CN108164549B - COFs materials based on flexible modules and their preparation methods and uses - Google Patents
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
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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
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Abstract
本发明属于有机多孔材料吸附剂领域,具体涉及基于柔性模块构筑的COFs材料及其制备方法和用途。本发明提供了一种基于柔性模块构筑的COFs材料,其结构如式Ⅰ所示。本发明还提供了上述基于柔性模块构筑的COFs材料的制备方法,以及其作为碘吸附剂的用途。本发明以柔性模块制备的一系列大晶格尺寸的COFs材料均表现出极高的碘富集能力,在常规及放射性碘的富集和分离领域具有极大的实用前景。
The invention belongs to the field of organic porous material adsorbents, and in particular relates to a COFs material constructed based on flexible modules and a preparation method and application thereof. The present invention provides a COFs material constructed based on flexible modules, the structure of which is shown in formula I. The present invention also provides a preparation method of the above-mentioned COFs material constructed based on flexible modules, and its use as an iodine adsorbent. A series of COFs materials with large lattice size prepared by the flexible module of the present invention all show extremely high iodine enrichment ability, and have great practical prospects in the field of enrichment and separation of conventional and radioactive iodine.
Description
技术领域technical field
本发明属于有机多孔材料吸附剂领域,具体涉及基于柔性模块构筑的COFs材料及其制备方法和用途。The invention belongs to the field of organic porous material adsorbents, and in particular relates to a COFs material constructed based on flexible modules and a preparation method and application thereof.
背景技术Background technique
共价有机框架材料(Covalent Organic Frameworks,COFs)是由有机分子构筑基元通过共价键连接而制备的一类多孔晶态材料。COFs具有大的比表面积,优异的化学和生物稳定性,易于功能化修饰以及高度有序的周期性的序列等特性,在气体储存、分离、催化、检测、光电子学和能量储存材料等方面具有重要的应用价值。尽管过去十年间,特别是近五年来,COFs的研究取得了巨大的进展,但对于如何简单有效地制备结构规整、高结晶度的COFs仍然存在较大的难度。为了获得好的晶型结构,COFs一般选用较为刚性的单体模块和特殊的成键方式,成键后的分子链通常整体呈直线型或接近直线型,如硼双氧键、碳氮双键、碳碳双键、炔键等,这种设计方式极大地限制了COFs的构成种类和结构类型。采用种类多样的柔性构筑模块制备COFs则为丰富COFs的结构多样性及复杂性创造了可能。特别是基于软性模块构筑的共价有机框架材料因其柔性模块比刚性单体具有更大的旋转自由度,所以具有更大的潜在的伸展性和更多样的堆叠方式。但是,也正是由于柔性模块大的旋转自由度,以柔性模块制备的COFs很难获得规则排布的空间结构和高的结晶度。因此,基于柔性模块构筑高度结晶和新颖的共价有机框架材料仍是一个具有挑战性的研究方向。Covalent Organic Frameworks (COFs) are a class of porous crystalline materials prepared by connecting organic molecular building blocks through covalent bonds. COFs have the characteristics of large specific surface area, excellent chemical and biological stability, easy functionalization and highly ordered periodic sequence, etc. important application value. Although the research on COFs has made great progress in the past ten years, especially in the past five years, there is still great difficulty in how to easily and effectively prepare COFs with regular structure and high crystallinity. In order to obtain a good crystal structure, COFs generally use relatively rigid monomer modules and special bonding methods. The molecular chain after bonding is usually linear or nearly linear as a whole, such as boron double oxygen bonds, carbon nitrogen double bonds. , carbon-carbon double bonds, alkyne bonds, etc., this design method greatly limits the composition and structure types of COFs. Using a variety of flexible building blocks to prepare COFs creates the possibility to enrich the structural diversity and complexity of COFs. In particular, covalent organic framework materials based on soft modules have greater potential stretchability and more diverse stacking methods because the flexible modules have greater rotational freedom than rigid monomers. However, due to the large rotational freedom of flexible modules, it is difficult to obtain regularly arranged spatial structures and high crystallinity for COFs prepared from flexible modules. Therefore, the construction of highly crystalline and novel covalent organic frameworks based on flexible modules remains a challenging research direction.
对于材料的实际应用而言,高的结晶度和规整有序的结构排布会大大增加材料在光学、电学等领域的应用性能。然而在很多时候,良好的结晶度并不意味着必然拥有良好的应用性能,如材料在吸附、分离、催化等领域的应用。因此,如何有效地控制共价有机框架材料结晶度并由此调节其相关的应用性能则是一个极具现实意义的研究课题,特别是对具有重要拓展价值的、基于柔性模块构筑的、大晶格尺寸的COFs材料更加具有重要的意义,这项研究可能带给COFs材料史无前例的性能和应用前景。For the practical application of materials, high crystallinity and regular and orderly structure arrangement will greatly increase the application performance of materials in the fields of optics, electricity and so on. However, in many cases, good crystallinity does not necessarily mean good application properties, such as the application of materials in the fields of adsorption, separation, and catalysis. Therefore, how to effectively control the crystallinity of covalent organic framework materials and thereby adjust their related application properties is a research topic of great practical significance, especially for the large-scale crystals with important development value based on flexible modules. Lattice-sized COFs materials are more important, and this research may bring unprecedented performance and application prospects to COFs materials.
