CN110606940B - A kind of porous aromatic skeleton material containing carbazole structural unit and its preparation method and application - Google Patents
A kind of porous aromatic skeleton material containing carbazole structural unit and its preparation method and application Download PDFInfo
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 69
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011630 iodine Substances 0.000 claims abstract description 49
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 49
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 230000002285 radioactive effect Effects 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 6
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- ZDRMMTYSQSIGRY-UHFFFAOYSA-N 1,3,5-triethynylbenzene Chemical compound C#CC1=CC(C#C)=CC(C#C)=C1 ZDRMMTYSQSIGRY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 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 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 8
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 6
- 125000001246 bromo group Chemical group Br* 0.000 claims description 5
- -1 carbazole organic compounds Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000001716 carbazoles Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 12
- 238000005406 washing Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 17
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9h-carbazole Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000013312 porous aromatic framework Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- JBWRZTKHMKVFMQ-UHFFFAOYSA-N 3,6-dibromo-9-phenylcarbazole Chemical compound C12=CC=C(Br)C=C2C2=CC(Br)=CC=C2N1C1=CC=CC=C1 JBWRZTKHMKVFMQ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010858 gaseous radioactive waste Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002900 solid radioactive waste Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- 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
- C08G61/124—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 with a five-membered ring containing one nitrogen atom in the ring
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Abstract
本发明属于化学新材料技术领域，具体涉及一种含咔唑结构单元的多孔芳香骨架材料，包括如下步骤：在氮气条件下，将含有溴基的咔唑类有机化合物与1,3,5‑三乙炔基苯置于反应容器中，加入催化剂、有机溶剂80℃反应3天；待反应结束后，冷却到室温，分别用N,N'‑二甲基甲酰胺、四氢呋喃、丙酮、二氯甲烷和甲醇多次洗涤，得到粗产品；再用四氢呋喃、二氯甲烷和甲醇对粗产品进行索氏提取；在90℃真空干燥10小时，得到多孔芳香骨架材料LNUs。本发明采用廉价的单体，反应条件温和，可以在一个反应器皿中一步完成。合成方法具有广泛的适用性。本发明得到的含咔唑结构单元的多孔芳香骨架材料可用于核废料中放射性碘的捕获，具有很好的应用前景。
The invention belongs to the technical field of new chemical materials, and in particular relates to a porous aromatic skeleton material containing carbazole structural units, comprising the following steps: under nitrogen conditions, mixing a bromine-containing carbazole-based organic compound with 1, 3, 5- Triethynylbenzene was placed in the reaction vessel, and a catalyst and an organic solvent were added to react at 80°C for 3 days; after the reaction was completed, it was cooled to room temperature, and N,N'-dimethylformamide, tetrahydrofuran, acetone, and dichloromethane were used respectively. The crude product was obtained by washing with methanol for several times; the crude product was then subjected to Soxhlet extraction with tetrahydrofuran, dichloromethane and methanol; and vacuum-dried at 90°C for 10 hours to obtain the porous aromatic skeleton material LNUs. The invention adopts inexpensive monomers, has mild reaction conditions, and can be completed in one reaction vessel in one step. The synthetic method has broad applicability. The porous aromatic skeleton material containing the carbazole structural unit obtained by the invention can be used for capturing radioactive iodine in nuclear waste, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of new chemical materials, and particularly relates to a porous aromatic skeleton material containing a carbazole structural unit, and a preparation method and application thereof.
Background
With the increasing demand of society for energy, the utilization of nuclear energy is also more and more emphasized in the daily life of human beings. A key issue today is how to safely and efficiently process nuclear waste generated from the nuclear fission of uranium fuel. Compared with solid radioactive wastes, the gaseous radioactive wastes have large fluidity and are easy to migrate along with the airflow, so the polluted area of the gaseous radioactive wastes is pollutedAnd the harm is stronger. Radioactive iodine has been a research hotspot for scientists because of its very long half-life (1.57 × 10)7Years) and can affect the human metabolic response and thus cause physical harm. Therefore, enrichment and storage of gaseous iodine in nuclear power plants has become the most important issue in radioactive waste gas treatment worldwide.
The solid phase adsorption method is the most commonly used method for enriching and storing radioactive gas iodine, and the currently adopted technology for capturing iodine vapor mainly uses zeolite molecular sieves and metal organic framework materials as iodine adsorbents. However, these solid adsorbents have their own drawbacks, such as lower adsorption capacity and poor thermochemical stability, which limit their further applications. Porous aromatic matrix materials are a recently developed class of highly crosslinked, nanoporous polymers. They have low framework density, continuous porosity and high thermochemical stability, so that the porous aromatic framework material has wide application prospects in the fields of gas adsorption, separation, heterogeneous catalysis and the like.
Carbazole is an important nitrogen-containing heterocyclic compound, is relatively stable to heat, acid and alkali, has a rigid main chain and a conjugated electron-rich system, is beneficial to forming a permanent porous material, and has a nitrogen-containing structure which can enhance the interaction between an adsorbate and an adsorbent, so that the adsorption capacity of the carbazole on guest molecules is improved. The invention adopts 1,3, 5-triethylalkynyl benzene and carbazole monomers with different structures as construction elements, prepares a porous aromatic skeleton material containing carbazole structural units through Sonogashira-Hagihara coupling reaction, and systematically characterizes the structure and the performance through analysis methods such as Fourier transform infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, a scanning electron microscope, a transmission electron microscope and the like. The porous aromatic skeleton material has excellent thermochemical stability, simultaneously has a large number of carbazole structural units and rich acetylene bonds, and has a unique skeleton structure which is very favorable for increasing the interaction force between the material and iodine molecules, so that the porous aromatic skeleton material is used as a stable and high-capacity novel solid adsorbent for capturing radioactive iodine in nuclear waste.
Disclosure of Invention
The invention aims to provide a simple and feasible preparation method of a porous aromatic skeleton material containing a carbazole structural unit and application of the porous aromatic skeleton material to radioactive iodine capture.
In order to achieve the purpose, the invention adopts the technical scheme that: a porous aromatic skeleton material LNus containing carbazole structural units is obtained by taking carbazole organic monomers with different structures and 1,3, 5-triethylalkynyl benzene as building elements and utilizing a Sonogashira-Hagihara coupling reaction under the catalysis of tetrakis (triphenylphosphine) palladium and cuprous iodide.
The porous aromatic skeleton material containing the carbazole structural unit has the following structural formula:
the preparation method of the porous aromatic skeleton material containing the carbazole structural unit comprises the following steps: under the condition of nitrogen, putting carbazole organic compounds containing bromo and 1,3, 5-triethynyl benzene into a reaction vessel, adding a catalyst and an organic solvent, and reacting for 3 days at 80 ℃; after the reaction is finished, cooling to room temperature, and respectively washing with N, N' -dimethylformamide, tetrahydrofuran, acetone, dichloromethane and methanol for multiple times to obtain a crude product; then carrying out Soxhlet extraction on the crude product by using tetrahydrofuran, dichloromethane and methanol; vacuum drying at 90 deg.C for 10 hr to obtain porous aromatic skeleton material LNUs.
In the preparation method of the porous aromatic skeleton material containing the carbazole structural unit, the carbazole organic compound containing the bromo group is 3, 6-dibromo-9-phenylcarbazole, 2, 7-dibromocarbazole or 3, 6-dibromocarbazole.
According to the preparation method of the porous aromatic skeleton material containing the carbazole structural unit, the carbazole organic compound containing the bromo group is prepared by the following steps of: 1,3, 5-triethynylbenzene ═ 3: 2.
in the preparation method of the porous aromatic skeleton material containing the carbazole structural unit, the catalyst is a mixture of cuprous iodide and tetrakis (triphenylphosphine) palladium.
The preparation method of the porous aromatic skeleton material containing the carbazole structural unit comprises the following steps of (by mass ratio): tetrakis (triphenylphosphine) palladium ═ 1: 3-5.
In the preparation method of the porous aromatic skeleton material containing the carbazole structural unit, the organic solvent is a mixture of anhydrous N, N' -dimethylformamide and anhydrous triethylamine.
The application of the porous aromatic skeleton material containing the carbazole structural unit as a solid adsorbent in capturing radioactive iodine.
The application and the method are as follows: and (3) placing the porous aromatic skeleton material containing the carbazole structural unit and solid iodine or iodine solution in a closed system to adsorb iodine.
The invention has the beneficial effects that:
1. the invention adopts cheap monomers, has mild reaction conditions and can be completed in one reaction vessel in one step.
2. The synthesis method adopted by the invention has wide applicability.
3. The porous aromatic skeleton material containing the carbazole structural unit prepared by the invention can be used for capturing radioactive iodine in nuclear waste, and has a good application prospect.
Drawings
FIG. 1 a: the infrared spectrogram of the porous aromatic skeleton material LNU-12 synthesized by the method and the reaction monomer;
FIG. 1 b: the infrared spectrogram of the porous aromatic skeleton material LNU-13 synthesized by the method and the reaction monomer;
FIG. 1 c: the infrared spectrogram of the porous aromatic skeleton material LNU-14 synthesized by the method and the reaction monomer;
FIG. 2: the thermogravimetric curve of the porous aromatic skeleton material synthesized by the invention;
FIG. 3: powder X-ray diffraction patterns of the synthetic porous aromatic matrix materials of the present invention;
FIG. 4: scanning electron micrographs of the porous aromatic skeleton material synthesized by the invention;
wherein, a is LNU-12; LNU-13; LNU-14;
FIG. 5: a transmission electron microscope image of the porous aromatic skeleton material synthesized by the invention;
wherein, a is LNU-12; LNU-13; LNU-14;
FIG. 6: the iodine adsorption curve chart of the porous aromatic skeleton material synthesized by the invention;
FIG. 7: the adsorption process of the porous aromatic skeleton material synthesized by the invention in iodine normal hexane solution;
wherein, a is LNU-12; LNU-13; LNU-14;
FIG. 8: the thermogravimetric curve of the porous aromatic skeleton material synthesized by the invention after iodine adsorption;
FIG. 9: the iodine release diagram of the porous aromatic skeleton material synthesized by the invention after absorbing iodine;
Detailed Description
EXAMPLE 1 preparation of porous aromatic framework materials LNUs
The following are examples of the present invention to aid understanding of the present invention, and the scope of the present invention is not limited thereto.
(II) porous aromatic skeleton material LNU-12
1. The synthetic route is as follows:
2. the preparation method comprises the following steps: 801mg (2.00mmol) of 3, 6-dibromo-9-phenylcarbazole, 200mg (1.33mmol) of 1,3, 5-triethylynylbenzene, 30mg of tetrakis (triphenylphosphine) palladium and 10mg of cuprous iodide were added to a 50mL three-necked flask under nitrogen, and then 20mL of anhydrous N, N' -dimethylformamide and 8mL of anhydrous triethylamine were added using a one-shot syringe, and heated to 80 ℃ for 3 days. After the reaction is finished, cooling to room temperature, carrying out suction filtration on the reactant to leave solid insoluble substances, and washing the insoluble substances with N, N' -dimethylformamide, tetrahydrofuran and acetone for multiple times respectively; followed by soxhlet extraction with tetrahydrofuran, dichloromethane and methanol as solvents for 1 day each. The product is dried in vacuum at 90 ℃ for 10h to obtain reddish brown powder which is LNU-12.
(II) porous aromatic skeleton material LNU-13
1. The synthetic route is as follows:
2. the preparation method comprises the following steps: 649mg (2.00mmol) of 2, 7-dibromocarbazole, 200mg (1.33mmol) of 1,3, 5-triethylynylbenzene, 30mg of tetrakis (triphenylphosphine) palladium and 10mg of cuprous iodide were added to a 50mL three-necked flask under nitrogen, and then 20mL of anhydrous N, N' -dimethylformamide and 8mL of anhydrous triethylamine were added using a one-shot syringe, and heated to 80 ℃ for 3 days. After the reaction is finished, cooling to room temperature, carrying out suction filtration on the reactant to leave solid insoluble substances, and washing the insoluble substances with N, N' -dimethylformamide, tetrahydrofuran and acetone for multiple times respectively; followed by soxhlet extraction with tetrahydrofuran, dichloromethane and methanol as solvents for 1 day each. The product is dried in vacuum at 90 ℃ for 10h to obtain reddish brown powder which is LNU-13.
(III) porous aromatic skeleton material LNU-14
1. The synthetic route is as follows:
2. the preparation method comprises the following steps: 649mg (2.00mmol) of 3, 6-dibromocarbazole, 200mg (1.33mmol) of 1,3, 5-triethylynylbenzene, 30mg of tetrakis (triphenylphosphine) palladium and 10mg of cuprous iodide were added to a 50mL three-necked flask under nitrogen, and then 20mL of anhydrous N, N' -dimethylformamide and 8mL of anhydrous triethylamine were added using a one-shot syringe, and heated to 80 ℃ for 3 days. After the reaction is finished, cooling to room temperature, carrying out suction filtration on the reactant to leave solid insoluble substances, and washing the insoluble substances with N, N' -dimethylformamide, tetrahydrofuran and acetone for multiple times respectively; followed by soxhlet extraction with tetrahydrofuran, dichloromethane and methanol as solvents for 1 day each. The product is dried in vacuum at 90 ℃ for 10h to obtain reddish brown powder which is LNU-14.
EXAMPLE 2 detection of porous aromatic framework materials LNUs
As shown in FIG. 1, the prepared porous aromatic skeleton material containing carbazole structural units LNU-12 (FIG. 1a), LNU-13 (FIG. 1b), LNU-14 (FIG. 1c) and the infrared spectra of the corresponding monomers thereof. The uppermost curve in each figure is the IR spectrum of the polymer and the lower curve belongs to the monomer. The characteristic absorption peak (495 cm) of (1) C-Br bond can be clearly observed-1) Disappearance in the product demonstrates the cleavage of the C-Br bond in the monomer; (2) C-H vibration of the product without the end of the alkynyl group (3300 cm)-1) Proves that the coupling reaction between the raw materials indeed occurs; (3) near 2200cm in the infrared spectrum of the final product-1Characteristic absorption peaks of alkynyl-C.ident.C-can be seen. The above results demonstrate the success of the coupling reaction.
As shown in FIG. 2, the thermogravimetric diagram of the porous aromatic skeleton material LNU-12(a), LNU-13(b), LNU-14(c) containing carbazole structural units prepared by the invention is at 10 ℃ for min in nitrogen atmosphere-1Thermogravimetric curves of the three samples under the test conditions. As can be seen from the figure, these polymer backbones are very stable and do not start to decompose until 350 ℃, indicating that these materials have very good thermal stability. Meanwhile, when the solubility of the polymer material is tested, the sample is not dissolved or decomposed in common organic solvents (such as methanol, ethanol, tetrahydrofuran, acetone, dichloromethane, chloroform, DMF, DMSO and the like), and the polymer is proved to have very good chemical stability.
As shown in FIG. 3, the powder X-ray diffraction patterns of the porous aromatic skeleton materials LNU-12(a), LNU-13(b) and LNU-14(c) containing carbazole structural units prepared by the invention are shown. No obvious XRD diffraction peak is observed from the figure, and the structure of the porous aromatic skeleton material is proved to be amorphous.
As shown in FIG. 4, the scanning electron microscope images of the porous aromatic skeleton materials LNU-12(a), LNU-13(b), LNU-14(c) containing carbazole structural units prepared by the invention are shown. From the photographs, LNU-12 is an irregular bulk morphology, LNU-13 and LNU-14 are spheroidal morphologies with a size of 500nm-10 μm.
As shown in FIG. 5, a transmission electron microscope image of the porous aromatic skeleton material LNU-12(a), LNU-13(b), LNU-14(c) containing carbazole structural units prepared by the invention is shown. It is clear from the photographs that the LNUs material has a worm-like channel structure.
EXAMPLE 3 use of porous aromatic framework materials LNUs for adsorption of vapor iodine
30mg of dried LNUs powder were placed in pre-weighed glass bottles and simultaneously with 10g of solid iodine in a closed system at 75 ℃ and the samples were weighed at different intervals during the iodine adsorption process. As shown in FIG. 6, the iodine adsorption by LNUs increased rapidly during the initial 5h, followed by a gradual decrease in the rate of mass increase, with no significant change in mass after 48h, indicating substantial saturation of the iodine adsorption by LNUs. The calculation results show that LNU-12, LNU-13 and LNU-14 all have higher iodine adsorption amounts, which are respectively 2.9g/g, 2.1g/g and 2.2 g/g. The experiments prove that the adsorption capacity of LNUs to iodine is obviously higher than that of most porous materials, and the porous material has a very good application prospect in the field of radioactive iodine capture.
EXAMPLE 4 use of porous aromatic framework materials LNUs for adsorption of iodine in solution
At room temperature, 25mg of LNU-12, LNU-13, LNU-14 material was immersed in 3mL of a pre-formulated solution of elemental iodine in n-hexane (300mg L)-1) In (1). As shown in FIG. 7, the porous aromatic skeleton materials LNU-12(a), LNU-13(b), LNU-14(c) containing carbazole structural units prepared by the invention are adsorbed in iodine normal hexane solution. As can be seen from the figure, the color of the initial solution is purple of the iodine simple substance, but with the lapse of time, the normal hexane solution containing the iodine simple substance is almost colorless when the adsorption time is 24h, which proves that the LNUs material can adsorb iodine molecules from the normal hexane solution, and the LNUs have strong adsorption performance on iodine in the solution.
As shown in FIG. 8, the thermogravimetric curves of the porous aromatic skeleton materials LNU-12(a), LNU-13(b), LNU-14(c) containing carbazole structural units prepared by the invention after iodine adsorption. Thermogravimetric analysis showed similar thermogravimetric curves for all samples of LNU-12, LNU-13, and LNU-14 loaded with iodine, with a significant mass loss observed from 90 ℃ to 350 ℃ (184 ℃ for elemental iodine boiling point) due to volatilization of iodine located on the polymer surface and in the channels inside the backbone.
EXAMPLE 4 Cyclic use Properties of porous aromatic backbone materials LNUs
Iodine release experiments were performed on LNUs material after iodine capture at 120 ℃. Firstly, adsorbing iodine for 48h by LNUs material at 75 ℃, then heating for 320min at 120 ℃, and carrying out iodine release experiment in air to obtain the iodine release efficiency of the LNUs at different time. FIG. 9 is a graph showing the iodine release of porous aromatic skeleton materials LNU-12, LNU-13, LNU-14 containing carbazole structural units prepared in the present invention. As can be seen from the figure, the release rates of LNU-12, LNU-13 and LNU-14 for iodine are respectively 98%, 97% and 89%, and it can be seen that the porous aromatic skeleton material containing carbazole structural units has higher release rate of iodine. The material can be recycled, which is very important in the practical application of capturing iodine simple substance.
Claims (5)
1. The application of a porous aromatic skeleton material containing carbazole structural units as a solid adsorbent in capturing radioactive iodine is characterized in that the method comprises the following steps: placing a porous aromatic skeleton material containing a carbazole structural unit and solid iodine or iodine solution in a closed system to adsorb iodine; the porous aromatic skeleton material containing the carbazole structural unit is prepared by taking carbazole organic monomers with different structures and 1,3, 5-triethylalkynyl benzene as construction elements and utilizing Sonogashira-Hagihara coupling reaction under the catalysis of tetrakis (triphenylphosphine) palladium and cuprous iodide to obtain the porous aromatic skeleton material LNUs containing the carbazole structural unit, and has the following structural formula:
2. The use according to claim 1, wherein the porous aromatic skeleton material comprising carbazole structural units comprises the following steps: under the condition of nitrogen, putting carbazole organic compounds containing bromo and 1,3, 5-triethylalkynyl benzene into a reaction vessel, adding tetrakis (triphenylphosphine) palladium, cuprous iodide and an organic solvent, and reacting for 3 days at 80 ℃; after the reaction is finished, cooling to room temperature, and respectively usingN,N'-dimethylformamide, tetrahydrofuran, acetone, dichloromethane and methanol are washed for a plurality of times to obtain a crude product; then carrying out Soxhlet extraction on the crude product by using tetrahydrofuran, dichloromethane and methanol; vacuum drying at 90 deg.C for 10 hr to obtain porous aromatic skeleton material LNUs.
3. The use according to claim 2, characterized in that the organic bromine group-containing carbazoles compounds are, in molar ratios: 1,3, 5-triethynylbenzene = 3: 2.
4. use according to claim 2, characterized in that the ratio by mass of cuprous iodide: tetrakis (triphenylphosphine) palladium = 1: 3-5.
5. Use according to claim 2, wherein the organic solvent is anhydrousN,N'-a mixture of dimethylformamide and anhydrous triethylamine.
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