)C=C1 RXFWPOMAJBVGRU-UHFFFAOYSA-N 0.000 description 1
- QBFNGLBSVFKILI-UHFFFAOYSA-N 4-ethenylbenzaldehyde Chemical group C=CC1=CC=C(C=O)C=C1 QBFNGLBSVFKILI-UHFFFAOYSA-N 0.000 description 1
- UHVUOKPBZLPYMK-UHFFFAOYSA-N CCOC(C=C1)=CC(C2=C(C(NN)=O)C(C(NN)=O)=CC=C2)=C1OCC Chemical compound CCOC(C=C1)=CC(C2=C(C(NN)=O)C(C(NN)=O)=CC=C2)=C1OCC UHVUOKPBZLPYMK-UHFFFAOYSA-N 0.000 description 1
- 239000013474 COF-1 Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method 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
- 238000001132 ultrasonic dispersion Methods 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
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- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
-
- B01J35/39—
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- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- 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
Abstract
本发明为一种含恶二唑连接基元的共价有机框架材料。该材料的制备方法包括以下步骤:(1)在Schlenk管中加入芳香醛、芳香甲酰肼、第一有机溶剂和无机酸水溶液,100~130℃下反应3~7天后得到含N‑酰基腙连接基元的COFs;(2)将COFs、铜盐和碳酸盐加入到第二有机溶剂中,在90~120℃下反应3~7天后,得到含恶二唑连接基元的COFs。本发明提供的COFs合成后修饰策略,不仅拓宽了COFs在可见光区域的吸收范围,而且能更好地促进光生载流子的分离和运输,从而提高了光催化水产氢的性能。
Description
技术领域
本发明属于新能源材料领域,具体涉及一种含恶二唑连接基元的共价有机框架材料的制备及在可见光催化反应中的应用。
背景技术
共价有机框架(Covalent Organic Frameworks,COFs)是由有机结构单元通过共价键连接形成的二维或三维有序结构的晶态多孔材料,具有比表面积大、合成方法多样、可模块化合成和容易修饰改性等特点,在气体吸附与分离、光电、催化和储能等领域表现出了好的应用前景。目前普遍认为COFs的功能来自于其构筑模块,而稳定性则归因于连接构筑模块的共价键。因此可以基于网状化学和动态共价化学的基本原理,将各种类型的构筑模块通过可逆的共价键连接起来,形成具有特定结构和性能的COFs。然而,COFs共价键固有的可逆性和高度极化的特性通常导致低的化学稳定性和主体骨架中不连续的π电子离域,从而限制了其在光催化等领域的应用。因此,构建全共轭的COFs对拓展其应用范围尤为重要。一种可行的方法是将COFs的可逆共价键连接基元进行合成后修饰,转化为芳香性的连接基元,来提高其稳定性和共轭性。
1,3,4-恶二唑的衍生物由于其独特的光电性能和生物学特性,在材料科学和药物化学等领域引起了极大的兴趣。传统上含有恶二唑基元的聚合物制备主要是通过酰氯和酰肼反应生成甲酰肼功能基元,然后利用三氯氧磷进行氧化环化。由于酰氯和酰肼反应的不可逆性,通常导致非晶态聚合物的形成,目前含恶二唑基元的COFs仍没有被报道。因此开发一种含恶二唑基元的晶态的聚合物的制备方法,对于拓宽COFs材料的应用范围具有重要意义。
发明内容
本发明的目的为针对当前技术中存在的不足,提供了一种含恶二唑连接基元的COFs及其制备方法,并将其应用于光催化水产氢反应中。该COFs中含有的芳香性恶二唑连接基元,是在保持晶态结构不被破坏的前提下,将COFs中的N-酰基腙连接基元通过铜催化的不可逆氧化环化反应制备而成。本发明提供的COFs合成后修饰策略,不仅拓宽了COFs在可见光区域的吸收范围,而且能更好地促进光生载流子的分离和运输,从而提高了光催化水产氢的性能。
本发明的技术方案为:
一种含恶二唑连接基元的共价有机框架材料,该材料的制备方法包括以下步骤:
(1)在Schlenk管中加入芳香醛、芳香甲酰肼、第一有机溶剂和无机酸水溶液,将所得混合物超声处理10-60分钟,密封、抽真空,100~130℃下反应3~7天后。将生成的固体粉末经洗涤、真空干燥,得到含N-酰基腙连接基元的COFs;
其中,芳香醛的醛基单元和芳香甲酰肼的酰肼单元的摩尔比为1:1;每mmol芳香醛的醛基单元加入6~70mL的第一有机溶剂;无机酸和第一有机溶剂的体积比为1:8~12;
(2)将步骤(1)中得到COFs、铜盐和碳酸盐加入到第二有机溶剂中,在90~120℃下反应3~7天后,将所得到的固体粉末洗涤,并用EDTA-2Na水溶液处理以除去残留的铜离子,经过索氏提取,真空干燥后得到含恶二唑连接基元的COFs;
其中,摩尔比为,COFs:铜盐:碳酸盐=1:1~3:2~3;每1mmol COFs加入200~400mL第二有机溶剂;
步骤(1)中所述的芳香醛是1,3,5-三甲酰基苯,1,3,5-三(4-甲酰苯基)苯,1,3,6,8-四(4-甲酰基苯基)芘,2,4,6-三(4-甲酰苯基)-1,3,5-三嗪四(4-醛基苯基)乙烯,三(4-甲酰苯基)胺,2,4,6-三(4-甲酰苯氧基)-1,3,5-三嗪,1,3,5-三(4′-醛基苯乙炔基)苯,2,2′-联吡啶-5,5′-二甲醛或对苯二醛。
步骤(1)中所述的芳香甲酰肼是2,5-二乙氧基对苯二甲酰肼,对苯二甲酰肼,均苯三甲酰肼,4,4′-联苯二甲酰肼或5,5′-二甲酰肼二联吡啶。
步骤(1)中所述的第一有机溶剂是均三甲苯、二氧六环、邻二氯苯,正丁醇,N,N-二甲基甲酰胺、甲苯和N-甲基吡咯烷酮中的任意一种或多种。
步骤(1)中所述的无机酸水溶液是盐酸、乙酸或硝酸,浓度范围是1~10mol L-1。
步骤(2)中的铜催化剂优选为分成2-4批均量加入,间隔时间为1-2天。
步骤(2)中所述的铜盐是三氟甲磺酸铜、硫酸铜、醋酸铜、氯化铜或溴化铜。
步骤(2)中所述的碳酸盐是碳酸铯,碳酸钾、碳酸钠和碳酸锂中的任意一种。
步骤(2)中所述的第二有机溶剂是N,N-二甲基甲酰胺、二甲基亚砜、乙腈、甲苯和二氧六环中的任意一种或多种。。
步骤(2)中所述的EDTA-2Na水溶液的浓度为0.1~0.5mol L-1。
步骤(2)中所述索氏萃取的溶剂是四氢呋喃、二氯甲烷或乙腈。
本发明的有益效果为:
(1)本发明提供了一种含恶二唑连接基元COFs简单可行的制备方法。通过COFs中N-酰基腙连接基元的合成后修饰,解决了含恶二唑基元COFs难以合成的问题,对于理解该类COFs结构和光电性能的关系提供了理想平台。
(2)本发明提供的含恶二唑基元的COFs具有良好的稳定性。该COFs不仅在水、有机溶剂和光照条件下具有高的稳定性,而且在盐酸、三氟甲磺酸和氢氧化钠等酸性或碱性溶液中长时间浸泡仍具有较好的晶型和孔性质,而含N-酰基腙连接基元的COFs在相同的条件下,很难保持其晶态结构。
(3)本发明提供的含恶二唑连接基元的COFs增加了主体骨架的π电子离域程度。在N-酰基腙连接基元转化为恶二唑后,不仅拓宽了该COFs在可见光区域的吸收范围,同含N-酰基腙连接基元的COFs相比,其带隙从2.8eV降低2.0eV,而且能更好地促进光生载流子的分离和运输,从而提高了光催化水产氢的性能。含恶二唑连接基元的COFs在可见光照射下5小时内H2的产量是13075umol g-1,而含N-酰基腙连接基元的COFs在同样条件下,H2的产量只有3045umol g-1,不到含恶二唑连接基元COFs的四分之一。
附图说明
图1为本发明实施例1含恶二唑连接基元COFs的制备示意图。
图2为本发明实施例1中含N-酰基腙连接基元COF(H-COF)和恶二唑连接基元COF(ODA-COF)的红外谱图。
图3为本发明实施例1含N-酰基腙连接基元COF(H-COF)和恶二唑连接基元COF(ODA-COF)的电化学阻抗谱。
图4为本发明实施例1含N-酰基腙连接基元COF(H-COF)和恶二唑连接基元COF(ODA-COF)的光催化水产氢图。
具体实施方式
为了对本发明的方法有进一步的理解,现结合附图以实施例方式做具体说明。下述实施例仅仅是对本发明的具体制备方法,而不限制本发明的范围。
实施例1
在Schlenk管中,加入1,3,5-三甲酰基苯(32.4mg,0.2mmol),2,5-二乙氧基对苯二甲酰肼(84.9mg,0.3mmol),均三甲苯(6mL),无水二氧六环(2mL)和乙酸水溶液(0.8mL,6M),将所得混合物超声10分钟,然后用液氮经“冷冻-抽真空-解冻”循环三次去除管中的空气,将Schlenk管密封,在120℃下加热3天后,将生成的固体粉末过滤,分别用四氢呋喃和丙酮多次洗涤,在60℃真空干燥12小时得到含N-酰基腙连接基元的COFs。
将含N-酰基腙连接基元的COFs(10mg,0.05mmol)、三氟甲磺酸铜(18mg,0.05mmol)、碳酸铯(32mg,0.1mmol)和N,N-二甲基甲酰胺(15mL)装入干燥的烧瓶中,在120℃下加热72小时,反应期间,再两次加入相同量的三氟甲磺酸铜(即均为18mg,0.05mmol)(每次24小时的间隔)。反应完成后将生成的固体粉末过滤,分别用水和四氢呋喃多次洗涤,加入EDTA-2Na水溶液(0.3mol L-1)在60℃下搅拌12小时以去除残留的铜离子。然后用四氢呋喃进行索氏提取2天进一步纯化,在60℃真空干燥12小时后得到含恶二唑连接基元的COFs。
图1中,本发明实施例1制备的含N-酰基腙连接基元的COF(H-COF)转化为含恶二唑连接基元COF(ODA-COF)的示意图。H-COF中的N-酰基腙连接基元在N,N-二甲基甲酰胺(DMF)溶剂中通过三氟甲烷磺酸铜的催化,氧化环化形成恶二唑连接基元。
图2中,为本发明实施例1中的H-COF和ODA-COF的红外谱图的测试在Perkin-Elmer仪器上,使用溴化钾片上进行测试。在H-COF的红外谱图中,C=N和C=O的伸缩振动分别出现在1625和1670cm-1,而在ODA-COF的红外谱图中,1655和1611cm-1归属于恶二唑环中的C=N特征峰,另外1230和950cm-1归属于恶二唑环中C-O-C的特征峰。这表明了COFs的N-酰基腙连接基元已转化为恶二唑连接基元。
图3中,本发明实施例1制备的含恶二唑连接基元COF(ODA-COF)比含N-酰基腙连接基元COF(H-COF)表现更低的电化学阻抗。光生载流子的分离和传输对材料的光电性能至关重要。由于ODA-COF表现出更小的半圆半径,所以其界面电子传递阻抗较小,因此ODA-COF更有利于光生载流子分离和传输。电化学阻抗的测试在辰华CHI660E工作站上进行。称取5mgCOFs分散在含有Nafion 5%的乙醇溶液中,超声分散均匀。导电玻璃用乙醇和丙酮超声清洗干净,晾干备用。将COFs的分散液均匀滴到导电玻璃一端上面积为1cm2。其余面积用环氧树脂涂抹覆盖。晾干测试。
图4中,本发明实施例1制备的含恶二唑连接基元COF(ODA-COF)比含N-酰基腙连接基元COF(H-COF)在可见光照射下表现更高的光催化水产氢的活性。在300W氙灯(PLS-SXE300D,Beijing Perfectlight)的可见光(≥420nm)照射下,Pt(5μL,9wt%H2PtCl6的水溶液)作为助催化剂和TEOA作为牺牲剂。5小时内ODA-COF产生了13075umol g-1的H2,而同等条件下H-COF仅仅产生了3045umol g-1的H2。气体分析在福立气相色谱(FL 9790PIUS)上进行。
实施例2
在Schlenk管中,加入2,4,6-三(4-甲酰苯基)-1,3,5-三嗪(80.5mg,0.2mmol),2,5-二乙氧基对苯二甲酰肼(84.6mg,0.3mmol),均三甲苯(2.7mL),无水二氧六环(1.3mL)和乙酸水溶液(0.4mL,6M),将所得混合物超声10分钟,然后用液氮经“冷冻-抽真空-解冻”循环三次去除管中的空气,将Schlenk管密封,在120℃下加热3天后,将生成的固体粉末过滤,分别用四氢呋喃和丙酮多次洗涤,在60℃真空干燥12小时得到含N-酰基腙连接基元的COFs。
将含N-酰基腙连接基元的COFs(13mg,0.05mmol)、三氟甲磺酸铜(18mg,0.05mmol)、碳酸铯(32mg,0.1mmol)和超干N,N-二甲基甲酰胺(15mL)装入干燥的烧瓶中,在115℃下加热72小时,反应期间,再两次加入相同量的三氟甲磺酸铜(即均为18mg,0.05mmol)(每次24小时的间隔)。反应完成后将生成的固体粉末过滤,分别用水和四氢呋喃多次洗涤,使用EDTA-2Na水溶液(0.3mol L-1)在60℃下搅拌12小时以去除残留的铜离子。然后用四氢呋喃索氏提取2天进一步纯化,在60℃真空干燥12小时后得到含恶二唑连接基元的COFs。
实施例3
在Schlenk管中,加入1,3,5-三(4-甲酰苯基)苯(78.0mg,0.2mmol),均苯三甲酰肼(50.4mg,0.2mmol),均三甲苯(20mL)、无水二氧六环(20mL)和乙酸水溶液(4mL,6M),将所得混合物超声10分钟,然后用液氮经“冷冻-抽真空-解冻”循环三次去除管中的空气,将Schlenk管密封,在120℃下加热3天后,将生成的固体粉末过滤,用四氢呋喃和丙酮多次洗涤,在60℃真空干燥12小时得到含N-酰基腙连接基元的COFs。
将含N-酰基腙连接基元的COFs(9.8mg,0.05mmol)、三氟甲磺酸铜(18mg,0.05mmol)、碳酸钾(13.8mg,0.1mmol)和超干甲苯(15mL)装入干燥的烧瓶中,在120℃下加热72小时,反应期间,再两次加入相同量的三氟甲磺酸铜(即均为18mg,0.05mmol)(每次24小时的间隔)。反应完成后将生成的固体粉末过滤,分别用水和四氢呋喃多次洗涤,使用EDTA-2Na水溶液(0.3mol L-1)在60℃下处理12小时以去除残留的铜离子。然后用四氢呋喃索氏提取2天进一步纯化,在60℃真空干燥12小时后得到含恶二唑连接基元的COFs。
本发明未尽事宜为公知技术。
Claims (9)
1.一种含恶二唑连接基元的共价有机框架材料,其特征为该材料的制备方法包括以下步骤:
(1)在Schlenk管中加入芳香醛、芳香甲酰肼、第一有机溶剂和无机酸水溶液,将所得混合物超声处理10-60分钟,密封、抽真空,100~130℃下反应3~7天后。将生成的固体粉末经洗涤、真空干燥,得到含N-酰基腙连接基元的COFs;
其中,芳香醛的醛基单元和芳香甲酰肼的酰肼单元的摩尔比为1:1;每mmol芳香醛的醛基单元加入6~70mL的第一有机溶剂;无机酸和第一有机溶剂的体积比为1:8~12;
(2)将步骤(1)中得到COFs、铜盐和碳酸盐加入到第二有机溶剂中,在90~120℃下反应3~7天后,将所得到的固体粉末洗涤,并用EDTA-2Na水溶液处理以除去残留的铜离子,经过索氏提取,真空干燥后得到含恶二唑连接基元的COFs;
其中,摩尔比为,COFs:铜盐:碳酸盐=1:1~3:2~3;每mmol COFs加入200~400mL第二有机溶剂。
2.如权利要求1中所述的含恶二唑连接基元的共价有机框架材料,其特征为步骤(1)中所述的芳香醛是1,3,5-三甲酰基苯,1,3,5-三(4-甲酰苯基)苯,1,3,6,8-四(4-甲酰基苯基)芘,2,4,6-三(4-甲酰苯基)-1,3,5-三嗪四(4-醛基苯基)乙烯,三(4-甲酰苯基)胺,2,4,6-三(4-甲酰苯氧基)-1,3,5-三嗪,1,3,5-三(4′-醛基苯乙炔基)苯,2,2′-联吡啶-5,5′-二甲醛或对苯二醛。
3.如权利要求1中所述的含恶二唑连接基元的共价有机框架材料,其特征为步骤(1)中所述的芳香甲酰肼是2,5-二乙氧基对苯二甲酰肼,对苯二甲酰肼,均苯三甲酰肼,4,4′-联苯二甲酰肼或5,5′-二甲酰肼二联吡啶。
4.如权利要求1中所述的含恶二唑连接基元的共价有机框架材料,其特征为步骤(1)中所述的第一有机溶剂是均三甲苯、二氧六环、邻二氯苯,正丁醇,N,N-二甲基甲酰胺、甲苯和N-甲基吡咯烷酮中的任意一种或多种;步骤(2)中所述的第二有机溶剂是N,N-二甲基甲酰胺、二甲基亚砜、乙腈、甲苯和二氧六环中的任意一种或多种。
5.如权利要求1中所述的含恶二唑连接基元的共价有机框架材料,其特征为步骤(1)中所述的无机酸水溶液是盐酸、乙酸或硝酸,浓度范围是1~10mol L-1。
6.如权利要求1中所述的含恶二唑连接基元的共价有机框架材料,其特征为步骤(2)中铜催化剂优选为分成2-4批均量加入,间隔时间为1-2天。
7.如权利要求1中所述的含恶二唑连接基元的共价有机框架材料,其特征为步骤(2)中所述的铜盐是三氟甲磺酸铜、硫酸铜、醋酸铜、氯化铜或溴化铜。
8.如权利要求1中所述的含恶二唑连接基元的共价有机框架材料,其特征为步骤(2)中所述的碳酸盐是碳酸铯,碳酸钾、碳酸钠和碳酸锂中的一种。
9.如权利要求1中所述的含恶二唑连接基元的共价有机框架材料,其特征为步骤(2)中所述的EDTA-2Na水溶液的浓度为0.1~0.5mol L-1;
步骤(2)中所述索氏萃取的溶剂是四氢呋喃、二氯甲烷或乙腈。
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