CN113831510B - 一种基于苯并硒二唑的共价有机框架及其制备方法与应用 - Google Patents
一种基于苯并硒二唑的共价有机框架及其制备方法与应用 Download PDFInfo
- Publication number
- CN113831510B CN113831510B CN202110705123.5A CN202110705123A CN113831510B CN 113831510 B CN113831510 B CN 113831510B CN 202110705123 A CN202110705123 A CN 202110705123A CN 113831510 B CN113831510 B CN 113831510B
- Authority
- CN
- China
- Prior art keywords
- benzoselenadiazole
- organic framework
- covalent organic
- diacetonitrile
- diyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 65
- TVNJKAZMPQNGGE-UHFFFAOYSA-N 1,2,3-benzoselenadiazole Chemical compound C1=CC=C2[se]N=NC2=C1 TVNJKAZMPQNGGE-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- 239000000203 mixture Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- MVYRQFKGUCDJAB-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzoselenadiazole Chemical compound BrC1=CC=C(Br)C2=N[se]N=C12 MVYRQFKGUCDJAB-UHFFFAOYSA-N 0.000 claims description 7
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- YKVMTTIYBSVPEQ-UHFFFAOYSA-N [4-(cyanomethyl)phenyl]boronic acid Chemical compound OB(O)C1=CC=C(CC#N)C=C1 YKVMTTIYBSVPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000010257 thawing Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 35
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- -1 palladium ions Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000003708 ampul Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSIFGMFVGDBOQC-UHFFFAOYSA-N 3-iminobutanenitrile Chemical compound CC(=N)CC#N CSIFGMFVGDBOQC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BUOKUWQCVSZNCF-UHFFFAOYSA-N selenadiazole Chemical group C1=C[se]N=N1 BUOKUWQCVSZNCF-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3244—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing only one kind of heteroatoms other than N, O, S
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/52—Luminescence
- C08G2261/522—Luminescence fluorescent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1491—Heterocyclic containing other combinations of heteroatoms
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
本发明涉及有机多孔晶体材料和荧光传感技术领域,具体涉及一种基于苯并硒二唑的共价有机框架及其制备方法与应用。基于苯并硒二唑的共价有机框架结构式如式Ⅰ所示。
Description
