Process for the production of metal-organic framework (MOF-structured) composite materials

Abstract

A method (10) for producing a metal-organic framework (MOF)-polymer composite material, the method comprising: (25) Forming a homogeneous solution by combining a MOF mother liquor and a polymer solution; (40) synthesizing a MOF structure in the homogeneous solution by crystallizing the homogeneous solution; (45) wherein crystallization of the MOF structure in the homogeneous solution yields the MOF structure dispersed in a residual solution; and (60) demixing the residual solution to form a polymer-rich phase; wherein the MOF structure is surrounded by the polymer-rich phase to produce a MOF-polymer composite material, wherein: the polymer solution comprises a solvent and a polymer; the polymer is soluble in the solvent; demixing the residual solution involves applying a release agent to the residual solution with the MOF structure dispersed in the residual solution to form the polymer-rich phase; the polymer is not soluble in the release agent; and the MOF structure is not soluble in the release agent, further comprising: (35) spreading the homogeneous solution onto a substrate prior to crystallization of the MOF structure; and separating the MOF-polymer composite from the substrate to provide a MOF-structured article, wherein: the MOF structure is characterized by a pore size distribution; and The pore size distribution of the MOF structure dispersed in the residual solution is essentially unchanged after demixing to form the polymer-rich phase. The MOF structure is homogeneously distributed in the polymer-rich phase, so that the MOF-polymer composite is a homogeneous composite material. wherein: the polymer solution comprises a solvent and a polymer; the polymer is soluble in the solvent; and the polymer reverses during demixing from a solvent phase to form the polymer-rich phase, wherein: the MOF mother liquor includes: a first solvent, a metal salt and a reactant; wherein the reactant can be synthesized to form an organic linker during the formation of the MOF structure; the polymer solution includes: a second solvent and a polymer; and wherein the polymer is soluble in the second solvent, where the polymer is polysulfone.

Description

INTRODUCTION

[0001] The present disclosure relates to a metal-organic framework (MOF) structured article made of a composite material including a MOF structure dispersed in a polymer phase, and to a method according to the invention for producing a MOF-structured article, including forming a composite material including a MOF structure dispersed in a polymer phase.

[0002] DE 10 2005 017 195 A1 relates to a composite material, in particular a composite membrane, particularly for gas separation, vapor separation, or pervaporation, comprising at least a first polymer and a second polymer. Furthermore, a method for producing a composite material, in particular a composite membrane.

[0003] CN 1 03 922 290 A describes a method for the confined growth of nanoscale coordination polymers (NCPs) using metal oxide nanotubes as templates. A soluble metal salt and an organic ligand are dissolved in an organic solvent, and a substrate with grown nanotubes is introduced into the solution, allowing the NCPs to grow within the nanotubes. The method utilizes the confinement and enrichment properties of the nanotubes. BACKGROUND

[0004] The crystallization of metal-organic frameworks (MOFs) almost exclusively results in polydisperse microcrystalline powders. The polydispersity of the microcrystalline MOF powder limits the applicability of MOF powder in applications such as energy storage, separations, catalysts, sensor materials, etc. Forming the MOF into an article may require the addition of a binder and / or the application of pressure to densify the MOF article. For example, when casting or molding a thin article such as a film or membrane, the surface smoothness and / or surface texture of the thin article is difficult to control, and / or the surface of the thin article may be rough due to the variation in the particle size of the contained MOF powder and a non-uniform distribution of MOF particles of variable size within the thin article.Crystalline MOF particles are inherently brittle with a high tendency to fracture. When blended into a polymer, for example, prior to casting and drying the polymer-MOF blend into an article such as a film or membrane, the crystalline MOF particles may fracture into different sizes. This can contribute to non-uniform mixing of MOF particles in the polymer during casting and to a non-uniform distribution of the MOF particles in the film or membrane formed from the polymer-MOF blend. The non-uniformity of the blend and the variation in distribution, size, and morphology of the MOF particles in the cast article can lead to a lack of homogeneity in the properties and characteristics of the resulting thin article. SUMMARY

[0005] The object of the invention is to eliminate the above-mentioned disadvantages. This object is achieved by a method according to claim 1

[0006] Methods for preparing a metal-organic framework (MOF)-polymer composite material that can be formed as a macroscopic metal-organic framework (MOF-structured) article, such as a membrane or a film, and a metal-organic framework (MOF-structured) article fabricated by the method are described. In one example, a method for preparing a metal-organic framework (MOF)-polymer composite material includes forming a homogeneous solution by combining a MOF mother liquor and a polymer solution and synthesizing, via crystallization of the homogeneous solution, a MOF structure in the homogeneous solution. Crystallization of the MOF structure in the homogeneous solution yields the MOF structure dispersed in a residual solution.The method further includes separating the residual solution to form a polymer-rich phase, wherein the dispersed MOF structure is surrounded by the polymer-rich phase to produce a MOF-polymer composite. According to the invention, the MOF structure is homogeneously distributed in the polymer-rich phase, so that the MOF-polymer composite is a homogeneous composite.

