CN104151336A - Preparation method of metal-organic framework compound with hierarchical pore structure - Google Patents

Preparation method of metal-organic framework compound with hierarchical pore structure Download PDF

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CN104151336A
CN104151336A CN201410388223.XA CN201410388223A CN104151336A CN 104151336 A CN104151336 A CN 104151336A CN 201410388223 A CN201410388223 A CN 201410388223A CN 104151336 A CN104151336 A CN 104151336A
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陈道勇
易俊琦
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Fudan University
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Abstract

本发明属于纳米复合材料技术领域,具体为一种多级孔结构的金属有机框架化合物的制备方法。本发明首先两嵌段共聚物在溶剂中自组装形成核壳结构的柔性聚合物纳米线,交联核后获得溶剂稳定的聚合物纳米线;在纳米线溶液中加入金属离子及有机配体,形成混合溶液;室温下结晶得到金属有机框架/核壳结构聚合物纳米线复合物;煅烧后除去聚合物纳米线,获得既有MOFs自身的微孔,又有由聚合物纳米线壳层煅烧后形成的小介孔和核层煅烧后形成的大介孔的多级孔材料。这种多级孔MOFs材料结合了微孔和介孔的优点,改善了MOFs材料的传质速度,有利于较大分子进入,提高了其在催化、吸附等领域的应用潜能。

The invention belongs to the technical field of nanocomposite materials, in particular to a preparation method of a metal organic framework compound with a hierarchical porous structure. In the present invention, the two-block copolymer self-assembles in a solvent to form a flexible polymer nanowire with a core-shell structure, and obtains a solvent-stabilized polymer nanowire after cross-linking the core; adding metal ions and organic ligands to the nanowire solution, Form a mixed solution; crystallize at room temperature to obtain a metal-organic framework/core-shell polymer nanowire composite; remove the polymer nanowire after calcination, and obtain both the micropores of the MOFs itself and the calcined polymer nanowire shell A hierarchical porous material with small mesoporous pores and large mesopores formed after calcination of the core layer. This kind of hierarchical porous MOFs material combines the advantages of micropores and mesoporous materials, improves the mass transfer rate of MOFs materials, facilitates the entry of larger molecules, and improves its application potential in the fields of catalysis and adsorption.

Description

一种多级孔结构的金属有机框架化合物的制备方法A kind of preparation method of the metal-organic framework compound of hierarchical pore structure

技术领域 technical field

本发明属于纳米复合材料技术领域,具体涉及多级孔结构的金属有机框架化合物的制备方法。 The invention belongs to the technical field of nanocomposite materials, and in particular relates to a preparation method of a metal organic framework compound with a hierarchical porous structure.

背景技术 Background technique

多孔材料,如分子筛、介孔硅和活性炭等是一类非常重要的材料。由于它们巨大的比表面积,使得其在催化、气体吸附、离子交换等方面都有广泛的应用。近几年新兴的一种有机无机结合的多孔材料——金属有机框架化合物(MOFs),由于其优异的性能,以及结构和功能的可调控性受到了广泛的关注。MOFs是一类由金属离子和有机配体组成的晶体材料。MOsF的结构和功能可以根据金属离子的选择和合成不同的有机配体来获得。其可以被应用与气体储存、分离、检测和催化等领域。 Porous materials, such as molecular sieves, mesoporous silicon, and activated carbon, are a very important class of materials. Due to their huge specific surface area, they are widely used in catalysis, gas adsorption, ion exchange and so on. Metal-organic frameworks (MOFs), a newly emerging organic-inorganic porous material, have attracted extensive attention due to their excellent properties and the controllability of structure and function. MOFs are a class of crystalline materials composed of metal ions and organic ligands. The structures and functions of MOsFs can be obtained according to the selection of metal ions and the synthesis of different organic ligands. It can be applied in the fields of gas storage, separation, detection and catalysis.