技术领域
本发明涉及有机多孔晶体材料和荧光传感技术领域,具体涉及一种基于苯并硒二唑的共价有机框架及其制备方法与应用。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解,而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
共价有机框架(COFs)材料是一种纯有机的晶态多孔材料,具有组成和结构的多样性、较大的比表面积、规则的孔道结构及孔道尺寸可调控等特点。COFs是完全依靠共价键连接构建而成的,具有较好的机械稳定性和化学稳定性。基于以上特点,COFs材料在气体的存储和分离、有机物的吸附、药物分子的负载与运输、光催化、电催化和传感等方面具有广泛的应用价值。
现有技术中通常构筑COFs材料的反应为硼酸脱水反应、硼酸和酚类的反应和席夫碱反应等。目前报道的大多数COFs材料中的连接键为硼氧键和亚胺键,由于其是可逆共价键,在严苛的环境中,会分解而导致COFs骨架的坍塌,这限制了COFs材料的应用。如何构筑更加稳定的COFs材料,这一难题制约着COFs材料的发展。从2016年,基于碳碳双键连接的COFs(sp2 COFs)首次被合成出来,自此,碳碳双键连接的COFs材料开始发展。为了丰富sp2COFs的种类及开发其新的应用,构筑新的sp2 COFs材料非常重要。
硒二唑结构具有优良的光电化学性质,在光电催化和传感中有广泛用途。但由于基于硒二唑的衍生分子在合成上具有一定的难度,使得用于构筑含苯并硒二唑多孔聚合物的单体种类十分有限。sp2 COFs由碳碳双键连接,碳碳双键可逆性差,更加难以得到高质量高结晶性的sp2 COFs材料。在此之前并未有基于苯并硒二唑的碳碳双键连接的共价有机框架材料被制备出来。
因此发明人发现克服合成方面的困难来制备含有苯并硒二唑结构的合适的单体,将其引入到sp2 COFs材料中,不仅丰富了sp2 COFs材料的种类,还能开发其新的应用。
发明内容
针对现有技术中存在的问题,本发明的目的是提供一种基于苯并硒二唑的共价有机框架及其制备方法与应用,本发明通过利用4,4'-(苯并硒二唑-4,7-二基)二乙腈和1,3,6,8-四(4-甲酰基苯基)芘之间发生Knoevenagel缩合反应,填补了之前没有含有苯并硒二唑的碳碳双键连接的共价有机框架材料的空白,所述共价有机框架材料对钯离子有快速响应性和高选择性,荧光强度在2分钟内达到稳定,检测限为0.45μM;本发明方法对设备要求低,制备方法简单,制备的基于苯并硒二唑的碳碳双键连接的共价有机框架材料具有较高的比表面积和较强的化学稳定性,在光电催化和分离方面有很高的应用价值。
为了实现上述目的,本发明的技术方案如下所述:
在本发明的第一方面,提供一种基于苯并硒二唑的共价有机框架,其结构式如式Ⅰ所示:
在本发明的第二方面,提供一种第一方面所述基于苯并硒二唑的共价有机框架的制备方法,所述制备方法为:先将4,7-二溴-2,1,3-苯并硒二唑和4-氰甲基苯硼酸反应生成4,4'-(苯并硒二唑-4,7-二基)二乙腈,结构如式(a)所示;然后4,4'-(苯并硒二唑-4,7-二基)二乙腈和1,3,6,8-四(4-甲酰基苯基)芘发生Knoevenagel缩合反应,得到PY-SE-COF,如式(Ⅰ)所示。
在本发明的第三方面,提供一种第二方面所述基于苯并硒二唑的共价有机框架在钯离子荧光传感器中的应用。
发明的具体实施方式具有以下有益效果:
1、本发明通过利用4,4'-(苯并硒二唑-4,7-二基)二乙腈和1,3,6,8-四(4-甲酰基苯基)芘之间发生Knoevenagel缩合反应,填补了之前没有含有苯并硒二唑的碳碳双键连接的共价有机框架材料的空白;制备方法对设备要求低,制备方法简单,制备的基于苯并硒二唑的共价有机框架材料具有较高的比表面积和较强的化学稳定性,在光电催化和分离方面有很高的应用价值;
2、本发明中的基于苯并硒二唑的共价有机框架材料具有高的比表面积,良好的结晶性和化学稳定性;该材料对钯离子有快速响应性和高选择性,荧光强度在2分钟内达到稳定,检测限为0.45μM。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。
图1为本发明实施例1制得的4,4'-(苯并硒二唑-4,7-二基)二乙腈的核磁共振氢谱图;
图2是本发明实施例1制得的基于苯并硒二唑的共价有机框架材料的粉末X射线衍射图;
图3是本发明实施例1制得的基于苯并硒二唑的共价有机框架材料的红外图谱;
图4是本发明实施例1制得的基于苯并硒二唑的共价有机框架材料的吸脱附曲线图和孔径分布图;
图5本发明实施例1制得的基于苯并硒二唑的共价有机框架材料的扫描电镜图;
图6是本发明实施例1制得的基于苯并硒二唑的共价有机框架材料的钯离子荧光传感图。
图7是本发明实施例1制得的基于苯并硒二唑的共价有机框架材料的荧光强度和钯离子浓度的线性曲线图。
具体实施方式
应该指出,以下详细说明都是例示性的,旨在对本申请提供进一步的说明。除非另有指明,本申请使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本申请的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