[0007] The method may include controlling the crystallization of the MOF structure in the homogeneous solution, for example, by controlling the crystallization time and / or crystallization temperature, by controlling the ratio of reactants in the mother liquor, and / or by controlling the type and / or ratio of solvent, such that the MOF structure is uniform in at least one of crystal size, pore size, and morphology. According to the invention, the MOF-polymer composite material formed by the method described herein is characterized by a pore size distribution of the MOF structure dispersed in the residual solution that remains substantially unchanged after demixing to form the polymer-rich phase, such that the MOF-polymer composite material and the MOF structure crystallized in the homogeneous solution have substantially the same pore size distribution.The metal-organic framework (MOF)-polymer composite material may also be referred to herein as a MOF-polymer composite or a MOF-polymer composite material.

[0008] According to the invention, the method includes distributing the homogeneous solution onto a substrate prior to crystallizing the MOF structure and separating the MOF-polymer composite from the substrate after forming the MOF-polymer composite to provide a metal-organic framework (MOF-structured) article. In one example, the MOF-structured article is formed as a thin article, such as a film or a membrane. The substrate may be configured such that the substrate defines a final shape of the MOF-structured article, which may be a thin film or a membrane. In one example, the MOF-structured article may be formed as a thin sheet, which may be further fabricated, for example, by cutting or trimming, into a final shape film or membrane.In one example, the thin MOF-polymer composite sheet can be laminated to at least one other sheet, which can be another MOF-polymer composite sheet or a sheet of another material, to form a laminated article. The metal-organic framework (MOF-structured) article may also be referred to herein as a MOF-structured article.

[0009] As described herein, the homogeneous solution from which the MOF-polymer composite is formed includes a MOF mother liquor and a polymer solution. The MOF mother liquor includes MOF reactants according to the invention, including a solvent, a metal salt, and an organic reactant that can be synthesized to provide an organic linker during the formation of the MOF structure. According to the invention, the polymer solution includes a solvent and a polymer, wherein the polymer is soluble in the solvent. Crystallization of the MOF structure in the homogeneous solution yields a MOF structure dispersed in a residual solution, wherein the residual solution is the homogeneous solution depleted by the formation of the MOF structure.According to the invention, the residual solution is separated by applying a release agent to the residual solution with the MOF structure dispersed in the residual solution to form the polymer-rich phase. As the polymer-rich phase forms, it surrounds and / or encloses the MOF structure to form the MOF-polymer composite. Thus, the MOF structure remains in the dispersed state in which it was crystallized in the homogeneous solution, providing a high degree of uniformity of the MOF structure in the polymer matrix, resulting in a homogeneous MOF-polymer composite.

[0010] In one example, demixing is accomplished by immersing the residual solution in the release agent while the MOF structure remains dispersed in the residual solution in its crystallized state, such that the release agent reacts with the residual solution to cause the polymer dissolved in the release agent to undergo phase inversion, inverting the polymer from a solvent phase to form a non-solvent phase surrounding the MOF structure in its crystallized state. The non-solvent phase of the polymer after inversion is referred to herein as the polymer-rich phase. According to the invention, the release agent is selected such that both each polymer and the MOF structure are insoluble in the release agent. In one illustrative example, the polymer comprises polyvinylidene difluoride (PVDF) dissolved in a solvent comprising dimethylformamide (DMF).In this example, the mother liquor contains a copper salt and a reactant comprising benzene-1,3,5-benzene tricarboxylic acid (H3BTC), so that during the synthesis, a copper benzene-1,3,5-tricarboxylate MOF (Cu-BTC MOF) is crystallized in the homogeneous solution. In this example, the polymer is separated from the residual solution by a separating agent comprising water. According to the invention, the polymer is polysulfone. The polymer can comprise at least one of a crystalline polymer and an amorphous polymer, so that during the separation, the polymer-rich phase inversions are carried out by at least one recrystallization and gelation.