大多数MOFs的孔径为微孔(小于2nm),使其具有大的比表面积,然而却不利于较大的分子进入,其内部的传质也受到了限制,这就限制了其在催化、储存、分离、药物运输等方面的应用。因此制备介孔的MOFs特别是既具有介孔又具有微孔的多级孔MOFs就非常有意义了。例如Zhou Hongcai等的报道(J. Am. Chem. Soc. 2012, 134, 126-129.),用表面活性做为产生介孔的致孔剂。白俊峰等的报道(Crystal Growth & Design, 2010, 10, 2451-2454.)用纳米MOF颗粒通过范德华力聚集起来形成晶粒间隙介孔,Yaghi等的报道(J. Am. Chem. Soc. 2011, 133, 11920-11923.)通过加入单官能度的配体使晶体产生缺陷从而产生介孔或大孔等。但是,表面活性剂的除去往往导致整体结构的坍塌,而利用范德华力和特殊的配体方法又具有特异性。因此,发展一种具有普适性的方法制备多级孔结构的MOFs,并且保持MOFs的晶体颗粒的稳定性就十分有意义了。 The pore size of most MOFs is microporous (less than 2nm), which makes it have a large specific surface area, but it is not conducive to the entry of larger molecules, and its internal mass transfer is also limited, which limits its use in catalysis, storage, etc. , separation, drug delivery and other applications. Therefore, it is very meaningful to prepare mesoporous MOFs, especially hierarchically porous MOFs with both mesoporous and micropores. For example, as reported by Zhou Hongcai et al. (J. Am. Chem. Soc. 2012, 134, 126-129.), surface activity was used as a porogen to generate mesopores. Reports by Bai Junfeng et al. (Crystal Growth & Design, 2010, 10, 2451-2454.) used nano-MOF particles to gather together through van der Waals force to form interstitial mesoporous grains. Yaghi et al. reported (J. Am. Chem. Soc. 2011, 133, 11920-11923.) By adding monofunctional ligands to make crystals have defects to produce mesopores or macropores, etc. However, the removal of surfactants often leads to the collapse of the overall structure, and the use of van der Waals forces and special ligands is specific. Therefore, it is very meaningful to develop a universal method to prepare MOFs with hierarchical porous structure and maintain the stability of MOFs crystal particles.

发明内容 Contents of the invention

本发明的目的在于提供一种能确保多级孔结构稳定性好的多级孔金属有机框架化合物(MOFs)的制备方法。 The object of the present invention is to provide a method for preparing hierarchical porous metal organic frameworks (MOFs) that can ensure the stability of the hierarchical porous structure.

本发明提供的多级孔金属有机框架化合物(MOFs)的制备方法,具体步骤为: The preparation method of the hierarchical porous metal organic framework compound (MOFs) provided by the present invention, the specific steps are:

(1)首先,两嵌段共聚物在溶剂中自组装形成核壳结构的柔性聚合物纳米线,然后交联纳米线的核层;再将纳米线溶液的溶剂切换到MOFs结晶所需要的溶剂;  (1) First, the diblock copolymer self-assembles in a solvent to form a flexible polymer nanowire with a core-shell structure, and then cross-links the core layer of the nanowire; then switch the solvent of the nanowire solution to the solvent required for MOFs crystallization ;

(2)然后,在聚合物纳米线溶液中,加入金属盐溶液和有机配体溶液,形成混合溶液;室温下静置结晶,得到金属有机框架/核壳结构聚合物纳米线复合物; (2) Then, add a metal salt solution and an organic ligand solution to the polymer nanowire solution to form a mixed solution; stand and crystallize at room temperature to obtain a metal-organic framework/core-shell polymer nanowire composite;

(3)最后,一定温度下煅烧, 除去聚合物纳米线,获得既有MOF自身的微孔,又有由聚合物纳米线壳层煅烧后形成的小介孔和核层煅烧后形成的大介孔的多级孔材料;此外,煅烧后的多级孔颗粒保持了晶体颗粒的几何外形,保证了结构的稳定性。 (3) Finally, calcine at a certain temperature to remove the polymer nanowires, and obtain both the micropores of the MOF itself, and the small mesopores formed by the calcination of the polymer nanowire shell and the large mesopores formed by the calcination of the core layer. The hierarchical porous material; in addition, the calcined hierarchical porous particles maintain the geometric shape of the crystal particles and ensure the stability of the structure.

