Additive manufacturing techniques and ink formulations to incorporate sorbent particles

Abstract

Ink compositions are provided for forming contactor structures and / or structures for use in adsorption or absorption contactors using solvent-based additive manufacturing (SBAM) techniques. Methods for forming contactors using SBAM are also provided. The ink compositions can include a substantial amount of sorbent particles to enhance adsorption by the contactor. Metal-organic framework (MOF) structures and zeotype framework structures are examples of types of sorbent particles that can be incorporated into the ink compositions for forming contactor structures by SBAM. The inks can further include polymeric components that can function as structural components of polymeric structural materials produced by additive manufacturing. Such structural materials can correspond to polymeric materials with incorporated sorbent particles. In some aspects, the polymeric structural materials and / or sorbent particles can be selective for adsorption of CO2 from process fluid streams.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application is a Patent Cooperation Treaty (PCT) application claiming priority under PCT Article 8 to U.S. Provisional Application No. 63 / 195,310, filed June 1, 2021, U.S. Provisional Application No. 63 / 191,640, filed May 21, 2021, and U.S. Provisional Application No. 63 / 191,715, filed May 21, 2021, the entireties of which are incorporated by reference herein as if fully set forth below.

[0002] (Technical field) Ink formulations and corresponding additive manufacturing techniques are provided for forming adsorbent contactor structures based on structural materials corresponding to the polymeric materials that encase the adsorbent particles. [Background technology]

[0003] Mitigating CO2 emissions from various types of CO2 sources, both industrial and small scale, is a current area of ​​interest. One type of strategy for mitigating CO2 emissions is to use adsorbents or absorbents to remove CO2 from potential exhaust gas streams and then desorb this CO2 as part of a stream that can be treated to reduce, minimize, or eliminate the release of CO2 into the atmosphere.

[0004] Although various materials capable of adsorbing or absorbing CO2 are known, implementing such adsorbents / absorbents in effective contactor structures remains challenging. Some of the difficulties in designing contactor structures relate to the limited types of contactor designs that can be implemented using conventional materials. Conventional contactor designs typically incorporate the adsorbent / absorbent as part of a packed bed or monolith. A packed bed structure can be effective for incorporating large amounts of adsorbent / absorbent in a volume. The particles in the packed bed can represent sorbent particles, a combination of sorbent particles and binder or diluent, or particles of support material on which the sorbent is deposited. However, packed beds typically cause a large pressure drop compared to the amount of fluid flowing through the packed bed, making it difficult to scale up packed bed adsorbents to large volumes for applications such as CO2 capture. Metal or ceramic monoliths can offer an option to packed beds and can provide flow paths that reduce the pressure drop challenges. However, the density of adsorbent sites that can be introduced into a metal or ceramic monolith is often limited to the surface of the flow paths. In addition, managing the temperature within the monolith can present another set of challenges. In particular, cooling the monolith structure typically requires the introduction of a heat transfer fluid into the interior of the monolith. Due to the difficulty of machining composite structures into ceramic or metal monoliths after fabrication, it can be difficult to provide a targeted amount of heat transfer fluid to the interior of the monolith structure while reducing or minimizing the risk of intermixing of the heat transfer fluid with the process fluid stream.

[0005] What is needed is a system and method for forming at least a portion of a contactor structure that improves the density of sorption sites within the contactor structure over conventional monoliths while reducing or minimizing the fluid flow restrictions associated with packed bed adsorbents. Rather, the resulting contactor structure may be suitable for processing large volumes of fluid streams, such as may be required to remove CO from industrial scale flue gas streams.

[0006] US Patent Application Publication No. 2021 / 0040343 describes a method for using a three-component ink composition including a polymer, a solvent, and a non-solvent for solvent-based additive manufacturing. In three-dimensional printing, after depositing an ink layer, a polymer structure is formed by phase inversion after evaporating a portion of the solvent from the ink.

[0007] The paper entitled "Defect-free asymmetric hollow fiber membranes of Torlon®, a polyamide-imide polymer, for high pressure CO2 separation" (Kosuri, MR, Koros, W. I, Journal of membrane Science, 2008, 320, 65) describes the determination of the binodal lines of ternary phase diagrams by the cloud point method. Summary of the Invention

[0008] In various embodiments, a solvent-based additive manufacturing ink composition is provided. The ink composition comprises 2.0 wt% or more of an adsorbent material by weight of the ink composition. The ink composition further comprises 35 wt% or less of a polymer. The ink composition further comprises a solvent for the polymer. The ink composition further comprises a structure-forming component for the polymer, and the ratio of the weight of the polymer to the combined weight of the solvent and non-solvent is 0.7 or less.