[0011] The method described herein for fabricating a metal-organic framework (MOF)-structured article is facilitated by forming the MOF composite from a homogeneous solution, which is demixed after synthesis of the MOF structure to invert the polymer in the residual solution into a polymer-rich phase surrounding the MOF structure and integrating it into a polymer matrix while the MOF structure remains in the residual solution, thereby forming the MOF-polymer composite. As such, the MOF-polymer composite is formed from the homogeneous solution directly and in a continuous process that does not require removing and transporting the MOF structure from one container to another. Furthermore, no mixing step for blending the MOF structure into the polymer is required because the MOF structure is synthesized and dispersed in the residual solution from which the polymer-rich phase is demixed.As such, breakage of the MOF structure during transportation and mixing is avoided, and the MOF structure remains synthesized in the resulting MOF-polymer composite. The uniformity, distribution, and continuity of the MOF structure formed on the substrate in the homogeneous solution are maintained and integrated into the polymer matrix formed around the distributed MOF structure to yield a homogeneous MOF-polymer composite exhibiting uniformity of properties and characteristics throughout the composite. As such, a MOF-structured article formed and / or fabricated from the composite is favored by uniformity of properties, including controlled pore size, crystal size, and morphology.

[0012] A MOF-structured article, which may be a thin article such as a membrane or film, formed by the method described herein is advantageous due to the uniform distribution of the MOF structure incorporated into the MOF-polymer composite, wherein the crystallization of the MOF structure can be controlled in situ on the substrate to produce a MOF structure with a controlled and / or predetermined size and morphology such that the polymer-rich phase, as it separates from the residual solution, surrounds the MOF structure to produce a smooth surface on the thin article membrane or film. As used herein, the term "MOF-polymer composite thin article" can encompass either a membrane or a film of a MOF composite, or both, using the method described herein.Due to their encapsulation in the polymer-rich phase, the integrity, distribution, and uniformity of the MOF structure in the thin article is maintained during movement and processing of the MOF-polymer composite, for example, during the fabrication of MOF-structured articles from the thin article by cutting, trimming, folding, lamination, etc., and / or during the assembly of the MOF-structured article with other components.

[0013] The above features and advantages, as well as other features and advantages of the present teachings, will become more apparent from the following detailed description of some of the best modes and other embodiments for carrying out the present teachings, as defined in the appended claims, with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] In the following, one or more embodiments are described by way of example with reference to the accompanying drawings, in which: Fig. 1 schematically illustrates a method for preparing a metal-organic framework (MOF)-polymer composite material according to the disclosure; and Fig. Figure 2 schematically illustrates a pore size distribution of a MOF structure and a MOF-polymer composite including the MOF structure.

[0015] It should be understood that the accompanying drawings are not necessarily to scale and present a somewhat simplified representation of various preferred features of the present disclosure as disclosed herein, including, for example, specific dimensions. Details pertaining to such features will be determined in part by the particular intended application and use environment. DETAILED DESCRIPTION

[0016] The components of the disclosed embodiments described and illustrated herein can be arranged and constructed in a variety of different configurations. Therefore, the following detailed description of the embodiments is not intended to limit the scope of the disclosure as claimed, but is merely representative of possible embodiments thereof. Moreover, although numerous specific details are set forth in the following description to provide a thorough understanding of the embodiments disclosed herein, some embodiments may be practiced without some of these details. Moreover, for the sake of clarity, certain technical material understood in the related art has not been described in detail to avoid unnecessarily obscuring the disclosure.Furthermore, the disclosure as illustrated and described herein may be practiced in the absence of any element not expressly disclosed herein.

[0017] Methods for preparing a metal-organic framework (MOF)-polymer composite material, which can be formed as a macroscopic metal-organic framework (MOF-structured) article, such as a membrane or a film, and a metal-organic framework (MOF-structured) article fabricated by the method are described herein. The metal-organic framework (MOF)-polymer composite material may also be referred to herein as a MOF-polymer composite or a MOF-polymer composite material. The metal-organic framework (MOF-structured) article may also be referred to herein as a MOF-structured article. The term "MOF," as used herein, is an acronym for a metal-organic framework.

[0018] With reference to Fig. Figure 1 is an exemplary method for preparing a metal-organic framework (MOF)-polymer composite material, generally designated 10. The method 10 includes providing a MOF mother liquor specified in step 20 and providing a polymer solution in step 25, which are combined in step 30 to form a homogeneous solution. The MOF mother liquor provided in step 20 includes a solvent, a metal salt, and a reactant, wherein the reactant can be synthesized to provide an organic linker to form organic ligands during the formation of the MOF structure. In one non-limiting example, the MOF mother liquor includes a copper salt and a reactant comprising benzene-1,3,5-tricarboxylic acid (H3BTC), such that upon synthesis, a copper-benzene-1,3,5-tricarboxylate MOF (Cu-BTC MOF) is crystallized in the homogeneous solution.As a non-limiting example, the solvent included in the MOF mother liquor may include a mixture of ethanol (EtOH), dimethylformamide (DMF), and water (H2O) in the required proportions in combination with the polymer solution to synthesize the formation of the MOF structure in the homogeneous solution. The examples provided herein are illustrative, and it is understood that other combinations of solvent, metal salt, and reactant may be used to form a MOF mother liquor, which, when combined with a polymer solution as described herein, can be synthesized to create a MOF framework. A MOF framework, as used herein, means a compound consisting of metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures, also referred to herein as MOF crystals.The MOF structure, as used herein, means the structure formed by and consisting of the MOF framework synthesized by crystallization in a homogeneous solution. The MOF structure is characterized by one or more of the crystal size distribution, the size of the MOF crystals in the MOF structure, and a pore size distribution (see ). Fig. 2) the pores formed in the MOF structures, by an indicator of the uniformity of the distribution of the MOF crystals in the MOF structure, by the morphology of the MOF crystals, and / or by an indicator of the uniformity of the morphology of the MOF crystals in the MOF structure.

[0019] The polymer solution provided in step 25 includes a solvent and a polymer, the polymer being soluble in the solvent. In a non-limiting example, the solvent contained in the polymer solution includes dimethylformamide (DMF), and the polymer includes polyvinylidene difluoride (PVDF) dissolved in a solvent comprising dimethylformamide (DMF). In this example, the polymer is separated from the residual solution by a separating agent comprising water (H2O). According to the invention, the polymer is polysulfone.

[0020] The method 10 combines, in step 30, the MOF mother liquor provided in step 20 and the polymer solution provided in step 25 to form a homogeneous solution. In step 35, the homogeneous solution is distributed on a substrate for synthesizing and crystallizing the MOF structure in the homogeneous solution. The substrate is configured to hold the homogeneous solution during further processing in steps 40, 45, 50, and 55. In one example, the substrate may be configured as a vessel that defines the shape of the MOF-polymer composite to be produced. For example, the substrate may be configured to enable the formation of the MOF-polymer composite configured as a MOF-structured article that is a thin article such as a membrane or a film.The thin article formed from the MOF-polymer composite material described herein may be referred to herein as a MOF-polymer thin article. In one example, the substrate may be configured to form the MOF-polymer thin article as a sheet, where the shape of the sheet, e.g., the perimeter of the sheet, is defined by the substrate. In another example, the substrate could be configured to form a thin sheet having a predetermined size and / or shape, where the predetermined shape may be a polygon, an ellipse, or another shape that may have a regular or irregular shape. The substrate may be configured to form a thin article with one or more openings, for example, in a ring shape, where, for example, the ring shape of the thin article may be required for the end application of the MOF-polymer thin article.It should be understood that the examples provided herein are not limiting, and that various substrates can be configured to support the homogeneous solution and the resulting MOF-polymer composite to form MOF-structured articles of various shapes. In another example, the substrate can be configured to form the thin MOF-polymer article as a continuous sheet, e.g., a sheet of fixed width and variable length, which can be rolled onto a carrier, for example, for storage or, optionally, for further processing for the final application, as in step 65 in FIG. Fig. 1 is specified.

[0021] With further reference to Fig. 1, at step 40, a MOF structure is synthesized by crystallizing the homogeneous solution in the homogeneous solution. The method 10 may include controlling the crystallization of the MOF structure in the homogeneous solution, for example, by controlling the crystallization time and / or the crystallization temperature, such that the MOF structure is uniform in at least one of crystal size, pore size, and morphology. As used herein, the term “uniform” may mean nonrandom, nonrandom, controlled to a predetermined range less than that which would result from uncontrolled conditions or random variation, and / or uniform in at least one of structure, properties, and characteristics. In one illustrative example, the distribution of pore sizes of the MOF structure formed in the residual solution is uniform within a predetermined range of about 5 to 9 angstroms (Å), as in Fig. 2 is represented by the graph line identified as “MOF”.

[0022] At step 45, crystallization of the MOF structure in the homogeneous solution results in the MOF structure dispersed in a residual solution, where the "residual solution," as used herein, is the remaining homogeneous solution depleted by the formation of the MOF structure. The uniform MOF structure crystallized from the homogeneous solution and dispersed on the substrate remains in its as-formed position and state in the residual solution on the substrate during the formation of the polymer-rich phase and polymer matrix at steps 50, 55, such that the MOF structure is substantially undisturbed, e.g., retaining its structure, pore distribution properties, particle size distribution, etc., during steps 50, 55.The method 10 described herein is therefore favored in that it is not necessary to remove the MOF structure from solution prior to formation of the MOF-polymer composite, so that the MOF structure in situ on the substrate is significantly less susceptible to fracture, changes in particle size, etc. during formation of the surrounding polymer-rich phase, and the MOF structure remains uniformly distributed in the resulting MOF-polymer composite formed during steps 50, 55.

[0023] In step 50, the residual solution is demixed to form a polymer-rich phase, wherein the dispersed MOF structure is encapsulated by the polymer-rich phase to produce a MOF-polymer composite. The residual solution is demixed in step 50 by applying a release agent to the residual solution, while the MOF structure remains as formed and dispersed in the residual solution to form the polymer-rich phase, such that the polymer-rich phase, as formed by the conversion from a solvent phase to a non-solvent phase, surrounds, encapsulates, and / or integrates the MOF structure to form the MOF-polymer composite. As such, the MOF structure remains in the dispersed state in which it was crystallized in the homogeneous solution, providing a high degree of uniformity of the MOF structure in the polymer matrix, yielding the homogeneous MOF-polymer composite.According to the invention, demixing is carried out by immersing the MOF structure dispersed in the residual solution into the release agent, such that the release agent causes the polymer dissolved in the release agent to undergo a phase inversion, whereby the polymer inverts a solvent phase to form a non-solvent phase. The non-solvent phase of the polymer after the inversion is referred to herein as the polymer-rich phase. In particular, the release agent is selected such that both each polymer and the MOF structure are insoluble in the release agent.

[0024] The MOF-polymer composite obtained in step 55 is characterized by the homogeneous distribution of the MOF structure in the polymer-rich phase, such that the resulting MOF-polymer composite material is formed as a homogeneous composite material whose structure, properties, and characteristics are substantially uniform. In one example, the MOF structure is encapsulated in the polymer-rich phase, e.g., in the polymer matrix, such that the surface of the MOF-polymer composite is substantially defined by the polymer-rich phase and has a smooth and uniform texture.In one example, the particle size of the MOF structure and the thickness of the polymer matrix are each controlled such that the MOF particles are completely encapsulated in the polymer-rich phase, so that the MOF particles do not protrude from the surface of the resulting MOF-polymer composite, and so that the surface finish and surface texture of the MOF-polymer composite are defined only by the polymer-rich phase. In the example described in . Fig. 2, the MOF-polymer composite material formed by the process described herein is characterized by a pore size distribution of the MOF structure dispersed in the residual solution which is substantially unchanged after demixing to form the polymer-rich phase, so that the MOF-polymer composite material, according to the method described in Fig. 2 as “MOF:Polymer”, and the MOF structure distributed in the residual solution, according to the diagram line in Fig.2 as “MOF”, have substantially the same pore size distribution, ie the pore size of the MOF remains uniform within a predetermined range of about 5 to 9 angstroms (Å) after formation of the MOF-polymer composite material.

[0025] At step 60, the MOF-polymer composite material is separated from the substrate to provide a MOF-structured article. In one example, the substrate is configured such that the MOF-structured article is a thin article such as a film or a membrane. As described herein, the substrate may be configured such that the substrate defines a final shape of the MOF-structured article, where "final shape" as used herein is substantially the final shape of the article during use.

[0026] In an optional step 65, the MOF-structured article removed from the substrate in step 60 may be further processed or manufactured for end use, for example, by cutting or trimming a net-shaped article from the MOF-structured article. In one example, the thin sheet of MOF-polymer composite may be removed from the substrate in step 60 and assembled with at least one other component to form an assembly. In one example, the MOF-structured article may be a thin article, such as a plate, membrane, or film, laminated to another plate, membrane, or film, or laminated between multiple plates, membranes, or films.The laminate formed from the MOF may include one or more layers of the MOF-polymer composite material formed by method 10, and / or may include at least one layer of the MOF-polymer composite material formed by method 10 and at least one layer of another material.