其中,所MOFs 为ZIF-8、ZIF-7、ZIF-67、HKUST-1或CD-MOF-1,这里,ZIF-8表示由二价锌离子和2-甲基咪唑形成的MOFs,ZIF-67表示由二价钴离子和2-甲基咪唑形成的MOFs,ZIF-7表示由二价锌离子和苯并咪唑形成的MOFs,HKUST-1表示二价铜离子和均苯三甲酸形成的MOFs,CD-MOF-1表示由一价钾离子和γ-环糊精形成的MOFs; Among them, the MOFs are ZIF-8, ZIF-7, ZIF-67, HKUST-1 or CD-MOF-1, here, ZIF-8 means MOFs formed by divalent zinc ions and 2-methylimidazole, ZIF- 67 represents the MOFs formed by divalent cobalt ions and 2-methylimidazole, ZIF-7 represents the MOFs formed by divalent zinc ions and benzimidazole, HKUST-1 represents the MOFs formed by divalent copper ions and trimesic acid , CD-MOF-1 means MOFs formed by monovalent potassium ions and γ-cyclodextrin;

本发明中,所述聚合物纳米线具有柔性,能弯曲以及相互缠绕;组成纳米线的壳层的聚合物能与金属离子发生相互作用,在金属离子与配体结晶形成MOFs时,聚合纳米线能被很好的包裹进MOFs颗粒中,形成颗粒保持晶体外形,纳米线贯穿包覆晶体颗粒。 In the present invention, the polymer nanowires are flexible, capable of bending and intertwining; the polymer forming the shell of the nanowires can interact with metal ions, and when metal ions and ligands crystallize to form MOFs, the polymer nanowires It can be well wrapped into MOFs particles, forming particles to maintain the crystal shape, and nanowires run through the coated crystal particles.

本发明中,所述聚合物纳米线的稳定性低于金属有机框架化合物。 In the present invention, the stability of the polymer nanowire is lower than that of the metal organic framework compound.

本发明中,煅烧后形成的多级孔MOFs具备海绵状结构,孔道是无序的,相互连通的,且与外界连通。  In the present invention, the hierarchically porous MOFs formed after calcination have a sponge-like structure, and the pores are disordered, connected to each other, and connected to the outside world. the

步骤(1)中,所述两嵌段共聚物为聚乙二醇-聚四乙烯基吡啶(PEG-b-P4VP,聚乙二醇链段分子量为2000-20000之间,聚(4-乙烯基吡啶)分子量为3000-20000之间;交联剂为1,4-二溴丁烷,交联程度为5%-100%的吡啶环被交联了。 In step (1), the two-block copolymer is polyethylene glycol-polytetravinylpyridine (PEG- b -P4VP, the polyethylene glycol segment molecular weight is between 2000-20000, poly(4-ethylene basepyridine) with a molecular weight of 3000-20000; the crosslinking agent is 1,4-dibromobutane, and the pyridine ring with a crosslinking degree of 5%-100% is crosslinked.

步骤(1)中,可以对聚合物纳米线进行改性,引入功能性基团、纳米粒子或其它无机成分,优化MOFs的功能性。例如,通过卤代烃与吡啶环的反应引入功能性官能团——吡啶基团、荧光基团;通过抗衡离子的交换引入氯金酸而引人Au或通过Brˉ与Ag+的反应引人Ag、AgBr;通过在聚合物核表面沉积较薄的SiO2,而把SiO2引入。 In step (1), polymer nanowires can be modified to introduce functional groups, nanoparticles or other inorganic components to optimize the functionality of MOFs. For example, functional functional groups—pyridine groups and fluorescent groups can be introduced through the reaction of halogenated hydrocarbons and pyridine rings; Au can be introduced through the exchange of counter ions to introduce chloroauric acid, or Ag , AgBr; SiO 2 was introduced by depositing a thinner SiO 2 on the surface of the polymer core.

步骤(1)中,切换溶剂的方法包括离心去上清液后再溶解,透析,冻干后再溶解中任意一种;溶剂为甲醇(对于ZIF-8、ZIF-67、ZIF-7)、乙醇(对于HKUST-1)、水(对于HKUST-1、CD-MOF-1)、DMF(对于ZIF-8、ZIF-67、ZIF-7)、以及它们的混合溶液乙醇/水(对于HKUST-1)中的一种。  In step (1), the method of switching the solvent includes centrifuging to remove the supernatant and then dissolving, dialysis, and freeze-drying and then dissolving; the solvent is methanol (for ZIF-8, ZIF-67, ZIF-7), Ethanol (for HKUST-1), water (for HKUST-1, CD-MOF-1), DMF (for ZIF-8, ZIF-67, ZIF-7), and their mixed solution ethanol/water (for HKUST- 1) One of. the

步骤(2)中,所述反应液聚合物纳米线的浓度为0.1mg/ml-10mg/ml。 In step (2), the concentration of the polymer nanowires in the reaction solution is 0.1 mg/ml-10 mg/ml.