碘-129是气载放射性核废物中最重要的放射性污染物,因其具有极长的放射性半衰期(1.57×107年)、易挥发性和生物相容性,对生态环境和人类健康产生极大的危害。因此,设计制备适合的材料用于碘的高效捕获和储存对公共安全和核能安全均至关重要。人们习惯使用天然的或人工合成的分子筛等无机复合材料吸附剂作为碘吸附剂,但该类材料对碘的吸附能力并不理想,吸附容量也比较低。多孔材料由于具有较为优越的比表面积和孔隙率,以及较为规则的孔径结构,是目前碘吸附材料研究的热点之一。其中主要包括无机多孔材料、金属有机框架材料(MOFs)和多孔有机聚合物(POPs)。无机多孔材料对碘的负载率通常在8%到175%之间,相对较低。同时因无机多孔材料循环使用能力差,限制了其在碘捕获中的应用。金属有机框架材料表现出比无机吸附材料更为优越的碘摄取能力,然而因其较差的水分和湿度稳定性以及酸碱稳定性,MOFs材料难以用于实际的核废气(含大量的水蒸气)中碘的捕获和储存。Iodine-129 is the most important radioactive pollutant in airborne radioactive nuclear waste, because of its extremely long radioactive half-life (1.57×10 7 years), volatility and biocompatibility, it is extremely harmful to the ecological environment and human health. big hazard. Therefore, the design and preparation of suitable materials for efficient capture and storage of iodine is crucial for both public safety and nuclear energy safety. People are used to using inorganic composite adsorbents such as natural or synthetic molecular sieves as iodine adsorbents, but the adsorption capacity of such materials for iodine is not ideal, and the adsorption capacity is relatively low. Porous materials are one of the hotspots in the research of iodine adsorption materials due to their superior specific surface area, porosity, and relatively regular pore structure. These mainly include inorganic porous materials, metal-organic frameworks (MOFs), and porous organic polymers (POPs). The loading rate of iodine by inorganic porous materials is usually between 8% and 175%, which is relatively low. At the same time, the poor recycling ability of inorganic porous materials limits their application in iodine capture. Metal-organic frameworks exhibit superior iodine uptake ability than inorganic adsorbents, however, due to their poor moisture and humidity stability and acid-base stability, MOFs are difficult to use in practical nuclear exhaust gas (containing a large amount of water vapor). ) capture and storage of iodine.
发明内容SUMMARY OF THE INVENTION
本发明提供了一种基于柔性模块构筑的COFs材料,其结构如式Ⅰ所示:The present invention provides a COFs material constructed based on flexible modules, the structure of which is shown in formula I:
其中,R1、R2独立地为-H或-OH。优选的,R1、R2均为-H。优选的,R1、R2均为-OH。wherein, R 1 and R 2 are independently -H or -OH. Preferably, both R 1 and R 2 are -H. Preferably, both R 1 and R 2 are -OH.
本发明还提供了上述基于柔性模块构筑的COFs材料的制备方法,包括以下步骤:The present invention also provides the above-mentioned preparation method of the COFs material constructed based on the flexible module, comprising the following steps:
a、2,4,6-三对甲酰苯氧基-1,3,5-三嗪的制备:将对羟基苯甲醛溶解于混合溶剂中,在0~5℃下加入碱,搅拌10~30min;缓慢滴加丙酮溶解的三聚氯氰溶液,持续在0~5℃反应0.5~2h;然后升温至回流反应1~5h,自然冷却,将反应后的溶液倒入蒸馏水中,过滤,固体用碱溶液洗涤,真空干燥,得到2,4,6-三对甲酰苯氧基-1,3,5-三嗪(TPT-CHO);a. Preparation of 2,4,6-tri-p-formylphenoxy-1,3,5-triazine: dissolve p-hydroxybenzaldehyde in mixed solvent, add alkali at 0~5℃, stir for 10~ 30min; slowly add acetone-dissolved cyanuric chloride solution dropwise, continue to react at 0-5°C for 0.5-2h; then heat up to reflux for 1-5h, cool naturally, pour the reacted solution into distilled water, filter, solid Washed with alkaline solution and dried in vacuo to obtain 2,4,6-tri-p-formylphenoxy-1,3,5-triazine (TPT-CHO);
b、基于柔性模块构筑的COFs材料的制备:将取代的联苯胺和混合溶剂、TPT-CHO和混合溶剂分别超声2~10min,都分别形成均匀分散液,然后在TPT-CHO分散液中缓慢加入乙酸,密封,于60~100℃下静置反应2~5天,获得基于柔性模块构筑的COFs材料。b. Preparation of COFs based on flexible modules: ultrasonically sonicated the substituted benzidine and mixed solvent, TPT-CHO and mixed solvent for 2-10 min respectively to form a uniform dispersion, and then slowly added to the TPT-CHO dispersion Acetic acid, sealed, and left to react at 60-100 °C for 2-5 days to obtain COFs materials based on flexible modules.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤a所述的混合溶剂为丙酮和水的混合溶剂;所述丙酮与水的体积比为5:1~1:2。In the above-mentioned preparation method of COFs materials based on flexible modules, the mixed solvent in step a is a mixed solvent of acetone and water; the volume ratio of acetone to water is 5:1 to 1:2.
上述的基于柔性模块构筑的COFs材料的制备方法中,所述的碱为NaOH、KOH、CsOH、Ca(OH)2、Sr(OH)2或Ba(OH)2中的任意一种;所述对羟基苯甲醛与碱的摩尔比为1︰1~1︰2。In the above-mentioned preparation method of COFs materials based on flexible modules, the alkali is any one of NaOH, KOH, CsOH, Ca(OH) 2 , Sr(OH) 2 or Ba(OH) 2 ; The molar ratio of p-hydroxybenzaldehyde to alkali is 1:1~1:2.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤a所述对羟基苯甲醛与三聚氯氰的摩尔比为5︰1~3︰1。In the above-mentioned preparation method of COFs material based on flexible module construction, the molar ratio of p-hydroxybenzaldehyde to cyanuric chloride in step a is 5:1 to 3:1.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤a所述碱溶液中的碱与对羟基苯甲醛的摩尔比为3︰2~3︰1;所述的碱溶液为饱和的NaHCO3溶液、8~16%的Na2CO3溶液或5~10%的NaOH溶液中的任意一种。In the above-mentioned preparation method of COFs material based on flexible module construction, the molar ratio of alkali to p-hydroxybenzaldehyde in the alkali solution described in step a is 3:2 to 3:1; the alkali solution is saturated NaHCO 3 Either solution, 8-16% Na 2 CO 3 solution or 5-10% NaOH solution.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤b所述的混合溶剂为均三甲苯(1,3,5-三甲苯)/二氧六环溶剂;所述均三甲苯与二氧六环的体积比为3︰1~1︰3。In the above-mentioned preparation method of COFs material based on flexible module construction, the mixed solvent described in step b is mesitylene (1,3,5-trimethylbenzene)/dioxane solvent; The volume ratio of the six rings is 3:1 to 1:3.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤b所述取代的联苯胺与TPT-CHO的摩尔比为7︰4~6︰5。In the above-mentioned preparation method of COFs material based on flexible module construction, the molar ratio of the substituted benzidine described in step b to TPT-CHO is 7:4 to 6:5.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤b所述乙酸的浓度为5~15M;所述乙酸与TPT-CHO的摩尔比为3︰1~15︰1。In the above-mentioned preparation method of COFs material based on flexible module construction, the concentration of acetic acid in step b is 5-15M; the molar ratio of acetic acid and TPT-CHO is 3:1-15:1.