本发明的一种实施方式中,提供了一种基于苯并硒二唑的共价有机框架,其结构式如式Ⅰ所示:
PY-SE-COF具有较高的结晶性,是AA堆积形成共价有机框架材料;具有高的比表面积和较强的化学稳定性,且该材料对钯离子有快速响应性和高选择性,检测限达到0.45μM。
本发明的一种实施方式中,提供了一种上述基于苯并硒二唑的共价有机框架的制备方法,所述制备方法为:先将4,7-二溴-2,1,3-苯并硒二唑和4-氰甲基苯硼酸反应生成4,4'-(苯并硒二唑-4,7-二基)二乙腈,然后4,4'-(苯并硒二唑-4,7-二基)二乙腈和1,3,6,8-四(4-甲酰基苯基)芘发生Knoevenagel缩合反应,得到PY-SE-COF,如式(Ⅰ)所示。
具体包括如下步骤:
(1)4,7-二溴-2,1,3-苯并硒二唑与4-氰甲基苯硼酸、四(三苯基膦)钯、碳酸钠混合,以四氢呋喃和水为溶剂,在氮气中回流,冷却后得到混合物,沉降、萃取、分离,得到4,4'-(苯并硒二唑-4,7-二基)二乙腈,如式(a)所示:
(2)将4,4'-(苯并硒二唑-4,7-二基)二乙腈和1,3,6,8-四(4-甲酰基苯基)芘中依次加入邻二氯苯、四丁基氢氧化铵溶液和水,进行冷冻-抽真空-解冻,三次循环后,封管加热,得到PY-SE-COF,如式(Ⅰ)所示。
进一步地,步骤(1)中,所述四氢呋喃和水的体积比为4~6:1;
进一步地,步骤(1)中,回流温度为80-90℃,回流时间为46~50小时;
进一步地,步骤(2)中,所述邻二氯苯、四丁基氢氧化铵和水的体积比为18~22:2~3:1;
进一步地,步骤(2)中,所述四丁基氢氧化铵溶液浓度为0.8~1.2M,溶剂优选甲醇;
进一步地,步骤(2)中,加热温度为110~130℃,加热时间为6~8天;
进一步地,所述冷冻-抽真空-解冻循环三次后,真空封管;
进一步地,步骤(2)中,封管加热后还包括冷却至室温后,将体系抽滤并用四氢呋喃和二氯甲烷洗涤的步骤;
合成路线如下:
本发明通过利用4,4'-(苯并硒二唑-4,7-二基)二乙腈和1,3,6,8-四(4-甲酰基苯基)芘之间发生Knoevenagel缩合反应,填补了之前没有含有苯并硒二唑的碳碳双键连接的共价有机框架材料的空白;制备方法对设备要求低,制备方法简单。
本发明的一种实施方式中,提供了一种上述基于苯并硒二唑的共价有机框架在钯离子荧光传感器中的应用。
基于苯并硒二唑的共价有机框架材料对钯离子有快速响应性和高选择性,荧光强度在2分钟内达到稳定,检测限达到0.45μM。
下面结合具体的实施例对本发明做进一步的解释和说明。
实施例1
(1)4,4'-(苯并硒二唑-4,7-二基)二乙腈的合成:将4,7-二溴-2,1,3-苯并硒二唑(578mg,1.7mmol),4-氰甲基苯硼酸(820mg,5.1mmol)、四(三苯基膦)钯(250mg)、碳酸钠(1.27g)放入100mL圆底烧瓶中,加入30mL四氢呋喃和6mL水为溶剂,混合体系在氮气氛围中85摄氏度加热回流48小时。反应完成后冷却至室温,向体系中加入50mL水,并用二氯甲烷萃取,将粗产物以二氯甲烷为洗脱剂过硅胶柱可得黄绿色固体,为目标产物。4,4'-(苯并硒二唑-4,7-二基)二乙腈的核磁共振氢谱图如图1所示:1H NMR(400MHz,CDCl3)δ7.91(d,J=8.2Hz,4H),7.65(s,2H),7.51(d,J=8.2Hz,4H),3.86(s,4H)。
(2)PY-SE-COF的合成:向5mL安瓿瓶中依次加入4,4'-(苯并硒二唑-4,7-二基)二乙腈(26.46mg,0.064mmol),1,3,6,8-四(4-甲酰基苯基)芘(20mg,0.032mmol),2mL邻二氯苯,0.2mL四丁基氢氧化铵和0.1mL水,将混合体系超声分散均匀,用至于液氮中,冷冻-抽真空-解冻,三次循环三次后,真空封管。将安瓿瓶放置在烘箱中,120℃反应7天。冷却至室温后抽滤并用四氢呋喃和二氯甲烷洗涤,并用四氢呋喃索氏提取3天,得到橙色固体粉末PY-SE-COF,产率为93%。
图2中,粉末X射线衍射图谱看出PY-SE-COF在2.7°和5.5°有较强的衍射峰,表明PY-SE-COF具有较高的结晶性。通过对比理论模拟和实验结果,表明PY-SE-COF是AA堆积形成共价有机框架材料。图3中,1691cm-1峰的减弱和2248cm-1峰的消失的峰分别代表1,3,6,8-四(4-甲酰基苯基)芘中的醛基和4,4'-(苯并硒二唑-4,7-二基)二乙腈中的氰基参与了反应,在2210cm-1处新出现的新的氰基的峰证明Knoevenagel缩合反应的发生。如图4所示的吸附-脱附曲线表明PY-SE-COF的比表面积为786.68m2/g,非线性密度泛函模拟的孔径为2.67nm。图5中,扫描电子显微镜显示该材料的形貌为微米级的不规则的条状结构。图6为该材料对钯离子的荧光响应图,荧光强度在2分钟内达到稳定。图7为PY-SE-COF材料的荧光强度和钯离子浓度的线性曲线,检测限为0.45μM。
实施例2