步骤(2)中,所述金属盐和有机配体对应关系为:Zn(NO3)2或ZnCl2对应 2-甲基咪唑(ZIF-8),Co(NO3)2对应2-甲基咪唑(ZIF-67),Zn(NO3)2对应苯并咪唑(ZIF-7),Cu(NO3)2或Cu(Ac)2对应均苯三甲酸(HKUST-1),KOH对应γ-环糊精(CD-MOF-1);反应体系中金属盐的浓度为10mM-150mM,有机配体的浓度为10mM-200mM。  In step (2), the corresponding relationship between the metal salt and the organic ligand is: Zn(NO 3 ) 2 or ZnCl 2 corresponds to 2-methylimidazole (ZIF-8), and Co(NO 3 ) 2 corresponds to 2-methyl Imidazole (ZIF-67), Zn(NO 3 ) 2 corresponds to benzimidazole (ZIF-7), Cu(NO3) 2 or Cu(Ac) 2 corresponds to trimesic acid (HKUST-1), KOH corresponds to γ-ring Dextrin (CD-MOF-1); the concentration of the metal salt in the reaction system is 10mM-150mM, and the concentration of the organic ligand is 10mM-200mM.

步骤(2)中,当制备的MOFs为CD-MOF-1时,聚合物纳米线和KOH、γ-环糊精均以水为溶剂,采用混合后将等体积的甲醇扩散到水溶液中的方法来制备复合物。 In step (2), when the prepared MOFs are CD-MOF-1, the polymer nanowires, KOH, and γ-cyclodextrin all use water as the solvent, and use the method of diffusing an equal volume of methanol into the aqueous solution after mixing to prepare the compound.

步骤(2)中,静置时间为24小时-3天(对于ZIF-8、ZIF-67、ZIF-7),7-14天(对于HKUST-1、CD-MOF-1)。 In step (2), the standing time is 24 hours-3 days (for ZIF-8, ZIF-67, ZIF-7), 7-14 days (for HKUST-1, CD-MOF-1).

步骤(3)中,所述煅烧的温度为150℃-500℃,煅烧时间为0.5小时-10小时;优选煅烧的温度为300℃-400℃,煅烧时间为3小时-4小时。 In step (3), the calcination temperature is 150°C-500°C, and the calcination time is 0.5-10 hours; preferably, the calcination temperature is 300-400°C, and the calcination time is 3-4 hours.

本发明的特点在于: The present invention is characterized in that:

1、该方法制得由聚合物纳米线壳层煅烧后形成小介孔,核层煅烧后形成大介孔以及MOFs本身的微孔组成多级孔结构的MOFs材料。 1. This method produces MOFs materials with a hierarchical pore structure composed of small mesopores formed after the polymer nanowire shell is calcined, large mesopores formed after the core layer is calcined, and the micropores of the MOFs themselves.

2、聚合物纳米线在结晶形成MOFs前加入,单个MOFs颗粒中,聚合物纳米线形成网络状结构贯穿MOFs颗粒内外,因此煅烧后形成的无序孔,孔相互贯穿,并与外界相通。 2. Polymer nanowires are added before crystallization to form MOFs. In a single MOFs particle, the polymer nanowires form a network structure that runs through the inside and outside of the MOFs particle. Therefore, the disordered pores formed after calcination, the pores penetrate each other and communicate with the outside world.

3、煅烧去掉聚合物纳米线后MOFs结构没有坍塌,保持了原有的晶体外形,保证了多级孔结构的稳定性。 3. After calcining to remove the polymer nanowires, the MOFs structure does not collapse, maintains the original crystal shape, and ensures the stability of the hierarchical pore structure.

附图说明 Description of drawings

图1为实施例1中多级孔ZIF-8产物的场发射扫描电镜(a、b),高分辨透射电镜(c、d)。 Fig. 1 is the field emission scanning electron microscope (a, b) and the high resolution transmission electron microscope (c, d) of the hierarchically porous ZIF-8 product in Example 1.

图2实施例1中ZIF-8、ZIF-8/纳米线复合物、多级孔ZIF-8的氮气吸附脱附曲线。 The nitrogen adsorption and desorption curves of ZIF-8, ZIF-8/nanowire composite, and hierarchical porous ZIF-8 in Fig. 2 Example 1.

图3实施例1中ZIF-8、ZIF-8/纳米线复合物、多级孔ZIF-8的NLDFT孔径分布图。 Fig. 3 NLDFT pore size distribution diagram of ZIF-8, ZIF-8/nanowire composite, and hierarchically porous ZIF-8 in Example 1.

图4为实施例3中多级孔ZIF-7产物的场发射扫描电镜图(a),高分辨透射电镜图(b)。 Fig. 4 is a field emission scanning electron microscope image (a) and a high resolution transmission electron microscope image (b) of the hierarchically porous ZIF-7 product in Example 3.

图5为实施例4中多级孔HKUST-1产物的场发射扫描电镜图(a),高分辨透射电镜图(b)。 Fig. 5 is a field emission scanning electron microscope image (a) and a high resolution transmission electron microscope image (b) of the hierarchically porous HKUST-1 product in Example 4.

具体实施方式 Detailed ways

下面通过实施例对本发明做进一步的描述,但本发明的实施方式不限于此。 The present invention will be further described through examples below, but the embodiments of the present invention are not limited thereto.

实施例1、多级孔结构ZIF-8的制备。 Example 1. Preparation of hierarchically porous ZIF-8.

(1)反应瓶中加入10ml(2mg/ml)聚合物纳米线溶液,15ml甲醇,再加入25ml Zn(NO3)2(250mM)甲醇溶液,50ml 2-甲基咪唑(250mM)甲醇溶液。摇晃均匀后室温下静置。24h后得到白色沉淀,离心收集,用甲醇洗涤两次,真空烘箱抽干过夜,得到白色固体0.1238g。 (1) Add 10ml (2mg/ml) polymer nanowire solution, 15ml methanol, 25ml Zn(NO 3 ) 2 (250mM) methanol solution, and 50ml 2-methylimidazole (250mM) methanol solution into the reaction bottle. Shake well and let stand at room temperature. After 24 hours, a white precipitate was obtained, which was collected by centrifugation, washed twice with methanol, and dried overnight in a vacuum oven to obtain 0.1238 g of a white solid.

(2)将产物放入马弗炉中,350℃下煅烧4h,得到黄色固体0.0915g。产物的场发射扫描电镜,高分辨透射电镜,氮气吸附脱附实验结果如图1、2、3。 (2) The product was put into a muffle furnace and calcined at 350° C. for 4 hours to obtain 0.0915 g of a yellow solid. Field emission scanning electron microscopy, high resolution transmission electron microscopy, and nitrogen adsorption and desorption experimental results of the product are shown in Figures 1, 2, and 3.

实施例2、多级孔结构ZIF-8的制备。 Example 2. Preparation of hierarchically porous ZIF-8.

(1)反应瓶中加入2ml聚合物纳米线(2mg/ml)溶液,83ml甲醇,再加入5ml Zn(NO3)2· 6H2O(250mM)甲醇溶液,10ml 2-甲基咪唑(250mM)甲醇溶液。摇晃均匀后室温下静置。24h后得到白色絮状沉淀,离心收集,用甲醇洗涤两次,真空烘箱抽干过夜,得到白色固体0.0727g。 (1) Add 2ml polymer nanowire (2mg/ml) solution, 83ml methanol to the reaction bottle, then add 5ml Zn(NO 3 ) 2 · 6H 2 O (250mM) methanol solution, 10ml 2-methylimidazole (250mM) methanol solution. Shake well and let stand at room temperature. After 24 hours, a white flocculent precipitate was obtained, which was collected by centrifugation, washed twice with methanol, and dried overnight in a vacuum oven to obtain 0.0727 g of a white solid.

(2)将产物放入马弗炉中,将产物放入马弗炉中,350℃下煅烧4h,得到黄色固体0.0504g。 (2) The product was put into a muffle furnace, and calcined at 350° C. for 4 hours to obtain 0.0504 g of a yellow solid.

实施例3、多级孔结构ZIF-7的制备。 Example 3. Preparation of hierarchically porous ZIF-7.

(1)反应瓶中加入10ml(2mg/ml)聚合物纳米线溶液,15ml甲醇,再加入25ml Zn(NO3)2· 6H2O(250mM)甲醇溶液,50ml苯并咪唑(250mM)甲醇溶液。摇晃均匀后室温下静置。3天后得到白色沉淀,离心收集,用甲醇洗涤两次,真空烘箱抽干过夜,得到白色固体0.3216g。 (1) Add 10ml (2mg/ml) polymer nanowire solution and 15ml methanol to the reaction bottle, then add 25ml Zn(NO 3 ) 2 · 6H 2 O (250mM) methanol solution, 50ml benzimidazole (250mM) methanol solution . Shake well and let stand at room temperature. After 3 days, a white precipitate was obtained, which was collected by centrifugation, washed twice with methanol, and dried overnight in a vacuum oven to obtain 0.3216 g of a white solid.

(2)将产物放入马弗炉中,400℃下煅烧3h,得到白色固体0.2852g。产物的场发射扫描电镜,高分辨透射电镜实验结果如图4。 (2) The product was put into a muffle furnace and calcined at 400°C for 3 hours to obtain 0.2852 g of a white solid. The results of field emission scanning electron microscopy and high resolution transmission electron microscopy of the product are shown in Figure 4.

实施例4、HKUST-1。 Embodiment 4, HKUST-1.

(1)反应瓶中加入10ml(2mg/ml)表聚合物纳米线溶液,40ml乙醇/水(1:1),再加入25ml Cu(NO3)2·3H2O(375mM)水溶液,25ml 均苯三甲酸(250mM)乙醇溶液。摇晃均匀后室温下静置。3天后得到蓝色沉淀,离心收集,用乙醇洗涤两次,真空烘箱抽干过夜,得到白色固体0.2321g。 (1) Add 10ml (2mg/ml) epipolymer nanowire solution, 40ml ethanol/water (1:1) to the reaction bottle, then add 25ml Cu(NO 3 ) 2 ·3H 2 O (375mM) aqueous solution, 25ml Benzenetricarboxylic acid (250mM) ethanol solution. Shake well and let stand at room temperature. After 3 days, a blue precipitate was obtained, which was collected by centrifugation, washed twice with ethanol, and dried overnight in a vacuum oven to obtain 0.2321 g of a white solid.

(2)将产物放入马弗炉中,300℃下煅烧3h,得到黑色固体0.2018g。产物的场发射扫描电镜,高分辨透射电镜实验结果如图5。 (2) The product was put into a muffle furnace and calcined at 300°C for 3 hours to obtain 0.2018 g of a black solid. The results of field emission scanning electron microscopy and high resolution transmission electron microscopy of the product are shown in Figure 5.

Claims (2)

1. a preparation method for multi-stage porous organic frame compound, is characterized in that concrete steps are:
First, di-block copolymer self-assembly in solvent forms the flexible polymer nano wire of nucleocapsid structure, the then stratum nucleare of crosslinking nano line; Again the solvent of nano wire solution is switched to the needed solvent of MOFs crystallization;
Then, in polymer nano rice noodles solution, add metal salt solution and organic ligand solution, form mixing solutions; Crystallization under room temperature, obtains metal organic frame/nucleocapsid structure polymer nano rice noodles mixture;
Finally, calcining, removes polymer nano rice noodles, obtains the micropore of existing MOF self, has again the large mesoporous multilevel hole material forming by after the little mesoporous and stratum nucleare calcining forming after the calcining of polymer nano rice noodles shell;
Wherein, the MOFs of institute is ZIF-8, ZIF-7, ZIF-67, HKUST-1 or CD-MOF-1, here, ZIF-8 represents the MOFs being formed by divalent zinc ion and glyoxal ethyline, ZIF-67 represents the MOFs being formed by divalent cobalt ion and glyoxal ethyline, ZIF-7 represents the MOFs being formed by divalent zinc ion and benzoglyoxaline, and HKUST-1 represents the MOFs that bivalent cupric ion and trimesic acid form, and CD-MOF-1 represents the MOFs being formed by monovalence potassium ion and γ-cyclodextrin;
Described di-block copolymer is polyethylene glycol-four vinyl pyridines, and polyoxyethylene glycol chain segment molecular weight is between 2000-20000, and P4VP molecular weight is between 3000-20000; Linking agent is Isosorbide-5-Nitrae-dibromobutane, and the pyridine ring that crosslinking degree is 5%-100% has been crosslinked.
2. the preparation method of multi-stage porous organic frame compound according to claim 1, is characterized in that described calcining temperature is 150 DEG C-500 DEG C, and calcination time is 0.5 hour-10 hours.
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