上述基于柔性模块构筑的COFs材料的制备方法的反应式为:The reaction formula of the above-mentioned preparation method of COFs materials based on flexible modules is:
其中,R1、R2独立地为-H或-OH。优选的,R1、R2均为-H。wherein, R 1 and R 2 are independently -H or -OH. Preferably, both R 1 and R 2 are -H.
本发明还提供了上述基于柔性模块构筑的COFs材料作为碘吸附剂的用途。The present invention also provides the use of the above-mentioned COFs material constructed based on the flexible module as an iodine adsorbent.
本发明创造性地使用含三嗪环和醚键的大柔性单体,作为构筑模块采用醛胺缩合反应制备COFs材料。这种原位氮荷载的方式使产物结构中具备丰富的氮原子,从而可大大增加其对碘的负载率。同时,制备的COFs材料具有良好晶形和大晶格尺寸,这在以柔性模块构建的COFs领域极为少见。本发明通过理论计算和实验研究,首次深入探讨了COFs材料层内氢键含量对柔性模块构筑COFs的结晶度及其碘吸附性能的影响,研究发现,氢键降低了构筑单元的旋转自由度,使COFs部分结构被锁定,从而有效地增大了材料的结晶度。因此通过控制体系中氢键的含量即可有效地实现产物COFs结晶度的调控。然而,氢键的存在同时也占用了大量的吸附活性位点,使得材料对碘的捕获性能明显下降。而本发明以柔性模块制备的一系列大晶格尺寸的COFs材料均表现出极高的碘富集能力,最大吸附量高达未见报道的5.43g/g,是目前所有类型的吸附材料中最高的,这一特性使其在放射性核废物后处理放射性碘的富集领域具有极大的实用前景。The invention creatively uses a large flexible monomer containing a triazine ring and an ether bond as a building block to prepare a COFs material by an aldol-amine condensation reaction. This in-situ nitrogen loading method makes the product structure with abundant nitrogen atoms, which can greatly increase the loading rate of iodine. At the same time, the prepared COFs have good crystal shape and large lattice size, which are extremely rare in the field of COFs constructed with flexible modules. The present invention, through theoretical calculation and experimental research, for the first time deeply discusses the influence of the hydrogen bond content in the COFs material layer on the crystallinity and iodine adsorption performance of the flexible module constructed COFs. It is found that the hydrogen bond reduces the rotational freedom of the building unit, The partial structure of COFs is locked, thereby effectively increasing the crystallinity of the material. Therefore, the crystallinity of the product COFs can be effectively controlled by controlling the content of hydrogen bonds in the system. However, the existence of hydrogen bonds also occupies a large number of adsorption active sites, which makes the material's capture performance for iodine significantly decrease. However, a series of COFs materials with large lattice size prepared by flexible modules in the present invention all show extremely high iodine enrichment capacity, and the maximum adsorption capacity is as high as 5.43 g/g, which has never been reported, which is the highest among all types of adsorption materials at present. This feature makes it have great practical prospects in the field of enrichment of radioactive iodine in the reprocessing of radioactive nuclear waste.
附图说明Description of drawings
图1本发明提供的共价有机框架材料TPT-BD COF(化合物1)和TPT-DHBD COF(化合物2)的固体核磁谱图(a,b)和X射线光电子能谱图(c,d)。Fig. 1 Solid NMR spectra (a, b) and X-ray photoelectron spectra (c, d) of the covalent organic framework materials TPT-BD COF (compound 1) and TPT-DHBD COF (compound 2) provided by the present invention .
图2本发明提供的共价有机框架材料TPT-BD COF(化合物1)和TPT-DHBD COF(化合物2)的粉末X射线衍射图谱及Materials Studio计算模拟结构。Fig. 2 Powder X-ray diffraction patterns of the covalent organic framework materials TPT-BD COF (compound 1) and TPT-DHBD COF (compound 2) provided by the present invention and the computational simulation structures of Materials Studio.
图3本发明提供的共价有机框架材料TPT-BD COF(化合物1)和TPT-DHBD COF(化合物2)经总剂量105Gy的γ射线辐照前后的红外光谱图。Fig. 3 Infrared spectra of the covalent organic framework materials TPT-BD COF (compound 1) and TPT-DHBD COF (compound 2) provided by the present invention before and after irradiation with a total dose of 10 5 Gy of gamma rays.
图4化合物1~5对碘的吸附时间曲线。Figure 4. The adsorption time curves of compounds 1-5 for iodine.
图5化合物1~5对碘的解吸曲线。Figure 5. Desorption curves of compounds 1-5 for iodine.
图6本发明提供的共价有机框架材料TPT-BD COF(化合物1)和TPT-DHBD COF(化合物2)及三种反应原料的红外光谱图。Fig. 6 Infrared spectra of the covalent organic framework materials TPT-BD COF (compound 1) and TPT-DHBD COF (compound 2) provided by the present invention and three reaction raw materials.
图7化合物1~5的红外光谱图。Fig. 7 Infrared spectra of compounds 1-5.
图8本发明共价有机框架材料TPT-BD COF(化合物1)吸附碘前后的红外光谱图。Fig. 8 Infrared spectra of the covalent organic framework material TPT-BD COF (compound 1) of the present invention before and after adsorption of iodine.