(1)4,4'-(苯并硒二唑-4,7-二基)二乙腈的合成:将4,7-二溴-2,1,3-苯并硒二唑(1.15g,3.4mmol),4-氰甲基苯硼酸(1.64g,10.2mmol)、四(三苯基膦)钯(500mg)、碳酸钠(2.2g)放入250mL圆底烧瓶中,加入60mL四氢呋喃和12mL水为溶剂,混合体系在氮气氛围中85℃加热回流48小时。反应完成后冷却至室温,向体系中加入50mL水,并用二氯甲烷萃取,将粗产物以二氯甲烷为洗脱剂过硅胶柱可得黄绿色固体,为目标产物;
(2)PY-SE-COF的合成:向5mL安瓿瓶中依次加入4,4'-(苯并硒二唑-4,7-二基)二乙腈(52.92mg,0.128mmol),1,3,6,8-四(4-甲酰基苯基)芘(40mg,0.064mmol),4mL邻二氯苯,0.4mL四丁基氢氧化铵和0.2mL水,将混合体系超声分散均匀,用至于液氮中,冷冻-抽真空-解冻,三次循环三次后,真空封管。将安瓿瓶放置在烘箱中,120℃反应7天。冷却至室温后抽滤并用四氢呋喃和二氯甲烷洗涤,并用四氢呋喃索氏提取3天,得到橙色固体粉末PY-SE-COF,产率为90%。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种基于苯并硒二唑的共价有机框架在钯离子荧光传感器中的应用,其特征在于,其结构式如式Ⅰ所示:
2.一种权利要求1所述基于苯并硒二唑的共价有机框架在钯离子荧光传感器中的应用,其特征在于,所述苯并硒二唑的共价有机框架的制备方法为:先将4,7-二溴-2,1,3-苯并硒二唑和4-氰甲基苯硼酸反应生成4,4'-(苯并硒二唑-4,7-二基)二乙腈,然后4,4'-(苯并硒二唑-4,7-二基)二乙腈和1,3,6,8-四(4-甲酰基苯基)芘发生Knoevenagel缩合反应,得到PY-SE-COF,如式(Ⅰ)所示。
3.如权利要求2所述的应用,其特征在于,包括如下步骤:
(1)4,7-二溴-2,1,3-苯并硒二唑与4-氰甲基苯硼酸、四(三苯基膦)钯、碳酸钠混合,以四氢呋喃和水为溶剂,在氮气中回流,冷却后得到混合物,沉降、萃取、分离,得到4,4'-(苯并硒二唑-4,7-二基)二乙腈,如式(a)所示:
(2)将4,4'-(苯并硒二唑-4,7-二基)二乙腈和1,3,6,8-四(4-甲酰基苯基)芘中依次加入邻二氯苯、四丁基氢氧化铵溶液和水,进行冷冻-抽真空-解冻,三次循环后,封管加热,得到PY-SE-COF,如式(Ⅰ)所示。
4.如权利要求3所述的应用,其特征在于,步骤(1)中,四氢呋喃和水的体积比为4~6:1;
步骤(1)中,回流温度为80-90℃,回流时间为46~50小时。
5.如权利要求3所述的应用,其特征在于,步骤(2)中,邻二氯苯、四丁基氢氧化铵和水的体积比为18~22:2~3:1。
6.如权利要求3所述的应用,其特征在于,步骤(2)中,所述四丁基氢氧化铵溶液浓度为0.8~1.2M。
7.如权利要求3所述的应用,其特征在于,步骤(2)中,溶剂为甲醇。
8.如权利要求3所述的应用,其特征在于,步骤(2)中,加热温度为110~130℃,加热时间为6~8天。
9.如权利要求3所述的应用,其特征在于,冷冻-抽真空-解冻循环三次后,真空封管。
10.如权利要求3所述的应用,其特征在于,步骤(2)中,封管加热后还包括冷却至室温后,将体系抽滤并用四氢呋喃和二氯甲烷洗涤的步骤。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110705123.5A CN113831510B (zh) | 2021-06-24 | 2021-06-24 | 一种基于苯并硒二唑的共价有机框架及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110705123.5A CN113831510B (zh) | 2021-06-24 | 2021-06-24 | 一种基于苯并硒二唑的共价有机框架及其制备方法与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113831510A CN113831510A (zh) | 2021-12-24 |
CN113831510B true CN113831510B (zh) | 2024-04-16 |
Family
ID=78962746
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110705123.5A Active CN113831510B (zh) | 2021-06-24 | 2021-06-24 | 一种基于苯并硒二唑的共价有机框架及其制备方法与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113831510B (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112708090A (zh) * | 2020-12-25 | 2021-04-27 | 上海交通大学 | 一种碳碳双键桥连共价有机框架材料及其制备方法 |
-
2021