[0027] A thin MOF polymer article, which may be a thin article such as a membrane or film, formed by the method described herein is advantageous in that it has a uniform distribution of the MOF structure integrated and / or encapsulated within the MOF-polymer composite, wherein the crystallization of the MOF structure can be controlled in situ on the substrate to produce a MOF structure with a controlled and / or predetermined size and morphology such that during in situ demixing of the polymer-rich phase on the substrate, the polymer-rich phase demixes from the residual solution to surround and / or encapsulate the MOF structure to produce a smooth surface on the thin article membrane or film.The integrity, distribution, and uniformity of the MOF structure in the thin article is maintained during movement and processing of the MOF-polymer composite thin article due to the integration and / or encapsulation of the MOF structure into the surrounding polymer matrix, for example, during the fabrication of MOF-structured articles from the thin article by cutting, trimming, folding, lamination, etc., and / or during the assembly of the MOF-structured article with other components.

[0028] The examples provided herein are not limiting, and it is understood that a MOF-structured article and / or a MOF-polymer composite formed by the method described herein can be used in various applications, inserted into an assembly, installed as a membrane, applied as a film, etc. In one example, the membrane can be an absorbent electrolyte configured as a multicomponent dendrite barrier layer of a lithium metal battery. For example, the MOF-polymer composite formed by the method described herein could be configured as a MOF-structured article for use in one or more of sensing, catalysis, gas storage, separation, and / or purification processes.

[0029] The method described herein for fabricating a metal-organic framework (MOF)-structured article is facilitated by forming the MOF composite material from a homogeneous solution, which is demixed after synthesis of the MOF structure to invert the polymer surrounding the MOF structure in the residual solution into a polymer-rich phase that surrounds the MOF structure and integrates it into a polymer matrix. As such, the MOF composite material is formed from the homogeneous solution directly and in a continuous process that does not require removal and transport of the MOF structure from one container to another.The uniformity, distribution, and continuity of the MOF structure formed on the substrate in the homogeneous solution are maintained and integrated into the polymer matrix formed around the distributed MOF structure to yield a homogeneous MOF-polymer composite material exhibiting uniformity of properties and characteristics throughout the composite material. As such, a MOF-structured article formed and / or fabricated from the composite material is favored by uniformity of properties, including controlled pore size, crystal size, and morphology.

[0030] While the detailed description and drawings or figures support and describe the present teachings, the scope of the present teachings is defined solely by the claims. While some of the best modes and other modes for carrying out the present teachings have been described in detail, various alternative designs and embodiments are possible for practicing the present teachings, as defined in the appended claims.

Claims

[1] A process (10) for producing a metal-organic framework (MOF)-polymer composite material, the process comprising: (25) Forming a homogeneous solution by combining a MOF mother liquor and a polymer solution; (40) synthesizing a MOF structure in the homogeneous solution by crystallizing the homogeneous solution; (45) wherein crystallization of the MOF structure in the homogeneous solution yields the MOF structure dispersed in a residual solution; and (60) demixing the residual solution to form a polymer-rich phase; wherein the MOF structure is surrounded by the polymer-rich phase to produce a MOF-polymer composite material, wherein: the polymer solution comprises a solvent and a polymer; the polymer is soluble in the solvent; demixing the residual solution involves applying a release agent to the residual solution with the MOF structure dispersed in the residual solution to form the polymer-rich phase; the polymer is not soluble in the release agent; and the MOF structure is not soluble in the release agent, further comprising: (35) spreading the homogeneous solution onto a substrate prior to crystallization of the MOF structure; and separating the MOF-polymer composite from the substrate to provide a MOF-structured article, wherein: the MOF structure is characterized by a pore size distribution; and The pore size distribution of the MOF structure dispersed in the residual solution is essentially unchanged after demixing to form the polymer-rich phase. The MOF structure is homogeneously distributed in the polymer-rich phase, so that the MOF-polymer composite is a homogeneous composite material. wherein: the polymer solution comprises a solvent and a polymer; the polymer is soluble in the solvent; and the polymer reverses during demixing from a solvent phase to form the polymer-rich phase, wherein: the MOF mother liquor includes: a first solvent, a metal salt and a reactant; wherein the reactant can be synthesized to form an organic linker during the formation of the MOF structure; the polymer solution includes: a second solvent and a polymer; and wherein the polymer is soluble in the second solvent, where the polymer is polysulfone. [2] The process (10) of claim 1, wherein the polymer may comprise at least one of a crystalline polymer and an amorphous polymer such that during demixing the polymer-rich phase inversions are carried out by at least one of recrystallization and gelation.

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