图9化合物2(TPT-DHBD COF)吸附碘前后的热重曲线。Figure 9. Thermogravimetric curves of compound 2 (TPT-DHBD COF) before and after iodine adsorption.
图10化合物1(TPT-BD COF)的循环吸附实验。Figure 10 Cyclic adsorption experiment of compound 1 (TPT-BD COF).
具体实施方式Detailed ways
基于柔性模块构筑的COFs材料的制备方法,包括以下步骤:The preparation method of COFs material based on flexible module construction includes the following steps:
a、2,4,6-三对甲酰苯氧基-1,3,5-三嗪的制备:将对羟基苯甲醛溶解于混合溶剂中,在0~5℃下加入碱,搅拌10~30min;缓慢滴加丙酮溶解的三聚氯氰溶液,持续在0~5℃反应0.5~2h;然后升温至回流反应1~5h,自然冷却,将反应后的溶液倒入蒸馏水中,过滤,固体用碱溶液洗涤,真空干燥,得到2,4,6-三对甲酰苯氧基-1,3,5-三嗪(TPT-CHO);a. Preparation of 2,4,6-tri-p-formylphenoxy-1,3,5-triazine: dissolve p-hydroxybenzaldehyde in mixed solvent, add alkali at 0~5℃, stir for 10~ 30min; slowly add acetone-dissolved cyanuric chloride solution dropwise, continue to react at 0-5°C for 0.5-2h; then heat up to reflux for 1-5h, cool naturally, pour the reacted solution into distilled water, filter, solid Washed with alkaline solution and dried in vacuo to obtain 2,4,6-tri-p-formylphenoxy-1,3,5-triazine (TPT-CHO);
b、基于柔性模块构筑的COFs材料的制备:将取代的联苯胺和混合溶剂、TPT-CHO和混合溶剂分别超声2~10min,都分别形成均匀分散液,然后在TPT-CHO分散液中缓慢加入乙酸,密封,于60~100℃下静置反应2~5天,获得基于柔性模块构筑的COFs材料。b. Preparation of COFs based on flexible modules: ultrasonically sonicated the substituted benzidine and mixed solvent, TPT-CHO and mixed solvent for 2-10 min respectively to form a uniform dispersion, and then slowly added to the TPT-CHO dispersion Acetic acid, sealed, and left to react at 60-100 °C for 2-5 days to obtain COFs materials based on flexible modules.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤a所述的混合溶剂为丙酮和水的混合溶剂;所述丙酮与水的体积比为5:1~1:2。In the above-mentioned preparation method of COFs materials based on flexible modules, the mixed solvent in step a is a mixed solvent of acetone and water; the volume ratio of acetone to water is 5:1 to 1:2.
上述的基于柔性模块构筑的COFs材料的制备方法中,所述的碱为NaOH、KOH、CsOH、Ca(OH)2、Sr(OH)2或Ba(OH)2中的任意一种;所述对羟基苯甲醛与碱的摩尔比为1︰1~1︰2。In the above-mentioned preparation method of COFs materials based on flexible modules, the alkali is any one of NaOH, KOH, CsOH, Ca(OH) 2 , Sr(OH) 2 or Ba(OH) 2 ; The molar ratio of p-hydroxybenzaldehyde to alkali is 1:1~1:2.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤a所述对羟基苯甲醛与三聚氯氰的摩尔比为5︰1~3︰1。In the above-mentioned preparation method of COFs material based on flexible module construction, the molar ratio of p-hydroxybenzaldehyde to cyanuric chloride in step a is 5:1 to 3:1.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤a所述碱溶液中的碱与对羟基苯甲醛的摩尔比为3︰2~3︰1;所述的碱溶液为饱和的NaHCO3溶液、8~16%的Na2CO3溶液或5~10%的NaOH溶液中的任意一种。In the above-mentioned preparation method of COFs material based on flexible module construction, the molar ratio of alkali to p-hydroxybenzaldehyde in the alkali solution described in step a is 3:2 to 3:1; the alkali solution is saturated NaHCO 3 Either solution, 8-16% Na 2 CO 3 solution or 5-10% NaOH solution.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤b所述的混合溶剂为均三甲苯(1,3,5-三甲苯)/二氧六环溶剂;所述均三甲苯与二氧六环的体积比为3︰1~1︰3。In the above-mentioned preparation method of COFs material based on flexible module construction, the mixed solvent described in step b is mesitylene (1,3,5-trimethylbenzene)/dioxane solvent; The volume ratio of the six rings is 3:1 to 1:3.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤b所述取代的联苯胺与TPT-CHO的摩尔比为7︰4~6︰5。In the above-mentioned preparation method of COFs material based on flexible module construction, the molar ratio of the substituted benzidine described in step b to TPT-CHO is 7:4 to 6:5.
上述的基于柔性模块构筑的COFs材料的制备方法中,步骤b所述乙酸的浓度为5~15M;所述乙酸与TPT-CHO的摩尔比为3︰1~15︰1。In the above-mentioned preparation method of COFs material based on flexible module construction, the concentration of acetic acid in step b is 5-15M; the molar ratio of acetic acid and TPT-CHO is 3:1-15:1.
实施例1 2,4,6-三对甲酰苯氧基-1,3,5-三嗪(TPT-CHO)的制备Example 1 Preparation of 2,4,6-tri-p-formylphenoxy-1,3,5-triazine (TPT-CHO)
称取7.45g对羟基苯甲醛溶解于丙酮和水(1:1v/v,100mL)混合溶剂中,在冰浴条件下加入2.48g NaOH,搅拌30min。缓慢滴加50mL丙酮溶解的三聚氯氰(3.68g)溶液于反应器中,冰浴下搅拌1h后使其在80℃下回流2h,自然冷却。将反应后的溶液倒入300mL蒸馏水中,形成大量白色固体。过滤,固体用10%的Na2CO3溶液洗涤2~3次,真空干燥。将获得的白色固体粉末于乙酸乙酯中重结晶,得到白色晶体粉末TPT-CHO,产率88.9%。Weigh 7.45 g of p-hydroxybenzaldehyde and dissolve it in a mixed solvent of acetone and water (1:1 v/v, 100 mL), add 2.48 g of NaOH under ice bath conditions, and stir for 30 min. Slowly add 50 mL of acetone-dissolved cyanuric chloride (3.68 g) solution dropwise into the reactor, stir under an ice bath for 1 h, reflux at 80° C. for 2 h, and cool naturally. The reacted solution was poured into 300 mL of distilled water to form a large amount of white solid. After filtration, the solid was washed 2-3 times with 10% Na 2 CO 3 solution and dried in vacuo. The obtained white solid powder was recrystallized from ethyl acetate to obtain TPT-CHO as a white crystalline powder with a yield of 88.9%.
1H NMR(400MHz,CDCl3)δ:9.99(s,3H),7.92(d,J=8.7Hz,6H),7.32(d,J=8.5Hz,6H)。 1 H NMR (400 MHz, CDCl 3 ) δ: 9.99 (s, 3H), 7.92 (d, J=8.7 Hz, 6H), 7.32 (d, J=8.5 Hz, 6H).
实施例2共价有机框架材料TPT-BD COF(化合物1)的制备Example 2 Preparation of covalent organic framework material TPT-BD COF (compound 1)
称取2,4,6-三对甲酰苯氧基-1,3,5-三嗪(TPT-CHO)(88.4mg,0.2mmol)和联苯胺(BD)(55.2mg,0.3mmol)分别置于10mL玻璃小瓶中,各加入溶剂均三甲苯/二氧六环(1:1v/v,1mL),超声5min,形成均匀分散液。然后将TPT-CHO分散液加入3,3'-二羟基联苯胺分散液中,最后缓慢加入乙酸(6M,0.2mL),密封,于85℃下静置反应4d,获得黄色结晶固体产物,产率61.3%。分子式((C14H9N2O)n),元素分析(%计算/测量):C 76.01/72.80,H4.10/4.35,N12.66/11.36,O 7.23/11.49)。Weigh out 2,4,6-tri-p-formylphenoxy-1,3,5-triazine (TPT-CHO) (88.4mg, 0.2mmol) and benzidine (BD) (55.2mg, 0.3mmol) respectively It was placed in a 10 mL glass vial, each solvent was added with mesitylene/dioxane (1:1 v/v, 1 mL), and ultrasonicated for 5 min to form a uniform dispersion. Then, the TPT-CHO dispersion was added to the 3,3'-dihydroxybenzidine dispersion, and finally acetic acid (6M, 0.2 mL) was slowly added, sealed, and allowed to stand at 85°C for 4d to obtain a yellow crystalline solid product. rate 61.3%. Molecular formula ((C 14 H 9 N 2 O) n ), elemental analysis (% calculated/measured): C 76.01/72.80, H4.10/4.35, N12.66/11.36, O 7.23/11.49).
实施例3共价有机框架材料TPT-DHBD COF(化合物2)的制备Example 3 Preparation of covalent organic framework material TPT-DHBD COF (compound 2)
称取2,4,6-三对甲酰苯氧基-1,3,5-三嗪(TPT-CHO)(88.4mg,0.2mmol)和3,3'-二羟基联苯胺(DHBD)(64.8mg,0.3mmol)分别置于10mL玻璃小瓶中,各加入溶剂均三甲苯/二氧六环(1:1v/v,1mL),超声8min,形成均匀分散液。然后将TPT-CHO分散液加入3,3'-二羟基联苯胺分散液中,最后缓慢加入乙酸(6M,0.3mL),密封,于70℃下静置反应5d,获得黄色结晶固体产物,产率62.5%。分子式((C14H9N2O2)n),元素分析(%计算/测量):C70.87/65.46,H3.83/4.05,N 11.81/9.87,O 13.49/20.62)。Weigh out 2,4,6-tri-p-formylphenoxy-1,3,5-triazine (TPT-CHO) (88.4 mg, 0.2 mmol) and 3,3'-dihydroxybenzidine (DHBD) ( 64.8 mg, 0.3 mmol) were placed in 10 mL glass vials, respectively, and the solvent mesitylene/dioxane (1:1 v/v, 1 mL) was added to each, and ultrasonicated for 8 min to form a uniform dispersion. Then, the TPT-CHO dispersion was added to the 3,3'-dihydroxybenzidine dispersion, and finally acetic acid (6M, 0.3 mL) was slowly added, sealed, and allowed to stand at 70 °C for 5 d to obtain a yellow crystalline solid product. rate 62.5%. Molecular formula ((C 14 H 9 N 2 O 2 ) n ), elemental analysis (% calculated/measured): C70.87/65.46, H3.83/4.05, N 11.81/9.87, O 13.49/20.62).
从图1a,b分析可见,TPT-BD COF和TPT-DHBD COF谱图中均在154ppm处出现了尖锐的亚氨基碳的特征共振峰,证实材料结构中亚胺键的存在。图1c,d为X射线光电子能谱图(XPS)测量的N 1s核心层图谱,TPT-BD COF(化合物1)和TPT-DHBD COF(化合物2)分别在399.4eV、398.7eV和399.4eV、399.0eV结合能处的峰属于三嗪环的C=N键和亚胺键的峰,图谱中仅有两种峰存在,且其面积基本相同,说明材料中仅三嗪环氮原子和亚胺氮原子存在,比例为1:1,与结构相匹配。由此可见,本发明成功制备了以醛胺缩合方式结合的COFs材料。From the analysis in Figure 1a,b, it can be seen that sharp characteristic resonance peaks of imino carbon appear at 154ppm in both TPT-BD COF and TPT-DHBD COF spectra, confirming the existence of imine bonds in the material structure. Figure 1c,d are the
实施例4共价有机框架材料TPT-DHBD25COF(化合物3)的制备Example 4 Preparation of covalent organic framework material TPT-DHBD 25 COF (compound 3)
将联苯胺(BD)(82.8mg,0.45mmol)和3,3'-二羟基联苯胺(DHBD)(32.4mg,0.15mmol)置于20mL玻璃耐压瓶中,加入2mL均三甲苯/二氧六环(1:1v/v)混合溶剂,超声8min,形成均匀分散液。再取单体2,4,6-三对甲酰苯氧基-1,3,5-三嗪(TPT-CHO)(176.8mg,0.4mmol)同样分散于2mL均三甲苯/二氧六环(1:1v/v)中于形成均匀分散液。然后将TPT-CHO分散液转移至耐压瓶中,超声20s混匀,接着缓慢加入乙酸(6M,0.6mL),密封,于90℃下静置反应3d,获得黄色结晶固体产物,产率59.8%。分子式((C56H36N8O5)n),元素分析(%计算/测量):C 74.66/71.19,H 4.03/4.46,N 12.44/11.21,O 8.88/13.14)。Benzidine (BD) (82.8 mg, 0.45 mmol) and 3,3'-dihydroxybenzidine (DHBD) (32.4 mg, 0.15 mmol) were placed in a 20 mL glass pressure bottle, and 2 mL of mesitylene/dioxygen was added. Hexacyclic (1:1v/v) mixed solvent was sonicated for 8min to form a uniform dispersion. Then take the
实施例5共价有机框架材料TPT-DHBD50COF(化合物4)的制备Example 5 Preparation of covalent organic framework material TPT-DHBD 50 COF (compound 4)
将联苯胺(BD)(55.2mg,0.3mmol)和3,3'-二羟基联苯胺(DHBD)(64.8mg,0.3mmol)置于20mL玻璃耐压瓶中,加入2mL均三甲苯/二氧六环(1:1v/v)混合溶剂,超声5min,形成均匀分散液。再取单体2,4,6-三对甲酰苯氧基-1,3,5-三嗪(TPT-CHO)(176.8mg,0.4mmol)同样分散于2mL均三甲苯/二氧六环(1:1v/v)中于形成均匀分散液。然后将TPT-CHO分散液转移至耐压瓶中,超声20s混匀,接着缓慢加入乙酸(6M,0.4mL),密封,于80℃下静置反应4d,获得黄色结晶固体产物,产率78.4%。分子式((C56H36N8O6)n),元素分析(%计算/测量):C73.35/69.34,H 3.96/4.27,N 12.22/10.87,O 10.47/15.52)。Benzidine (BD) (55.2 mg, 0.3 mmol) and 3,3'-dihydroxybenzidine (DHBD) (64.8 mg, 0.3 mmol) were placed in a 20 mL glass pressure-resistant bottle, and 2 mL of mesitylene/dioxygen was added. Hexacyclic (1:1 v/v) mixed solvent was sonicated for 5 min to form a uniform dispersion. Then take the
实施例6共价有机框架材料TPT-DHBD75COF(化合物5)的制备Example 6 Preparation of covalent organic framework material TPT-DHBD 75 COF (compound 5)
将联苯胺(BD)(27.6mg,0.15mmol)和3,3'-二羟基联苯胺(DHBD)(97.2mg,0.45mmol)置于20mL玻璃耐压瓶中,加入2mL均三甲苯/二氧六环(1:1v/v)混合溶剂,超声6min,形成均匀分散液。再取单体2,4,6-三对甲酰苯氧基-1,3,5-三嗪(TPT-CHO)(176.8mg,0.4mmol)同样分散于2mL均三甲苯/二氧六环(1:1v/v)中于形成均匀分散液。然后将TPT-CHO分散液转移至耐压瓶中,超声20s混匀,接着缓慢加入乙酸(6M,0.5mL),密封,于75℃下静置反应5d,获得黄色结晶固体产物,产率68.7%。分子式((C56H36N8O7)n),元素分析(%计算/测量):C 72.10/67.29,H 3.89/4.21,N 12.01/10.87,O 12.00/17.63)。Benzidine (BD) (27.6 mg, 0.15 mmol) and 3,3'-dihydroxybenzidine (DHBD) (97.2 mg, 0.45 mmol) were placed in a 20 mL glass pressure bottle, and 2 mL of mesitylene/dioxygen was added. Hexacyclic (1:1 v/v) mixed solvent was sonicated for 6 min to form a uniform dispersion. Then take the
实施例7化合物1和化合物2的粉末X射线衍射(PXRD)和理论模拟实验Example 7 Powder X-ray Diffraction (PXRD) and theoretical simulation experiments of
粉末X射线衍射(PXRD)是晶态材料结构的主要表征手段之一。由于多数COF材料的PXRD主衍射峰出现在2θ为2-5°范围,因此,本发明采用X射线衍射仪的测试范围为2-40°。并采用PXRD实验测试值和理论模拟值的对照研究确定材料TPT-BD COF和TPT-DHBD COF的确切结构。Powder X-ray diffraction (PXRD) is one of the main characterization methods for the structure of crystalline materials. Since the PXRD main diffraction peaks of most COF materials appear in the 2θ range of 2-5°, the testing range of the X-ray diffractometer used in the present invention is 2-40°. The exact structures of the materials TPT-BD COF and TPT-DHBD COF were determined by the comparative study of PXRD experimental test values and theoretical simulation values.
PXRD显示,TPT-DHBD COF(化合物1)具有多个明显的衍射峰(图2a),其主要的衍射峰由(100)面引起,位于2.27°。其它清晰可见的峰位于2θ为4.07°、4.69°、6.22°、8.13°、10.18°处,分别归功于(110)、(200)、(210)、(220)、(xxx)晶面。PXRD showed that TPT-DHBD COF (compound 1) had multiple distinct diffraction peaks (Fig. 2a), and its main diffraction peak was caused by the (100) plane, located at 2.27°. Other clearly visible peaks are located at 2θ of 4.07°, 4.69°, 6.22°, 8.13°, 10.18°, attributed to (110), (200), (210), (220), (xxx) crystal planes, respectively.
TPT-DHBD COF(化合物2)的晶体结构使用Materials Studio 7.0软件进行模拟,结果表明,模拟的PXRD图谱以AA堆叠的方式与实验值相似。Pawley精修的晶胞参数为 α=β=90°,andγ=120°,相关系数为RP=2.80%和RWP=3.91%。Pawley精修值与实验观测值能很好的匹配。材料TPT-BD COF在2θ为2.27、4.03、4.53、6.16、8.12°处有较为明显的衍射峰(图2b),他们分别由(100)、(110)、(200)、(210)、(220)晶面产生。结构模拟显示实验值各晶面的衍射峰与AA堆叠方式基本相同,PawleyPawley精修的晶胞参数为α=β=90°,γ=120°,相关系数为RP=4.48%和RWP=6.11%。通过PXRD对比发现TPT-DHBD COF的XRD衍射峰强度大,图谱受基线干扰小,而TPT-BD COF其(100)衍射峰峰强较弱,受基线干扰严重,且在2θ为21.5°附近有较强的无定型峰的出现。说明TPT-DHBD COF比TPT-BD COF具有更好的结晶度,这可能是由于TPT-DHBD COF中形成了氢键的缘故。The crystal structure of TPT-DHBD COF (compound 2) was simulated using Materials Studio 7.0 software, and the results showed that the simulated PXRD pattern was similar to the experimental value in the way of AA stacking. The unit cell parameters of the Pawley refinement are α=β=90°, and γ=120°, the correlation coefficients are R P =2.80% and R WP =3.91%. The Pawley refinement values are well matched to the experimental observations. The material TPT-BD COF has obvious diffraction peaks at 2.27, 4.03, 4.53, 6.16, and 8.12° at 2θ (Fig. 2b), which are represented by (100), (110), (200), (210), ( 220) crystal planes are generated. The structural simulation shows that the diffraction peaks of each crystal plane in the experimental value are basically the same as the AA stacking method, and the unit cell parameters refined by PawleyPawley are: α=β=90°, γ=120°, the correlation coefficients are R P =4.48% and R WP =6.11%. Through PXRD comparison, it is found that the XRD diffraction peak intensity of TPT-DHBD COF is high, and the pattern is less disturbed by the baseline, while the (100) diffraction peak of TPT-BD COF is weaker and seriously disturbed by the baseline, and there is a 2θ near 21.5°. The appearance of stronger amorphous peaks. It shows that TPT-DHBD COF has better crystallinity than TPT-BD COF, which may be due to the formation of hydrogen bonds in TPT-DHBD COF.
实施例8化合物1和化合物2的γ射线辐照实验Example 8 γ-ray irradiation experiment of
从设计的结构可知,本发明制备的系列共价有机框架材料TPT-DHBDX COF具有富氮的结构(C=N)和丰富的π-π共轭体系,这样的结构特性为其与碘的相互作用提供了许多可能。为了考察材料在可能的真实应用环境中耐受射线辐照的稳定性情况,本发明利用60Co的γ射线辐射源对化合物1和化合物2进行了总剂量为105Gy的γ射线辐照,并通过辐照前后的红外光谱图对比说明材料的辐照稳定性。From the designed structure, it can be seen that the series of covalent organic framework materials TPT-DHBD X COF prepared by the present invention have nitrogen-rich structure (C=N) and rich π-π conjugated system, and such a structural characteristic is that it has a structure with iodine. Interactions offer many possibilities. In order to investigate the stability of the material to withstand ray irradiation in a possible real application environment, the present invention uses a γ-ray radiation source of 60 Co to irradiate
图3的红外光谱显示,材料在辐照前后几乎没有发生改变,说明材料具有很好的辐照稳定性,至少能够承受总剂量为105Gy的γ射线的辐照。这表明制备的共价有机框架材料在放射性碘的捕获(如129I和131I)领域具有潜在的应用价值。此外,制备材料还具有较好的热稳定性,特别是TPT-BD COF(化合物1),当温度从25~400℃时仅失重7%。因此制备材料非常适合用于实际环境中碘蒸气的吸附-解吸应用。The infrared spectrum of Fig. 3 shows that the material hardly changes before and after irradiation, indicating that the material has good radiation stability and can at least withstand the irradiation of γ-rays with a total dose of 10 5 Gy. This indicates that the prepared covalent organic framework materials have potential applications in the field of radioactive iodine capture (such as 129 I and 131 I). In addition, the prepared materials also have good thermal stability, especially TPT-BD COF (compound 1), which only loses 7% in weight when the temperature is from 25 to 400 °C. The prepared materials are therefore very suitable for adsorption-desorption applications of iodine vapors in practical environments.
实施例9化合物1~5对碘的吸附实验Example 9 Adsorption experiment of compounds 1-5 on iodine
为了评估材料对碘蒸气的富集能力,将制备的化合物1~5粉末暴露于一个封闭的含有过量碘的体系内,体系的温度恒定于75℃,压力为环境压力,该体系环境与典型的核燃料后处理环境接近。通过重量测量法检测不同吸附时间下材料对碘的吸附容量。具体操作如下:10mg的吸附剂粉末放置于2mL的敞口玻璃管中,并将玻璃管放入含有500mg碘的玻璃小瓶中,密封,于75℃常压下进行吸附实验。一段时间后(0-48h)取出样品,冷却称量,计算其不同时间下的吸附容量。通过重量的增加计算吸附剂对碘的吸附容量:Cu=(W2-W1)/W1×100wt%;其中Cu是吸附容量,W1,W2是材料吸附碘蒸气前后的质量。To evaluate the material's ability to enrich iodine vapor, the prepared powders of
图4的结果显示,在最初的6h小时内,吸附容量几乎呈线性趋势极速增加,达到总吸附量的70%以上;到12h时,吸附基本趋近于平衡;吸附时间超过32h后,碘的负载量几乎不再发生变化,说明吸附已经达到平衡。吸附过程中,材料的颜色不断加深,最终由黄色逐渐变为深黑色,吸附碘以后的材料被表示为TPT-DHBDX COFs@I2。从吸附曲线我们可知,吸附前段和后段速率相差很大,这表明碘富集是化学吸附和物理吸附的共同作用。吸附动力学研究发现,化学吸附为主要作用方式,具有较快的吸附动力学。在这种条件下,1g的化合物1~5材料分别对应能够吸附碘的量大约为5.43g/g、3.88g/g、4.63g/g、4.30g/g、4.12g/g。由此可见化合物1~5系列材料均有超高的碘饱和吸附容量,特别是材料TPT-BD COF(化合物1)对碘的富集量最高可达5.43g/g,高于已报道的所有的吸附材料,如MOFs、amorphousPOPs和其他COFs材料。更重要的是,我们制备的克量级的TPT-DHBD COF(化合物2)对碘的富集量仍可高达4.03g/g,这为该类材料的规模化生产并实践应用创造了条件,使其在核事故现场等特定环境中对放射性碘的富集和去除领域具有巨大的潜在应用价值。The results in Figure 4 show that in the first 6h, the adsorption capacity increased rapidly in an almost linear trend, reaching more than 70% of the total adsorption capacity; by 12h, the adsorption basically approached equilibrium; after the adsorption time exceeded 32h, the iodine The loadings hardly changed, indicating that the adsorption had reached equilibrium. During the adsorption process, the color of the material continued to deepen, and finally changed from yellow to dark black. The material after adsorption of iodine was denoted as TPT-DHBD X COFs@I 2 . From the adsorption curve, we can see that the rates of the first and last stages of adsorption are very different, which indicates that the iodine enrichment is the combined effect of chemisorption and physical adsorption. The adsorption kinetics study found that chemisorption is the main mode of action and has a faster adsorption kinetics. Under this condition, the amounts of 1 g of
图8的红外光谱分析发现,吸附碘前后材料的峰发生了较大的移动,如TPT-BD COF苯环中C=C键和C-H键位于1499cm-1和815cm-1处,移动到了1492cm-1、805cm-1;三嗪环的C=N双键从1566cm-1和1363cm-1移动到1562cm-1和1359cm-1;特别是亚胺键的峰,从1622cm-1移动到1631cm-1,有一个巨大的变化。其余材料均有相似的规律,说明碘吸附可能同时发生在了材料的亚胺键、三嗪环和苯环上。The infrared spectrum analysis in Fig. 8 shows that the peaks of the material before and after the adsorption of iodine have shifted greatly. For example, the C=C bond and CH bond in the benzene ring of TPT-BD COF are located at 1499cm -1 and 815cm -1 , and move to
实施例10化合物1~5对碘的解吸实验Example 10 Desorption experiment of iodine by
碘的解吸附实验于125℃下进行(图5),操作流程如下:30mg吸附碘蒸气后的材料TPT-DHBDX COFs@I2放置于2mL的敞口玻璃管中,并将其放入敞口的玻璃小瓶中(50mL),于125℃常压下进行脱附实验。碘的解吸效率由Er=(30–Wt)/WX×100wt%进行计算,其中Er代表解吸效率,Wt代表在相应时间内(0-420min)TPT-DHBDX COFs@I2加热释放后的质量,WX代表30mg TPT-DHBDX COFs@I2中碘的含量。The desorption experiment of iodine was carried out at 125 °C (Fig. 5). The operation process was as follows: 30 mg of the material TPT-DHBD X COFs@ I2 after adsorbed iodine vapor was placed in a 2 mL open glass tube, and it was placed in an open glass tube. In a glass vial (50 mL), the desorption experiment was carried out at 125 °C under normal pressure. The desorption efficiency of iodine is calculated by Er=(30–Wt)/W X ×100wt%, where Er represents the desorption efficiency and Wt represents the thermal release of TPT-DHBD X COFs@ I2 within the corresponding time (0-420 min). Mass, W X represents the content of iodine in 30 mg TPT-DHBD X COFs@ I2 .
实验表明,在40min内所有的材料均能释放出80%以上的碘,具有一个较快的解吸速率。6h时后,解吸基本可达到平衡,几乎所有的碘被解吸出(见表1)。通过TGA表征(图9)对TPT-DHBD COF(化合物2)的碘负载量进行了计算,负载量分别是4.77g/g(400℃)、4.24g/g(350℃)、3.77g/g(250℃),这一结果与重量测定法测得的值基本一致,少量的差别可能是由于在计算碘负载量温度下仍有部分碘未完全释放出来。复用性实验表明,TPT-BD COF(化合物1)在第一个循环完成后,可以保持515wt%的碘吸附容量(高达96%的回收率)。在第三次循环后,它仍然保留了472wt%的碘吸附容量(87.9%的回收量)(图10)。由此可见,本发明制备的系列COF材料对碘蒸气的吸附是高效、可逆的过程,其在挥发性碘的富集和储存方面具有很大的可操作性。Experiments show that all materials can release more than 80% of iodine within 40min, with a faster desorption rate. After 6h, the desorption could basically reach equilibrium, and almost all the iodine was desorbed (see Table 1). The iodine loading of TPT-DHBD COF (compound 2) was calculated by TGA characterization (Fig. 9), and the loadings were 4.77 g/g (400 °C), 4.24 g/g (350 °C), 3.77 g/g, respectively. (250°C), this result is basically consistent with the value measured by gravimetry, and a small difference may be due to the incomplete release of some iodine at the temperature of calculating the iodine loading. The reusability experiment showed that the TPT-BD COF (compound 1) could maintain an iodine adsorption capacity of 515 wt% (up to 96% recovery) after the first cycle was completed. After the third cycle, it still retained 472 wt% iodine adsorption capacity (87.9% recovery) (Figure 10). It can be seen that the adsorption of iodine vapor by the series of COF materials prepared by the present invention is an efficient and reversible process, which has great operability in the enrichment and storage of volatile iodine.
表1碘的解吸附量随时间变化表(125℃)Table 1 Variation of desorption amount of iodine with time (125℃)
本发明以柔性模块制备的一系列大晶格尺寸的COFs材料均表现出极高的碘富集能力,最大吸附量高达未见报道的5.43g/g,是目前所有类型的吸附材料中最高的,这一特性使其在放射性核废物后处理放射性碘的富集领域具有极大的实用前景。A series of COFs materials with large lattice size prepared by the flexible module of the present invention all show extremely high iodine enrichment capacity, and the maximum adsorption capacity is as high as 5.43 g/g, which has never been reported, which is the highest among all types of adsorption materials at present. , this feature makes it have great practical prospects in the field of enrichment of radioactive iodine in the reprocessing of radioactive nuclear waste.
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