- 2021-06-24 CN CN202110705123.5A patent/CN113831510B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112708090A (zh) * | 2020-12-25 | 2021-04-27 | 上海交通大学 | 一种碳碳双键桥连共价有机框架材料及其制备方法 |
Non-Patent Citations (3)
Title |
---|
"Designed synthesis of stable light-emitting two-dimensional sp2 carbon-conjugated covalent organic frameworks";Enquan Jin et al.;《Nature Communications》;第9卷(第1期);1-10 * |
"Fully Conjugated Donor-Acceptor Covalent Organic Frameworks for Photocatalytic Oxidative Amine Coupling and Thioamide Cyclization";Li, Shuai et al.;《ACS Catalysis》;第10卷(第15期);8717-8726 * |
"Fully Conjugated Donor-Acceptor Covalent Organic Frameworks for Photocatalytic Oxidative Amine Coupling and Thioamide Cyclization";Li, Shuai et al.;ACS Catalysis》;第10卷(第15期);8717-872 * |
Also Published As
Publication number | Publication date |
---|---|
CN113831510A (zh) | 2021-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108727402B (zh) | 一种氧杂螺环桥连脲基嘧啶酮化合物及其合成方法 | |
CN113372563B (zh) | 侧链修饰磷酸的共价有机框架化合物及其制备方法和应用 | |
CN110591109B (zh) | 一种碳碳双键桥联的全碳骨架二维共轭有机框架材料及其制备方法 | |
CN115286755B (zh) | 共价有机框架材料及制备方法和在二氧化碳吸附中的应用 | |
CN102070661A (zh) | 一种高纯草酸二氟硼酸锂的制备方法 | |
CN110894299A (zh) | 一种利用低共熔溶剂合成共价有机框架材料的方法 | |
CN110862551A (zh) | 孔道含氟基团多孔芳香骨架材料、制备方法及其在小分子烷烃吸附中的应用 | |
CN108676150A (zh) | 利用次级结构基块构筑的多孔芳香骨架材料 | |
CN111635523A (zh) | 以三聚喹唑啉为结点的二维共价有机框架材料及其制备方法和应 | |
CN113831510B (zh) | 一种基于苯并硒二唑的共价有机框架及其制备方法与应用 | |
CN110372862A (zh) | 一种三苯基菲并咪唑三嗪聚合物及其制备方法和用途 | |
CN113061088B (zh) | 一种不对称柱[5]芳烃及其制备方法和应用 | |
CN108997391B (zh) | 一种三聚茚基bodipy-富勒烯星型化合物的制备方法 | |
CN112479831B (zh) | 基于扭曲六苯并蔻的金属有机框架材料及制备方法与应用 | |
CN108117537B (zh) | 基于四硫富瓦烯单元的三维共价有机框架材料及合成方法 | |
CN113637131B (zh) | 全氟烷基链修饰的共价有机框架、制备方法及其应用 | |
CN112939751B (zh) | 一种芴[n]芳烃大环及其制备方法与在功能共轭带状化合物构建中的应用 | |
CN114456338B (zh) | 一种苯并咪唑基共价有机框架材料的光催化合成方法 | |
CN114605602A (zh) | 一种多级孔共价有机框架化合物及其制备方法与应用 | |
CN113773338B (zh) | 一种含硼有机自由基化合物及其制备方法与应用 | |
CN113150224B (zh) | 一种液晶气凝胶材料的制备方法和应用 | |
CN114805187A (zh) | 双吡啶基多孔有机笼、笼衍生的共价有机框架及应用 | |
CN113666928A (zh) | 一种新型氮原子掺杂于锯齿状边缘的Ovalene-2N的制备方法 | |
CN105175297A (zh) | 4-甲酰苯甲酸金刚烷酯缩邻氨基苯硫酚席夫碱镍配合物合成及应用 | |
CN115611906B (zh) | 一种四(溴乙氧基)含蒽基团的甘脲分子夹、制备方法及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |