CN114456337A - Preparation method of ionic porous organic cage material applied to radioactive iodine adsorption under high-temperature and low-concentration conditions - Google Patents
Preparation method of ionic porous organic cage material applied to radioactive iodine adsorption under high-temperature and low-concentration conditions Download PDFInfo
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- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 54
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011630 iodine Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000002285 radioactive effect Effects 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000007787 solid Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 150000005826 halohydrocarbons Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical class [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims 2
- 238000003795 desorption Methods 0.000 claims 2
- 239000011521 glass Substances 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- CZWSZZHGSNZRMW-UHFFFAOYSA-N 1,2-dibromobutane Chemical compound CCC(Br)CBr CZWSZZHGSNZRMW-UHFFFAOYSA-N 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract 1
- 239000011368 organic material Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000000643 oven drying Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001144 powder X-ray diffraction data Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001559 infrared map Methods 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation 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
- 238000004729 solvothermal method Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
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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
- 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
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a preparation method of an ionic porous organic cage material for radioactive iodine adsorption under the conditions of high temperature and low concentration, belonging to the technical field of porous organic material polymers. At present, most iodine adsorbing materials are only used at low temperature (T is less than or equal to 80 ℃) and high-concentration iodine steam (>10000ppmv) and difficult to be applied in industry (T is more than or equal to 150 ℃, I2Concentration: 150ppmv) application. The invention uses a four-aldehyde-group ring cup [4]]Aromatic hydrocarbon and 3, 5-diamino-1, 2, 4-triazole are used as reaction monomers to synthesize the porous organic cage material NKPOC-DT. Then using iodomethane to modify the mixture to obtain the ionic NKPOC-DT- (I)‑) Me. The obtained ionic porous organic cage can reach the ultra-high iodine adsorption performance of 48.35 wt% under the industrial application condition, and the material can be usedPrepared in batches in pressure-resistant bottles. The ionic porous organic cage material provides a new scheme for treating radioactive iodine in nuclear waste under the condition of industrial iodine adsorption, and the batch preparation of the material can further promote the practical application of the material.
Description
Technical Field
The invention belongs to the technical field of high-molecular organic porous materials, and particularly relates to batch preparation of an ionic porous organic cage material and application of the ionic porous organic cage material in efficient iodine absorption.
Background
Radioactive iodine is one of main harmful radioactive pollutants in nuclear waste, has long half-decay period, is volatile, has quick fluidity and high biological activity, and seriously threatens environmental safety and human health. Therefore, an efficient, economical and recyclable method is developed, and industrial application conditions (T is more than or equal to 150 ℃, I is satisfied2Concentration: 150ppmv) iodine adsorbent has a very important meaning.
Currently, radioiodination is the most commonly used method for adsorption. Wherein the silver impregnated molecular sieve, Al2O3、SiO2Are commonly used adsorbents. However, practical application of silver-based materials is limited by the problems of low specific surface area, low adsorption capacity, poor cyclability, high cost and the like. Although metal organic framework materials with higher BET specific surface area are used for iodine capture, at ≤ 80 deg.C and high concentration of iodine vapor (I>10000ppmv), but the low thermal/chemical stability of the material makes the material difficult to be applied in practical industrial conditions (T is more than or equal to 150 ℃, I2Concentration: 150 ppmv). Although a part of porous organic polymers have high thermal stability, the adsorption rate is slow, the preparation conditions are harsh, the batch preparation is difficult to realize, and the actual industrial application is also difficult to realize. In conclusion, the existing adsorbent cannot meet the requirements of the current industrial iodine adsorption application.
Porous Organic Cages (POCs) are cage-type organic molecules formed by covalent bonds of light elements such as C, H, O, N, B and having a three-dimensional structure. The material has the advantages of rigid skeleton structure, lasting shape, adjustable pore structure, large specific surface area, good thermal/chemical stability, easy post-modification and the like, is widely concerned by researchers, and has wide application prospects in the aspects of adsorption separation, energy storage, sensing, catalysis, pollutant capture and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method capable of efficiently adsorbing radioactive iodine under industrial application conditions (150 ℃, 150ppmv), and solves the problems of high energy consumption, high cost, poor chemical and thermal stability, poor iodine adsorption capacity, complex material synthesis process, slow adsorption rate, poor cyclability and the like of the existing radioactive iodine adsorption technology by preparing an ionic porous organic cage material.
In order to achieve the purpose, the invention provides the following technical scheme:
an ion functionalized porous organic cage material has the following structure, and the synthetic route and the structure after modification (taking methyl iodide modification as an example) of the structure:
BET specific surface area of NKPOC-DT of 1000m2g-1Left and right, ion modified NKPOC-DT- (I)-) Me has a BET specific surface area of 30m2g-1Left and right, ion modified NKPOC-DT- (I)-) Me Industrial iodine adsorption conditions at 150 ℃ (150 ℃, I)2: 150ppmv) can reach an ultra-high iodine adsorption performance of 48.35 wt%. The preparation method comprises the following specific steps:
A. preparation method of NKPOC-DT
Adding tetra-formylcyclopcalix [4] arene (C4 RACHO), 3, 5-diamino-1, 2, 4-triazole and a reaction solvent into a reaction container, uniformly mixing the mixed solution, placing the sealed container into an oven for reaction for a certain time, and carrying out post-treatment on the obtained product such as filtration, washing, drying and the like to obtain the product NKPOC-DT.
Wherein, the tetracyclic [4] arene (C4 RACHO) is synthesized according to the following route, and the specific method is disclosed in J.org.chem.2013,78, 11597-.
Further, in the synthesis of NKPOC-DT, N-Dimethylformamide (DMF) is selected as a reaction solvent, and the molar ratio of the ligand to the solvent is as follows: c4 RACHO: 3, 5-diamino-1, 2, 4-triazole: solvent 1: 2: 775.76. the reaction temperature of the oven is 100 ℃, and the reaction time is 24 h.
Specifically, the method comprises the following steps: adding 1.025g (1.25mmol) of tetra-formyl-intercylcyclo [4] arene (C4 RACHO), 247.73mg (2.5mmol) of 3, 5-diamino-1, 2, 4-triazole and 75mL of DMF (N, N-dimethylformamide) into a 350 mL pressure-resistant bottle, carrying out ultrasonic treatment for 5min, placing the sealed pressure-resistant bottle in an oven at 100 ℃ for reaction for 24h, and carrying out post-treatment on the obtained product by filtering, washing, oven drying and the like to obtain the NKPOC-DT.
In addition to the above preferred modes, the reaction solvent of the invention can also be one or more of N, N-dimethylformamide, N-dimethylacetamide, dioxane, ethanol, methanol, acetonitrile, tetrahydrofuran, mesitylene, trichloromethane and dichloromethane; the molar ratio of ligand to solvent may be selected as: c4 RACHO: 3, 5-diamino-1, 2, 4-triazole: solvent 1: 1-50: 50-50000, the reaction temperature of the oven can be set to 50-150 ℃, and the reaction time is 1-120 h.
B、NKPOC-DT-(I-) Preparation method of Me
Adding NKPOC-DT, halohydrocarbon, reaction solvent and catalyst into a reaction vessel, stirring the reactants for reaction for a certain time, and carrying out post-treatment on the obtained product such as filtration, washing, drying and the like to obtain a product NKPOC-DT- (I)-)Me。
Further, the NKPOC-DT- (I)-) Synthesizing Me, selecting methyl iodide as halogenated hydrocarbon, selecting Diazabicyclo (DBU) as catalyst, selecting acetonitrile (MeCN) as reaction solvent, and the molar ratio of reactants to solvent is as follows: NKPOC-DT: methyl iodide: DBU: acetonitrile 1: 18: 21.6: 10862.7. the stirring reaction temperature is 25 ℃, the stirring environment is nitrogen atmosphere, and the reaction time is 24 hours.
Specifically, the method comprises the following steps: 75mg (0.026mmol) of NKPOC-DT, 29.6 mu L (0.476mmol) of iodomethane, 85.3 mu L (0.571mmol) of DBU (slowly dropwise added) and 15mL (287.031mmol) of acetonitrile are added into a 50mL single-neck flask, the mixture is stirred for 24 hours under the condition of nitrogen at room temperature, and the obtained product is subjected to post-treatment such as filtration, washing, oven drying and the like to obtain the product NKPOC-DT- (I)-)Me。
In addition to the preferable mode, the invention comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dioxane, ethanol, methanol, acetonitrile, tetrahydrofuran, mesitylene, trichloromethane and dichloromethane; the catalyst can be selected from potassium hydroxide or sodium hydroxide besides Diazabicyclo (DBU); the molar ratio of reactants and solvent may be selected as: NKPOC-DT: halogenated hydrocarbon: catalyst: solvent 1: 0.1 to 100: 0.1 to 200: 1000-500000; the temperature of the stirring reaction can be set to be 10-150 ℃, and the reaction time is 1-120 h.
The ion functionalized porous organic cage material is used for adsorbing iodine
Further, the temperature at the time of adsorption was 150 ℃ and the iodine vapor concentration was 150 ppmv.
Furthermore, the iodine adsorption time is 2-20 h.
The ion functionalized porous organic cage after adsorbing iodine can be recycled after desorbing iodine.
The specific steps of desorbing iodine are as follows: and (3) carrying out ion functionalization on the porous organic cage material after iodine adsorption by using a volume ratio of 1: 1, soaking and washing for multiple times by using ethanol and saturated potassium iodide aqueous solution, washing for multiple times by using ultrapure water, and filtering to obtain solid powder, and drying for 12 hours by using an oven at 90-150 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses an ionic POCs material used under the condition of industrial application (150 ℃, I)2Concentration: 150ppmv) of radioactive iodine. Compared with the reported radioactive iodine adsorption material, the ionic POCs material designed by the invention has the advantages of simple synthesis method, batch production, strong thermal and chemical stability, strong iodine adsorption capacity, good cycle performance and the like.
Drawings
FIG. 1 is a PXRD map of NKPOC-DT;
FIG. 2 is an infrared diagram of NKPOC-DT;
FIG. 3 is a thermogram of NKPOC-DT;
FIG. 4 is a nitrogen adsorption diagram of NKPOC-DT;
FIG. 5 shows NKPOC-DT and NKPOC-DT- (I)-) PXRD pattern of Me;
FIG. 6 shows NKPOC-DT and NKPOC-DT- (I)-) An infrared map of Me;
FIG. 7 shows NKPOC-DT and NKPOC-DT- (I)-) Thermogravimetric plot of Me;
FIG. 8 shows NKPOC-DT and NKPOC-DT- (I)-) Nitrogen adsorption profile of Me;
FIG. 9 shows NKPOC-DT and NKPOC-DT- (I)-) Me iodine vapor sorption profile as a function of time;
FIG. 10 is a PXRD pattern of NKPOC-DT prepared under the conditions of example 5;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
Example 1
Adding 1.025g (1.25mmol) of tetra-formyl-intercylcyclo [4] arene (C4 RACHO), 247.73mg (2.5mmol) of 3, 5-diamino-1, 2, 4-triazole and 75mL of DMF (N, N-dimethylformamide) into a 350 mL pressure-resistant bottle, carrying out ultrasonic treatment for 5min, placing the sealed pressure-resistant bottle in an oven at 100 ℃ for reaction for 24h, and carrying out post-treatment on the obtained product by filtering, washing, oven drying and the like to obtain the NKPOC-DT.
Fig. 1 is the PXRD pattern corresponding to example 1, and it can be seen that the porous organic cage NKPOC-DT prepared in the present invention has good crystallinity, and the PXRD pattern obtained in the experiment corresponds well to the XRD pattern obtained by simulation of material studio, which indicates that the porous organic cage NKPOC-DT prepared in this condition has good crystallinity.
Fig. 2 is an infrared spectrum corresponding to example 1, and it can be seen that the successful synthesis of porous organic cage NKPOC-DT is confirmed by the appearance of new infrared characteristic peaks such as C-N, C ═ N.
FIG. 3 is a thermogram corresponding to example 1, and it can be seen that NKPOC-DT exhibits excellent thermal stability.
FIG. 4 is a graph showing the adsorption of nitrogen gas in example 1, wherein NKPOC-DT has a higher BET specific surface area (S)BET＝1003m2g-1). The results also prove that the porous organic cage material NKPOC-DT can be prepared in batches in a simple solvothermal mode and obtain good performance without complex equipment and operations such as a reaction kettle, a pyrex tube, vacuumizing and the like required when the traditional MOFs and POPs are prepared by a solvothermal method. And a solvent heating/volatilization method required by the traditional POCs preparation is not needed, and the product (J.Am.chem.Soc.2020,142,18060-18072) can be obtained by volatilizing for a plurality of weeks, so that the preparation efficiency is greatly improved. The simple preparation mode is beneficial to promoting the practical application of the material.
Example 2
75mg (0.026mmol) of NKPOC-DT obtained in example 1, 29.6. mu.L (0.476mmol) of methyl iodide, 85.3. mu.L (0.571mmol) of DBU (slowly dropwise added) and 15mL (287.031mmol) of acetonitrile were put into a 50mL single-neck flask, stirred at room temperature under nitrogen atmosphere for 24 hours, and the obtained product was subjected to post-treatment such as filtration, washing and oven drying to obtain the product NKPOC-DT- (I)-)Me。
FIG. 5 shows a PXRD pattern corresponding to example 2, which shows that NKPOC-DT- (I) is modified-) Compared with the PXRD pattern of NKPOC-DT, Me changes, but the main characteristic peak is still in, which shows that the modified porous organic cage still retains a better crystal structure.
FIG. 6 is an infrared spectrum corresponding to example 2, from which C-N, CH is shown3The appearance of new infrared characteristic peaks proves that the NKPOC-DT- (I) is a porous organic cage-) The successful synthesis of Me.
FIG. 7 is a thermogram corresponding to example 2, which shows that modified NKPOC-DT- (I)-) The thermal stability of Me is slightly lower than that of unmodified NKPOC-DT, but still shows good thermal stability.
FIG. 8 shows the nitrogen adsorption pattern in example 2, which shows that NKPOC-DT- (I) is modified-) The BET specific surface area of the Me phase is obviously reduced compared with that of the NKPOC-DT, which shows that the modified methyl iodide is successfully grafted to the NKPOC-DT framework.
Example 3
S1 preparation of porous organic cage NKPOC-DT- (I) from example 2-) Drying Me powder sample in 120 deg.C oven for 12 hr, taking appropriate amount of sample, and heatingStabilizing for 1h at 150 ℃ in a re-analyzer;
s2, setting a thermogravimetric analyzer to be at a constant temperature of 150 ℃, and introducing 150ppmv iodine steam purged by nitrogen into the thermogravimetric analyzer;
and S3, after the weight increasing curve is balanced for a period of time, stopping the test, and calculating the adsorption performance of the material to iodine vapor by a gravimetric method according to data recorded by the thermogravimetric curve.
FIG. 9 is a graph showing the adsorption of iodine vapor with time in example 3, which shows that the ionic porous organic cage NKPOC-DT- (I) prepared in example 2-) The adsorption amount of Me to iodine under industrial iodine adsorption conditions (150 ℃, 150ppmv) is 48.35 wt%, which is much higher than that of unmodified NKPOC-DT.
Example 4
The ion functionalized porous organic cage after adsorbing iodine can be reused after desorbing iodine, and specifically comprises the following steps: ion functionalized porous organic cage material NKPOC-DT- (I) after iodine adsorption-) Me was measured by volume ratio of (1: 1) soaking and washing the mixture with saturated potassium iodide solution for many times, washing the mixture with ultrapure water for many times, and filtering the mixture to obtain solid powder, and drying the solid powder for 12 hours in an oven at the temperature of 120 ℃.
Example 5
Adding 2.05g (2.5mmol) of tetra-formyl-intercylcyclo [4] arene (C4 RACHO), 495.46mg (5.0mmol) of 3, 5-diamino-1, 2, 4-triazole and 150mL of DMF (N, N-dimethylformamide) into a 350 mL pressure bottle, carrying out ultrasonic treatment for 5min, placing the sealed pressure bottle in an oven at 100 ℃ for reaction for 24h, and carrying out post-treatment on the obtained product by filtering, washing, oven drying and the like to obtain the NKPOC-DT.
FIG. 10 is a PXRD diagram corresponding to example 5, and it can be seen that the porous organic cage NKPOC-DT prepared by enlarging the reactant charge amount has good crystal form, which proves that the organic cage material can be prepared in bulk and maintain good crystal form.
Example 6
75mg (0.026mmol) of NKPOC-DT obtained in example 5, 19.7. mu.L (0.317mmol) of methyl iodide, 56.8. mu.L (0.381mmol) of DBU, and 15mL (287.031mmol) of acetonitrile were put into a 50mL single-neck flask, stirred at room temperature for 24 hours, and the obtained product was filtered,Washing, drying in a baking oven and the like to obtain the product NKPOC-DT- (I)-)Me。
Example 7
Adding 1.025g (1.25mmol) of tetra-aldehyde polycyclic [4] arene (C4 RACHO), 247.73mg (2.5mmol) of 3, 5-diamino-1, 2, 4-triazole and 60mL of DMF (N, N-dimethylformamide) into a 150mL pressure-resistant bottle, carrying out ultrasonic treatment for 5min, placing the sealed pressure-resistant bottle in an oven at 100 ℃ for reaction for 24h, and carrying out post-treatment on the obtained product by filtering, washing, oven drying and the like to obtain the product NKPOC-DT.
Example 8
75mg (0.026mmol) of NKPOC-DT obtained in example 7, 9.9. mu.L (0.159mmol) of iodomethane, 28.4. mu.L (0.191mmol) of DBU (slowly dropwise addition), and 15mL (287.031mmol) of acetonitrile were put into a 50mL single-neck flask, stirred at room temperature for 24 hours, and the resulting product was post-treated by filtration, washing, oven drying, etc. to obtain a product.
Example 9
75mg (0.026mmol) of NKPOC-DT obtained in example 5, 34.6. mu.L (0.476mmol) of iodoethane, 85.3. mu.L (0.571mmol) of DBU, and 15mL (287.031mmol) of acetonitrile were put into a 50mL single-neck flask, stirred at room temperature for 24 hours, and the obtained product was post-treated by filtration, washing, oven drying, etc. to obtain a product.
Example 10
75mg (0.026mmol) of NKPOC-DT obtained in example 5, 46.3. mu.L (0.476mmol) of bromoethane, 85.3. mu.L (0.571mmol) of DBU, and 15mL (287.031mmol) of acetonitrile were put into a 50mL single-neck flask, stirred at room temperature for 24 hours, and the obtained product was post-treated by filtration, washing, oven drying, etc. to obtain a product.
The invention designs and synthesizes an ionic porous organic cage NKPOC-DT- (I)-) Compared with the reported radioactive iodine adsorption material, the Me has the advantages of simple synthesis method, batch production, strong thermal and chemical stability, strong iodine adsorption capacity, good cycle performance and the like, and can realize the high-efficiency adsorption of iodine under the industrial iodine adsorption condition (150 ℃, 150 ppmv). Compared with MOFs and POPs, the material has simple synthesis process, does not need complex synthesis equipment such as a reaction kettle, a pyrex sealed tube and the like, does not need complex operations such as vacuumizing and the like, can realize batch preparation, and lays a good foundation for the actual industrial application of the materialAnd (4) a foundation. Compared with a solvothermal/volatilization method required by the preparation of the traditional POCs, the product can be obtained without volatilizing for a plurality of weeks, and the preparation efficiency of the POCs is obviously improved. In conclusion, the invention designs and synthesizes the ionic porous organic cage NKPOC-DT- (I)-) The Me is NKPOC-DT- (I) from the aspects of production cost, preparation efficiency, product performance and the like-) The industrial application of Me for realizing iodine adsorption provides great guarantee.
The embodiments described above are presented to enable those skilled in the art to make and use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art: including, but not limited to, modifying all ligands capable of synthesizing ionic POCs, modifying the solvents used for the ligands, modifying the reaction ligand ratios, solvent ratios, catalyst amounts, etc., modifying the reaction times, temperatures, etc., and applying the general principles described herein to other embodiments without undue inventive effort. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should, in light of the present disclosure, appreciate that various modifications and changes can be made without departing from the scope of the invention.
Claims (10)
1. The ionic porous organic cage material for radioactive iodine adsorption under the conditions of high temperature and low concentration is characterized in that the structure of the porous organic cage material and the structure after modification are as follows:
wherein, in the ion modification process, RX represents halohydrocarbon, and X represents F, Cl, Br or I.
2. A preparation method of an ionic porous organic cage material for radioactive iodine adsorption under the conditions of high temperature and low concentration is characterized by comprising the following steps:
A. preparation method of NKPOC-DT
Adding tetracarboxycycline [4] arene (C4 RACHO), 3, 5-diamino-1, 2, 4-triazole and a reaction solvent into a reaction container, uniformly mixing the mixed solution, placing the sealed container into an oven for reacting for a certain time, and filtering, washing and drying the obtained product to obtain a product NKPOC-DT;
B、NKPOC-DT-(X-) Preparation method of R
Adding NKPOC-DT, halohydrocarbon, reaction solvent and catalyst into a reaction vessel, stirring the reactants for reaction for a certain time, filtering, washing and drying the obtained product to obtain the product NKPOC-DT- (X)-)R。
3. The method for preparing the ionic porous organic cage material according to claim 2, wherein in the method for preparing NKPOC-DT, the reaction solvent includes but is not limited to one or more of N, N-dimethylformamide, N-dimethylacetamide, dioxane, ethanol, methanol, acetonitrile, tetrahydrofuran, mesitylene, chloroform, and dichloromethane; the reaction process uses or does not use a catalyst, such as a catalyst, the catalyst comprises but is not limited to trifluoroacetic acid or acetic acid, the reaction vessel comprises but is not limited to a glass bottle, a round-bottom flask or a pressure-resistant bottle, and the uniformly mixing mode comprises but is not limited to stirring and ultrasound.
4. The method of claim 2, wherein the NKPOC-DT is prepared in a molar ratio of ligand to solvent of: c4 RACHO: 3, 5-diamino-1, 2, 4-triazole: solvent 1: 1-50: 50-50000, the reaction temperature of the oven is 50-150 ℃, and the reaction time is 1-120 h.
5. The method for preparing an ionic porous organic cage material according to claim 2, wherein NKPOC-DT- (X)-) In the preparation method of R, the reaction solvent includes, but is not limited to, one or more of N, N-dimethylformamide, N-dimethylacetamide, dioxane, ethanol, methanol, acetonitrile, tetrahydrofuran, mesitylene, chloroform, and dichloromethane; with or without catalyst during the reaction, e.g. with catalysisCatalysts including but not limited to Diazabicyclo (DBU), potassium hydroxide or sodium hydroxide, halogenated hydrocarbons including but not limited to one of methyl iodide, ethyl bromide, 1, 2-dibromobutane, 1, 2-dichloroethane, reaction vessels including but not limited to glass bottles, round bottom flasks or pressure bottles.
6. The method for preparing an ionic porous organic cage material according to claim 2, wherein NKPOC-DT- (X)-) In the preparation method of R, the molar ratio of reactants to a solvent is as follows: NKPOC-DT: halogenated hydrocarbon: catalyst: solvent 1: 0.1 to 100: 0.1 to 200: 1000-500000 ℃, the stirring reaction temperature is 10-150 ℃, the stirring environment can be air or inert gas atmosphere, and the reaction time is 1-120 h.
7. Use of an ionic porous organic cage material according to claim 1 for the adsorption of iodine.
8. Use of an ionic porous organic cage material according to claim 7, wherein the concentration of iodine vapor upon adsorption is 150ppmv and the adsorption temperature is 150 ℃.
9. The use of the ionic porous organic cage material according to claim 7, wherein the time for adsorbing iodine is 1-50 h.
10. The use of the ionic porous organic cage material according to any one of claims 7 to 9, wherein the ionic functionalized porous organic cage after adsorption of iodine can be reused after desorption of iodine, and the specific steps of desorption of iodine are as follows: and (3) carrying out ion functionalization on the porous organic cage material after iodine adsorption by using a volume ratio of 1: 1, soaking and washing for multiple times by using ethanol and saturated potassium iodide aqueous solution, washing for multiple times by using ultrapure water, and filtering to obtain solid powder, and drying for 12 hours by using an oven at 90-150 ℃.
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| CN112608332A (en) * | 2021-01-21 | 2021-04-06 | 福州大学 | Covalent organic cage-shaped compound material with acid stimulation response function and preparation method and application thereof |
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| CN112608332A (en) * | 2021-01-21 | 2021-04-06 | 福州大学 | Covalent organic cage-shaped compound material with acid stimulation response function and preparation method and application thereof |
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