JP2012519171A - Coordination block copolymer - Google Patents

Abstract

The present invention provides compositions of crystalline coordination copolymers and methods for making and using the compositions. In the production method, a plurality of types of organic molecules are assembled to produce a porous skeleton material having a layered structure or a core-shell structure. These materials are synthesized by a sequential growth method such as a seed growth method. The present invention further provides a simple procedure for controlling functionality.
[Selection] Figure 1a

Description

  This invention was made with the award number (Award No.) DE-FC26-07NT42121 with the support of the National Energy Technology Laboratory of the US Government, US Department of Energy. The US government has certain rights to the invention.

  Known materials of the type porous solids are called organometallic structures (MOFs) or coordination polymers.

  Coordination bond theory developed by Alfred Werner [A. Werner, Z .; Anorg. Allg. Chem. 3 (1893) 267] made it possible for the first time to understand the experimental results of complex inorganic chemistry. A stable coordination polymer can be obtained by adding an organic molecule (such as diamine or diacid) capable of forming a complex to a dissolved inorganic salt. The distance between the metal ions as the coordination center can be set in a wide range depending on the structure of the organic component, and a microporous to mesoporous material can be obtained. Coordination polymers can therefore be varied and are well documented in the literature [S. Kitagawa et al. Angew. Chem. Int. Ed. 43 (2004) 2334].

  Since a coordination polymer having porosity can be synthesized, a new type of material called crystalline molecular sieve can be obtained. The crystal structure of any coordination polymer can be determined by X-ray crystal structure analysis and the pore or channel dimensions can be determined fairly accurately. The internal surface area of some porous coordination polymers is considerably larger than other porous materials. The diameter and shape of the pores can be adjusted considerably, and a larger pore diameter can be synthesized compared to known zeolites. Functionalization of the backbone or skeletal structure of these materials can be achieved by starting synthesis using organic linkers that already incorporate functional groups or by post-synthesis modifications.

  Recently, a coordination copolymerization method using two topologically distinguishable linkers has been reported. By this method, a microporous coordination polymer having a mesoporous structure which has not been achieved so far has been reported. (MCP) can be generated [K. Koh, A .; G. Wong-Foy and A.W. J. et al. Matzger, Angew. Chem. , Int. Ed. 47, (2008), 677]. The first example of this method [UMCM-1 (crystalline material at the University of Michigan)] is by adjusting the molar ratio of each organic linker instead of a mixture of crystalline phases resulting from individual assemblies of a single linker type. Have shown that new phases incorporating all organic components can be produced.

  The present invention describes a new class of materials, coordination copolymers. In order to manufacture these materials, a sequential growth method such as a seed growth method is used, and a layer function is created by three-dimensional growth of the second or more shells. The material can be used in a process such as a separation process and as a reaction catalyst.

  The novel material of the present invention is a coordination copolymer comprising at least a first coordination polymer and a second coordination polymer, wherein the first and second coordination polymers are not the same. The first coordination polymer and the second coordination polymer can be present in the first and second layered structures. If desired, at least the third coordination polymer can be layered on the second layer. The third coordination polymer may be the same as the first layer. The third coordination polymer may have a different composition or a different structure than either of the first and second coordination polymers. The first and second layered structures may form a core and shell structure. At least a third coordination polymer can be layered on the shell. The third coordination polymer may be the same as the core. The third coordination polymer may have a different composition or a different structure than either of the first and second coordination polymers.

  One method of making a coordination copolymer is to add at least one metal cation source and at least one organic linking compound to a solvent to form a first solution or colloidal suspension. Treating the first solution or colloidal suspension to form crystals of the first coordination polymer; adding at least one metal cation source and at least one organic linking compound to the solvent; Forming a second solution or colloidal suspension, wherein the second solution is not the same as the first solution or colloidal suspension; And treating the second solution or colloidal suspension to produce crystals of the second coordination polymer in one or more of the first coordination polymer. Forming as a layer covering the crystal, thereby forming a coordination copolymer, wherein the first coordination polymer is not the same as the second coordination polymer. The crystals of the first coordination polymer may be sized in the range of 10 nanometers to 1 micron. Coordination copolymers can also be produced by the “one pot” method. For example, a coordination copolymer can be prepared by adding at least one metal cation source and at least one organic linking compound to a solvent to form a solution or colloidal suspension; Forming a crystal of the first coordination polymer; at least one additional agent selected from the group consisting of a second metal cation source, a second organic linking compound, and combinations thereof in solution or Adding to the colloidal suspension; and treating the solution to form crystals of the second coordination polymer as a layer over the one or more crystals of the first coordination polymer, thereby distributing Forming a coordination copolymer, wherein the first coordination polymer is not the same as the second coordination polymer.

  The coordination copolymer is obtained by bringing the first component of the mixture into contact with the mixture by contacting the mixture with the coordination copolymer including at least the first coordination polymer and the second coordination polymer. It can be used in a method for separating from the second component, where the first and second coordination polymers are not identical. The coordination copolymer can also be used as a catalyst in chemical reactions. For example, the coordination copolymer comprises contacting a coordination copolymer comprising at least a first coordination polymer and a second coordination polymer with a feed comprising at least one reactant. Can be used to convert at least one reactant to obtain a converted product, wherein the first and second coordination polymers are not the same, and at least one coordination polymer. Has a catalytic function.

FIG. 1a is a microscopic image of the bilayer core-shell coordination copolymer of the present invention. FIG. 1b is a microscopic image of the bilayer core-shell coordination copolymer of the present invention. FIG. 2a is a photomicrograph of the multilayer coordination copolymer of the present invention. FIG. 2b is a photomicrograph of the multilayer coordination copolymer of the present invention. FIG. 3 shows (1) a coordination copolymer when two types of coordination polymers of the coordination copolymer are IRMOF-3 and MOF-5, and (2) two types of coordination copolymers. FIG. 2 is a plot of the amount of Nile Red adsorbed to a coordination copolymer when the coordination polymers are cyclohexyl-modified IRMOF-3 and MOF-5 as a function of exposure time.

  The present invention provides a new class of materials called coordination block copolymers, comprising at least two different coordination polymers. The two different coordination polymers are spatially continuous, and the coordination copolymer represents a zone or block of the first coordination polymer and a zone or block of the second coordination polymer. . The at least two different coordination polymers may be a porous coordination polymer, a non-porous coordination polymer, or a combination thereof.

  The method described herein illustrates the preparation of a coordination block copolymer comprising at least two non-identical coordination polymers. For example, the two coordination polymers may have different pore sizes, and when used to produce a single coordination copolymer, the resulting multicomponent coordination copolymer is It may have at least one portion having one pore size and at least one other portion having a second pore size. Three or more coordination polymers can be used to produce a multi-component coordination copolymer, resulting in multiple portions of composite material having different pore sizes. Therefore, a new kind of material having new characteristics can be created. One advantage of the method of the present invention is that the coordination polymer used to produce the composite material (and thus the pore size) can be selected depending on the application for which the composite material is used. Is a point. Further, depending on the method of manufacturing the composite material, adjustments can be made during the manufacture of the composite material to position a particular pore size in a specific area of the composite material. Therefore, if necessary, the coordination copolymer can be produced for a specific application by selecting the type of coordination polymer at the start and the method for producing the coordination copolymer. It is believed that coordination copolymers can be synthesized with high selectivity and high capacity in applications such as size selective separation and size and / or shape selective catalysts.

An example of a suitable coordination polymer for use in synthesizing the composite coordination copolymer is first described, followed by a method for producing the composite coordination copolymer.
The coordination polymer used to make the coordination copolymer composite defines the molecular backbone. The coordination polymer contains a plurality of metal atoms or metal clusters linked by a plurality of organic linking ligands. A linking ligand coordinates two or more metal atoms or metal clusters. The organic linking ligands may be the same or different. The organic linking ligand may be charge neutral, or each organic linking ligand is derived from a negatively charged multidentate ligand. The linking ligand of the coordination copolymer is characterized by including a first linking ligand having a first skeleton and a second linking ligand having a second skeleton. In the most common case, the first and second skeletons are the same, for example, having the same aromatic ring structure or linear hydrocarbon structure. However, it goes without saying that the first and second skeletons may be different. For example, the first and second skeletons may have different ring structures or linear structures; the first and second skeletons have the same ring structure or linear structure, but are substituted with different functional groups. Alternatively, the first and second skeletons may be hydrocarbons or have one or more atoms replaced with heteroatoms such as N, O, or S. The coordination copolymer may take a crystal form such as a crystal cluster, may be catalytically active, and the surface of the coordination polymer may be polar or nonpolar.

In one embodiment of the invention, each metal cluster of the coordination copolymer comprises one or more metal ions, with the organic linking ligand partially or completely offsetting the charge of the metal ions. In certain embodiments, each metal cluster comprises a metal ion or metalloid having a metal selected from the group consisting of metals from Groups 1-16 of the IUPAC periodic table, including actinides, lanthanides, and combinations thereof . Specific examples of useful metal ions include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , ^{Ta 3+, Cr 3+, Mo 3+} , W 3+, Mn 3+, Mn 2+, Re 3+, Re 2+, Fe 3+, Fe 2+, Ru 3+, Ru 2+, Os 3+, Os 2+, Co 3+, Co 2+, Rh + , Rh ²⁺ , Rh ³⁺ , Ir ⁺ , Ir ³⁺ , Ni ²⁺ , Ni ⁺ , Pd ²⁺ , Pd ⁴⁺ , Pt ²⁺ , Pt ⁴⁺ , Cu ²⁺ , Cu ⁺ , Ag ⁺ , Au ⁺ , Zn ²⁺ , Gd ²⁺ , H ²⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴ There are, but are not limited to, metal ions selected from the group consisting of ⁺ , Pb ²⁺ , As ⁵⁺ , As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ , and Bi ⁺ .

The coordination copolymer comprises a coordination polymer having an organic linking ligand. In one embodiment of the invention, the organic linking ligand is of the formula I:
XnY (I)
(Wherein X is a functional group; n is an integer greater than or equal to 2; and Y is a hydrocarbon group or a hydrocarbon group in which one or more carbon atoms are replaced with a heteroatom). Can be represented.

In one embodiment, X is CE ₂ ⁻ , C (Ar) ₂ ⁻ , RC (═G) C═C (G ′) R, or R ¹ C (ZR ² ) C═C (ZR ² ) R. ¹ , wherein E is O, S, Se, or Te, Z is N, P, or As, R, R ¹ , R ² are H, an alkyl group, or an aryl group, and A Is N, P, or As, and G is O, S, Se, or Te. Suitable examples for X include CO ₂ ⁻ , CS ₂ ⁻ , ROPO ₂ ⁻ , PO ₃ ⁻² , ROPO ₃ ⁻² , PO ₄ ⁻² , ROAsO ₂ ⁻ , AsO ₃ ⁻² , ROAsO ₃ ⁻² , SO ^{_{3 -, SO 4 -, SeO}} 3 -, SeO 4 -, TeO 3 -, or TeO ₄ ^- there are such as, but not limited to. In other embodiments, Y is a monocyclic aromatic ring, a polycyclic aromatic ring, a monocyclic heteroaromatic ring, a polycyclic heteroaromatic ring, an alkyl group having 10 to 10 carbon atoms, and combinations thereof And a site selected from the group consisting of: In other embodiments, Y is alkyl, alkylamine, arylamine, alkylarylamine, or phenyl. In still other embodiments, Y is a C _1-10 alkyl, C _6-50 aromatic ring, or C _4-24 heteroaromatic ring system. The organic linking ligand can be the same throughout the coordination polymer, or two or more organic linking ligands can be incorporated into the coordination polymer.

In one embodiment of the invention, the coordination copolymer is characterized by having an average pore size (measured by nitrogen adsorption) of 2-40 angstroms, 5-30 angstroms, or 8-20 angstroms. In another embodiment of the invention, the coordination copolymer has a surface area (measured by Langmuir method) of 2000 m ² / g or more. In another embodiment, the coordination copolymer is characterized by having a surface area (measured by the Langmuir method) of 1000 to 40000 m ² / g. In yet another embodiment, the coordination polymer has a pore volume (measured by nitrogen adsorption) of 0.1 cm ³ / g or more per gram of coordination polymer.

  Furthermore, the bulk properties of multi-component coordination copolymers can be controlled by varying the concentration of different linkers in solution during the synthesis of at least one coordination polymer (see Example 2). By controlling the bulk properties of the coordination copolymer, it is possible to synthesize a coordination copolymer for a specific purpose that requires specific bulk properties. For example, controlling the surface area of the coordination copolymer composite will allow the end user to use less material to accomplish a given task. This is because a larger surface area results in so many active sites.

  Controlling the order in which the linkers are added constitutes a method of making the coordination copolymer, and such control can be viewed as a seed growth method involving the epitaxial growth of metal organic coordination molecules containing different components. The resulting material composition is a layered material derived by skeletal nesting. Conventionally, several methods have been applied to the replacement of metal ions, resulting in a strong color contrast or a change in magnetism. The method of the present invention allows the engineering of multilayer crystal structures with different functionalities. First, two different coordination polymer (A and B) seeds are made separately, for example by the solvothermal method. By applying time and heating, seeds of coordination polymers A and B can be grown. Typical crystallization temperatures range from ambient temperature to 250 ° C., and reaction times range from minutes to months. Crystallization that takes several hours to several days at ambient temperatures to 125 ° C is most common. Examples of reaction time include 1 minute to 5 months, or 2 hours to 4 days. Suitable solvents include formaldehyde, sulfoxide, nitrile, ester, amine, ether, ketone, aromatic compound, aliphatic compound, water, and combinations thereof. Specific examples of solvents include ammonia, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylene chloride, tetrahydrofuran, ethanolamine, triethylamine, N, N- Dimethylformamide, N, N-diethylformamide, methanol, ethanol, propanol, alcohols, dimethyl sulfoxide, chloroform, bromoform, dibromomethane, iodoform, dimedmethane, halogenated organic solvent, N, N-dimethylacetamide, N, N-diethyl Examples include, but are not limited to, acetamide, 1-methyl-2-pyrrolidinone, amide solvents, methylpyridine, dimethylpyridine, and mixtures thereof.

  Next, a part of each reaction solution is exchanged. For example, a portion of the reaction solution containing the coordination polymer A species is added to the reaction solution for the coordination polymer B; and a portion of the reaction solution containing the coordination polymer B species is added to the coordination weight. Add to reaction solution for coalescence A. Of course, for purity, a portion containing the seed may be added to the fresh reaction solution instead of the reaction solution used to generate the seed. Time and heat are again applied to grow a new layer of coordination polymer on the already existing primary layer (see Example 3). At this point, the procedure is stopped, where the coordination copolymer comprises two coordination polymers, one as the first layer or core layer and the other over or surrounding the first layer (eg, shell). ) As. Alternatively, the procedure may be continued one or more times, thereby growing a further layer of coordination polymer. The original two coordination polymers can be used to form alternating layers, or additional different coordination polymers can be used to create layers of different composition. It is also within the scope of the present invention to grow the first layer on the support with the second layer (and so on) grown on the first layer.

  By selecting different coordination polymers for different layers, the coordination copolymer composition of the material can be engineered to suit a particular purpose. For example, the coordination polymer in the first layer or core layer may contain a larger pore size while the coordination polymer in the first layer above the first layer may contain a smaller pore size. Thus, the material of the present invention can be used as a high capacity selective adsorbent. The smaller pore coordination polymer layer acts to provide selectivity, while the larger pore coordination polymer in the first layer acts to provide higher capacity. Guest uptake and release kinetics can be adjusted. Other properties of the coordination copolymer can be adjusted in a similar manner. Furthermore, a multistage catalyst can be produced with a single material.

  By selecting at least one coordination polymer having a catalytic function, the coordination copolymer can be used as a catalyst for catalyzing the reaction. For example, a coordination copolymer is converted by contacting a feed comprising at least one reactant with a coordination copolymer comprising at least a first coordination polymer and a second coordination polymer. By obtaining the product, it can be used in a process for converting at least one reactant. Here, the first and second coordination polymers are not the same, and at least one of the coordination polymers includes a catalytic function. In another example, the reaction involves contacting a feed comprising a hydrocarbon with a coordination copolymer comprising at least a first coordination polymer and a second coordination polymer to obtain a conversion product. , May be a hydrocarbon conversion reaction. Here, the first and second coordination polymers are not the same, and at least one of the coordination polymers includes a catalytic function. Hydrocarbon conversion processes include cracking, hydrocracking, aromatic alkylation, isoparaffin alkylation, isomerization, polymerization, reforming, dewaxing, hydrogenation, dehydrogenation, alkyl exchange, dealkylation, hydration, dehydration, There are reactions such as hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanation, ring opening, and syngas shift. In other embodiments, the catalyst function can be added to the coordination copolymer after synthesis.

  Examples 5-7 further show that coordination polymers with specific crystal habits can be successfully layered on the crystals of coordination polymers with different crystal habits. In general, this is a difficult task to do well. This is because crystals grow most effectively on seeds with the same morphology and habit. For example, a prism grows best on a prism and a cube grows best on a cube. On the other hand, the crystals can also be heterogeneously nucleated on the nanoparticles present in the supersaturated reaction mixture with respect to the reagents necessary for nucleation and growth of a given crystalline material. For example, ice crystals are heterogeneously nucleated and then continue to grow as snowflakes on nanodust particles in the atmosphere.

  This process is made possible by preparing at least two types of crystals (especially the first layer, ie, the core layer) in small (ie nano) crystal size regimes. In one embodiment, the nanocrystals can range from 10-100 nm, but crystals close in size to 500 nm (or even 1 micron) can also be used as the core material. These nanocrystals are often more irregular in crystal habit and crystal morphology compared to larger crystals of the same material. However, despite their nanosize, as well as crystal habit and crystal morphology, which are often less obvious, crystals can be easily identified by a characteristic powder XRD pattern. Similarly, when the second layer is grown on the surface of the first layer, the characteristic XRD pattern of the second material appears as another set of peaks in the XRD pattern of the final product.

  An important advantage of this process is that crystals of the second material are grown on the crystals of the first layer (ie, the core layer) in the same reaction solution used to grow the first material. It is possible. Such in-situ synthesis, or “one-pot” synthesis, can be used to minimize waste or costly intermediate processing steps (e.g., before subjecting the first material to the second layer layering chemistry). It is practically extremely important because it is no longer necessary to isolate and purify the material. Nevertheless, in another embodiment of the invention, in order to grow the second material on the first material, the first layer of crystals is isolated and reconstituted in a supersaturated solution of the second material. Suspend. This processing may be required when the solution chemistry and other processing conditions of the two materials are incompatible.

  Another aspect of the “one pot” Examples 5-7 is to match the chemistry of the material of the first layer (ie, core layer) with the chemistry of the second layer. This is important, for example, because the solvent for the first layer must be similar to or the same as the solvent for the second layer. This is because the reagent for preparing the second layer must be added to the nanocrystal suspension of the first layer. If the reagents for preparing the second material are insoluble in the solvent from the preparation of the first material, or these reagents remain in solution from the preparation of the first material. Reaction with other soluble agents may result in undesirable by-products and / or precipitates. On the other hand, the chemistry of the preparation of the second material may be modified to react with the first material crystal, to modify the first material crystal, and / or to dissolve the first material crystal to some extent. Can be adjusted. Composite materials obtained by forming the second layer on the first material may have highly desirable physical properties (eg, increased porosity and crystal integrity).

In the examples, the selection of the core material and the shell material was based on the XRD peak offset placement for each of the two materials. The general experimental design for these experiments involves reducing the reactants for each product to a stoichiometric amount based on the molecular formula of the desired product. In order to facilitate coordination of the linker to the metal or metal cluster, an equimolar amount of base [eg triethylamine (TEA)] per carboxylic acid functional group was used. The reaction of the first material (ie, core material) is allowed to proceed for an appropriate time before the premixed reactant for the second material is added. Details are described in Examples 5-7. Abbreviations used in the examples include: H ₃ BTC-1,3,5-benzenetricarboxylic acid; DMF-N, N′-dimethylformamide; EtOH-ethyl alcohol; TEA-triethylamine; H ₂ BDC-1, 4-benzenedicarboxylic acid; and Bipy-4,4′-bipyridyl; The MOF formulas used in the examples are as follows: HKUST-1: Cu ₃ BTC ₂ (H ₂ O) ₃ ; MOF-508: ZnBDC (bipy) _1/2 DMF (H ₂ O) _1/2 ; IRMOF- 1: Zn ₄ O (BDC) ₃ ; and MIL-53: Al (OH) (BDC) (H ₂ BDC) _0.7 ;

  As used in the examples below, coordination copolymer abbreviations are as follows: describe the first MOF formula followed by the symbol @ followed by the second MOF formula To do. Multiple types of copolymers in a coordination copolymer are indicated by describing multiple MOF formulas, each separated from the others by the symbol @. For example, IRMOF-3 @ MOF-5 is used to denote a coordination copolymer comprising IRMOF-3 and MOF-5; MOF-5 @ IRMOF-3 @ MOF-508 is used as MOF-5 and MOF-5 -3 and MOF-508 are used to represent coordination copolymers. It should be noted that if the coordination copolymer has multiple layers of MOF, the layer order can be expressed in abbreviations.

A coordination copolymer derived from ditopic linkers benzene-1,4-dicarboxylate (BDC) and 2-aminobenzene-1,4-dicarboxylate (ABDC) Help explain the invention. As background, in the presence of zinc nitrate tetrahydrate and diethylformamide (DEF), pure benzene-1,4-dicarboxylic acid reacts to form coordination polymer MOF-5 (analysis of crystal structure) It should be noted that this is a simple cubic net in the Fm-3m space group. Similarly, pure 2-aminobenzene-1,4-dicarboxylic acid reacts to produce IRMOF-3, which has the same structure as MOF-5. As a first example, MOF-5 and IRMOF-3 seeds were made separately according to the same solvothermal method as in the synthesis of MOF-5. After 15 hours, each reaction solution was changed [ie, MOF-5 seed crystals were immersed in an unreacted solution of ABDC and Zn (NO ₃ ) ₂ (and vice versa)]. The solution was further heated for 15 hours to obtain a coordination copolymer. A microscopic image of the resulting product revealed a core-shell cube (see FIGS. 1a and 1b). The color contrast corresponds to white (MOF-5) and orange (IRMOF-3). FIG. 1a shows IRMOF-3 as a shell layer and MOF-5 as a core layer, while FIG. 1b shows MOF-5 as a shell layer and IRMOF-3 as a core layer. The scale bar in FIGS. 1a and 1b is 200 μm. In both cases using MOF-5 and IRMOF-3 as seeds, a core-shell-like MOF is appropriately obtained. ¹ H-NMR analysis after decomposition of the core-shell MOF shows that the molar composition of the block copolymer is BDC: ABDC = 1: 1, on the surface of the seed MOF, It shows that MOF shells growing from anchor points of the carboxylate group are properly formed. The N ₂ uptake of both core-shell MOFs is 820 cm ³ / g for both IRMOF-3 @ MOF-5 and MOF-5 @ IRMOF-3, and the uptake of MOF-5 (920 cm ³ / g) and the amount of IRMOF-3 uptake (750 cm ³ / g).

  Multi-layer crystals can also be generated by using seed growth in the presence of core-shell MOF. Growth of new layers from the core-shell species creates alternating layers of MOF-5 and IRMOF-3 layers. Two different multilayer MOFs were successfully obtained; MOF-5 @ IRMOF-3 @ MOF-5 shown in FIG. 2a and IRMOF-3 @ MOF-5 @ IRMOF-3 shown in FIG. 2b. The scale bar in FIGS. 2a and 2b is 200 μm.

Example 1: Core - Shell MOF Preparation H ₂ ABCD (48mg, 0.26 mmol) and _H 2 BDC (44mg, 0.26 mmol) was charged separately in vials of 20 ml. To both vials were added Zn (NO ₃ ) ₂ .4H ₂ O (0.208 g, 0.795 mmol) and 10 ml DEF. The mixture was sonicated for 15 minutes and heated at 100 ° C. After 15 hours, cubic crystals were formed in both solutions. Both solutions were then decanted and switched to each other. The mixture was heated at 100 ° C. for an additional 15 hours. The product was washed with DEF and then immersed in CHCl ₃ .

Example 2: Production of multilayer MOF Production of a core-shell MOF as a seed was carried out in the same manner as in Example 1. After formation of the core-shell MOF, the solution was decanted and Zn (NO ₃ ) ₂ .4H ₂ O (0.208 g, 0.795 mmol) and H ₂ ABCD (48 mg, 0.26 mmol) or H ₂ A fresh mixture comprising BDC (44 mg, 0.26 mmol) in 10 ml DEF was added. The resulting mixture was heated at 100 ° C. for an additional 15 hours. The product was washed with DEF and then immersed in CHCl ₃ .

Example 3 Post-Modification of Shell Part in Core-Shell MOF Wet core-shell MOF (IRMOF-3 @ MOF-5, 10 mg) and 10 mg cyclohexyl isocyanate were mixed in 1 ml chloroform. The mixture was stirred at room temperature for 3 days with a shaking bath. After the reaction, the product was washed with chloroform.

Example 4 Measurement of Nile Red Diffusion into MOF MOF was immersed in a solution obtained by mixing 5 ppm of Nile Red in chloroform. At a specified time, the absorbance of the solution was measured with a UV-visible spectrophotometer. A calibration curve was used to calculate the concentration of Nile Red in the solution. From the decrease in Nile Red concentration, the amount of Nile Red adsorbed on MOF was measured. FIG. 3 shows (1) a coordination copolymer when two types of coordination polymers of the coordination copolymer are IRMOF-3 and MOF-5, and (2) two types of coordination copolymers. Is a plot of the amount of Nile Red adsorbed as a function of exposure time when the coordination polymer is cyclohexyl modified IRMOF-3 and MOF-5.

Example 5: Nano MOF-508 on Nano HKUST-1
H ₃ BTC (0.5 g, 2.38 mmol), DMF (8.3 ml), EtOH (8.3 ml), water (8.3 ml), and copper (II) nitrate (0.83 g, 3.57 mmol) ) Was added to a glass jar with magnetic stirring at room temperature to prepare a nano HKUST-1 suspension. TEA (1 ml, 7.14 mmol) was added slowly, the jar was sealed and the cloudy blue suspension was stirred at room temperature for 3.5 hours. Meanwhile, H ₂ BDC (0.38 g, 2.37 mmol), DMF (50 ml), EtOH (50 ml), bipy (0.19 g, 1.18 mmol), and zinc (II) nitrate (0.70 g). , 2.37 mmol) was prepared in a glass beaker with magnetic stirring at room temperature. This clear colorless solution was added to the above nano HKUST-1 suspension, the jar was sealed and the mixture was stirred. After 3 hours, the pH of the suspension was 2-3. The TEA / DMF / EtOH (0.6 ml, 41.7 ml, 41.7 ml) solution was then slowly added dropwise to the mixture, and the resulting mixture was finally sealed and stirred overnight. The turquoise solid was separated from the clear colorless liquid (pH about 5) by filtration through 0.45 μm filter paper and dried in a 60 ° C. oven under a nitrogen atmosphere overnight. Elemental analysis by inductively coupled plasma (ICP) on the filtrate revealed that less than 0.0001% by mass of Zn and Cu remained in the solution after the reaction. On the other hand, the XRD powder pattern for the solid material showed peaks for both MOF-508 and HKUST-1, and ICP elemental analysis for the solid product revealed the presence of both metals (Cu and Zn).

Example 6: Nano MOF-508 on Nano IRMOF-1
Nano IRMOF-1 by adding H ₂ BDC (0.85 g, 5 mmol), DMF (100 ml), and zinc (II) nitrate (3.0 g, 10 mmol) to a glass jar with magnetic stirring at room temperature. A suspension of was prepared. TEA (1.4 ml, 10 mmol) was added slowly, the jar was sealed and the cloudy white suspension was stirred at room temperature for 3.5 hours. Meanwhile, H ₂ BDC (0.38 g, 2.37 mmol), EtOH (50 ml), bipy (0.19 g, 1.18 mmol), and zinc (II) nitrate (0.70 g, 2.37 mmol). ) Was prepared in a glass beaker with magnetic stirring at room temperature. This milky white suspension was added to the nano IRMOF-1 suspension above, the jar was sealed and the mixture was stirred. After 3 hours, the pH of the suspension was 3-3.5. A TEA / EtOH (0.7 ml, 50 ml) solution was slowly added dropwise to the mixture and the resulting mixture was finally sealed and stirred overnight. The white solid was separated from the colorless clear liquid (pH about 4) by filtration through 0.45 μm filter paper and dried in a 60 ° C. oven under a nitrogen atmosphere overnight. Elemental analysis of the filtrate revealed that 0.16% by mass of Zn remained in the solution after the reaction. On the other hand, the XRD powder pattern for the solid material showed peaks for both MOF-508 and IRMOF-1, and elemental analysis for the solid product revealed the presence of Zn.

Example 7: Nano MIL-53 on Nano HKUST-1
H ₃ BTC (0.5 g, 2.38 mmol), DMF (8.3 ml), EtOH (8.3 ml), water (8.3 ml), and copper (II) nitrate (0.83 g, 3.57 mmol) ) Was added to a glass jar with magnetic stirring at room temperature to prepare a nano HKUST-1 suspension. TEA (1 ml, 7.14 mmol) was added slowly, the jar was sealed and the cloudy blue suspension was stirred at room temperature for 3.5 hours. Meanwhile, H ₂ BDC (0.58 g, 3.5 mmol), DMF (10 ml), EtOH (10 ml), H ₂ O (10 ml), and aluminum (III) nitrate (2.6 g, 6.9 mmol). ) Was prepared in a glass beaker with magnetic stirring at room temperature. This cloudy white suspension was slowly added to the nano HKUST-1 suspension above, the jar was sealed and the mixture was stirred. After 3 hours, the pH of the suspension was 1.5-2.5. A solution of TEA / DMF / EtOH / H ₂ O (0.96 ml, 7.7 ml, 7.7 ml, 8.7 ml) was slowly added dropwise to the mixture, and the resulting mixture was finally sealed and stirred overnight. The blue suspension is centrifuged at 15,000 relative centrifugal force (rcf) for 1 hour, the mother liquor at pH 2-3 is decanted, and the resulting solid is placed in a 50 ° C. oven under a nitrogen atmosphere. Dried overnight. The XRD powder pattern for the solid material shows peaks for both MIL-53 and HKUST-1, and elemental analysis for the mother liquor shows that 0.094 wt% Cu and 0.11 wt% Al are present in the solution. Made clear.

Claims (10)

  A coordination copolymer comprising at least a first coordination polymer and a second coordination polymer, wherein the first and second coordination polymers are not the same.   The first and second coordination polymers comprise at least one metal atom or metal cluster selected from the group consisting of any of the elements of Groups 1-16 of IUPAC, actinides, and lanthanides. Item 5. The coordination copolymer according to Item 1. The first and second coordination polymers are
Wherein _X n Y (I)
(Wherein X is a functional group; n is an integer greater than or equal to 2; and Y is a hydrocarbon group or a hydrocarbon group in which one or more carbon atoms are replaced with a heteroatom). The coordination copolymer of claim 1, comprising the organic linking ligand shown.   The coordination copolymer according to claim 1, wherein the first and second coordination polymers are organometallic structures (MOF). The average pore size of the coordination copolymer is 2 to 40 angstroms as measured by nitrogen adsorption, where the surface area of the coordination copolymer is greater than 2,000 m ² / g as measured by the Langmuir method. The coordination copolymer according to claim 1, wherein the pore volume per gram of the coordination copolymer is greater than 0.1 cm ³ / g as measured by nitrogen adsorption.   The coordination copolymer according to claim 1, wherein the first coordination polymer and the second coordination polymer are present in the first and second layered structures or in a core-shell structure.   7. The coordination copolymer of claim 6, further comprising at least a third coordination polymer layered on the second layer or shell. The first and second coordination polymers are Cu ₃ BTC ₂ (H ₂ O) ₃ (HKUST-1), ZnBDC (bipy) _1/2 DMF (H ₂ O) _1/2 (MOF-508), The coordination of claim 1, selected from the group consisting of Zn ₄ O (BDC) ₃ (IRMOF-10), and Al (OH) (BDC) (H ₂ BDC) _0.7 (MIL-53). Copolymer. A method of using a coordination copolymer comprising at least a first coordination polymer and a second coordination polymer that are not identical,
a) separating the first component from the second component by contacting the mixture comprising the first component and the second component with the coordination copolymer and recovering the first component; or b) converting at least one reactant by contacting a feed comprising at least one reactant with a coordination copolymer to produce a converted product, wherein at least one coordination; The coordination polymer contains a catalytic function;
Including methods. a) adding at least one metal cation source and at least one organic linking compound to a solvent to produce a first solution or colloidal suspension;
b) treating the first solution or colloidal suspension to form crystals of the first coordination polymer;
c) adding at least one metal cation source and at least one organic linking compound to the solvent to produce a second solution or colloidal suspension, wherein the second solution is the first solution or Not the same as a colloidal suspension;
d) adding crystals of the first coordination polymer to the second solution or colloidal suspension; and e) treating the second solution or colloidal suspension to form the second coordination polymer of Forming a crystal as a layer covering one or more crystals of the first coordination polymer, thereby forming a coordination copolymer, wherein the first coordination polymer is a second coordination polymer; Not the same as the coordination polymer;
A method for producing a coordination copolymer, comprising:

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