[0009] In some embodiments, the ink composition can include one or more of the following characteristics: 10 wt% or more of adsorbent material, a ratio of the weight of adsorbent to the weight of polymer of 1.0 or more, 15 wt% or less of polymer, and / or a ratio of the weight of polymer to the combined weight of solvent and structure-forming components of 0.20 or less.

[0010] In some embodiments, such ink compositions can be used to form 3D printed polymer structures, i.e., such ink compositions can be printed and then a portion of the solvent can be evaporated to form a continuous polymer structure. In some embodiments, such continuous polymer structures formed by 3D printing are provided. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 shows nitrogen physisorption isotherms obtained for the MOF adsorbent and fibers formed by 3D printing incorporating the MOF adsorbent.

[0012] [Diagram 2] FIG. 2 shows the nitrogen physisorption isotherm of FIG. 1 on an expanded scale.

[0013] [Diagram 3] FIG. 3 illustrates an example of diffusion from a flow path in a contactor structure into the porous structural material that defines the flow path. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] All numerical values ​​in the detailed description and claims herein are modified by "about" or "approximately" the numerical value indicated to account for experimental error and variations that would be expected by one of ordinary skill in the art. [overview]

[0015] In various aspects, an ink composition is provided for forming contactor structures and / or structures for use in adsorption or absorption contactors using solvent-based additive manufacturing (SBAM) techniques. Methods for forming contactors using SBAM are also provided. The ink composition can include a substantial amount of sorbent particles to enhance the adsorption of components (such as CO2) by the contactor. Metal-organic framework (MOF) structures and zeotype framework structures are examples of types of sorbent particles that can be incorporated into the ink composition for forming contactor structures by SBAM. The ink can include a polymer component that can function as a structural component of a polymeric structural material produced by additive manufacturing. Such a structural material can correspond to a polymeric material with incorporated sorbent particles. In some aspects, the polymeric structural material and / or the sorbent particles can have selectivity for adsorbing CO2 from a process fluid stream. In some aspects, the polymeric structural material and / or the sorbent particles can have selectivity for adsorbing gas phase components from a gas phase stream containing a light gas.

[0016] Solvent-based additive manufacturing (SBAM) is a method for forming structures by three-dimensional (3D) printing. In SBAM, structures are formed by printing a target shape with an ink that includes at least a solvent, a polymer component, and an additive component, where the ink is capable of forming a structural material when the solvent evaporates. The amount of solvent, polymer, and additive component in the ink composition can be selected based on a phase diagram so that a continuous polymer phase is formed when a target amount of solvent evaporates. The additive component is referred to herein as a "structure-forming component." In some aspects, the additive component (i.e., the structure-forming component) can be a non-solvent in the ink composition. In some aspects, it has been found that a pore-forming component (alternatively referred to as a pore former) can be used as a structure-forming component in addition to and / or in place of the non-solvent. It is noted that temperature-induced phase separation is one type of SBAM process.

[0017] It has been found that the addition of a significant amount of sorbent particles to a latent ink composition results in a significant change in the rheology of the ink composition. This is in part because the sorbent particles are dispersed in the ink. As a result, the ink composition corresponds to a suspension, rather than a solution, of the polymer and added components in the solvent. In various aspects, an ink composition is provided that includes a significant amount of particles, which has a rheology suitable for performing SBAM to form a contactor and / or part of the contactor structure. In various aspects, the ink composition can correspond to a mixture of a solvent, a polymer component, sorbent particles, and a structure-forming component. The structure-forming component can correspond to a non-solvent, a pore-forming component, or a mixture thereof.

[0018] Some types of adsorbent materials, such as materials with MOFs and zeotype framework structures, can have relatively large surface areas, which contribute to the effectiveness of such materials for adsorption applications. It has been found that when the adsorbent material is incorporated into a polymer structure by the SBAM method, the resulting polymer structure has a surface area that is less than would be predicted based on the properties of the polymeric material and the adsorbent material in the polymeric structural material used to form the structure. Although the surface area and pore volume are less than predicted, it has been surprisingly found that the adsorption capacity of the adsorbent material can be substantially maintained.

[0019] Using SBAM techniques to form polymeric structural materials incorporating adsorbents can provide a variety of advantages over conventional methods for incorporating adsorbents into contactor structures. SBAM allows the fabrication of structures with internal geometries that are otherwise difficult to achieve in ceramic or metal monoliths. For example, while it is possible to add straight channels to a solid monolith, introducing geometries such as header structures or channels with multiple angular bends can be quite difficult. Fabrication techniques that involve forming ceramic or metal around a mold that is later removed may also be used, but this can pose significant reliability issues when used to create the small geometries typically desired in adsorption contactors. In addition, some structures, such as triple periodic minimal curve materials, cannot be formed by injection molding techniques. In contrast, many types of geometries can be directly formed by forming structures layer by layer from polymeric structural materials using SBAM.

[0020] In addition to allowing greater design flexibility with respect to the contactor geometry, using SBAM to form the contactor and / or structures for the contactor can increase the volume of the contactor that contributes to adsorption. In particular, in various embodiments, adsorbents (such as MOFs, zeolites, or other zeo-type materials) can be incorporated into the ink formulation used in the SBAM manufacturing process. This means that the adsorbent can be dispersed throughout the volume of the structural material used to form the contactor. Depending on the polymer selected for the polymer backbone, the ink composition, and / or the conditions for forming the polymer structure, a polymer structure can be formed with sufficient pore volume and / or complex flow paths, which allows fluids within the contactor structure to access the adsorbent material beyond the flow paths in some of the contactor structures. FIG. 3 shows an example of this. In FIG. 3, flow paths 310 correspond to the flow paths within the contactor structure. The flow paths 310 are defined by the structural material 330 that surrounds the flow paths 310. In the example shown in FIG. 3, arrows 315 indicate the direction of flow in the flow paths 310. Arrows 320 indicate the diffusion of fluid in the flow passages into the structural material 330. The diffusion indicated by arrows 320 corresponds to both diffusion into the structural material and diffusion from the structural material back to the flow passages 310. By forming a porous polymer structure, the process fluid passing through the flow passages of the porous polymer structure can diffuse into the pores of the polymer structure, thereby allowing a significant percentage of the volume of the polymer structure to participate in the adsorption / desorption cycle. This allows the adsorption to occur in an increased percentage of the contactor volume, which could potentially represent almost the entire volume of the contactor that is not just for managing the transport of the heat transfer fluid. This is in contrast to the situation with conventional monoliths, where the adsorbent capacity of the monolith corresponds to the adsorption sites on the surface of the flow passages. Conventional monoliths may have some porosity, as adsorbents are typically added to such monoliths by methods such as washcoating, but the ability to increase the volume of the monolith that provides adsorption sites accessible to the process fluid is limited.

[0021] Compared to packed bed adsorbents, the ability to form contactor structures with adsorption sites dispersed throughout the volume of the structural material allows contactors fabricated (at least in part) using SBAM to have the advantages of an increased volume of accessible adsorption sites, similar to packed beds, but with dedicated flow paths, so that fluid flow problems associated with packed beds, such as large pressure drops and unwanted flow "paths," may be reduced or minimized.

[0022] In various aspects, incorporating adsorbents into polymeric structural materials to form adsorbent contactors using ink compositions as described herein can also provide advantages over structures formed using other types of additive manufacturing methods. In various aspects, the ink compositions represent solutions and / or suspensions of polymeric materials, and therefore do not require a curing step as is required to form ceramic compositions. The resulting polymer structures can be formed during manufacturing by evaporating a portion of the ink, directly forming a polymer layer. This is in contrast to manufacturing methods that require a subsequent development step to form the structures. [Ink composition]

[0023] In various aspects, an ink composition for forming a polymer contactor structure containing adsorbent particles may include at least one solvent, at least one structure-forming component (corresponding to a non-solvent and / or pore-forming component), a polymeric material dissolved in the solvent, and particles of the adsorbent material dispersed and / or suspended in the solution.

[0024] In various embodiments, the polymer ink composition containing a substantial amount of adsorbent material can be used to form structures based on polymeric structural materials using 3D printing. The polymeric structures are formed by depositing the polymer as a solution in combination with a solvent and at least one structure-forming component, followed by solvent evaporation to trigger phase inversion to form the polymeric structures. The resulting polymeric structures have been found to have a lower surface area than would be predicted based on the ratio of polymeric material to adsorbent material in the polymeric structural material used to form the structures. Although the surface area and pore volume are lower than predicted, the adsorption capacity of the adsorbent material can be substantially maintained.

[0025] When 3D printing is performed using an ink composition that does not contain additional sorbent particles based on the ternary phase diagram, the ink composition can be selected so that the ink composition corresponds to a homogeneous phase, but the ink composition can cross the binodal line when the solvent evaporation reaches a target amount, which causes phase inversion. In some aspects, during 3D printing, the ink can be deposited in an atmosphere that contains a solvent, so that solvent evaporation is reduced or minimized until after the ink composition is "printed" onto the desired surface. For example, the print head for depositing the ink can include one or more additional nozzles for dispersing additional solvent as the printing occurs, so that phase inversion does not occur until the ink is deposited on the surface. After a layer of the ink composition is deposited or printed, the solvent can be allowed to evaporate. Optionally, the surface on which the ink is deposited can be heated to accelerate the evaporation of the solvent. As the solvent concentration is reduced, the solvent system eventually becomes unstable and the polymer dissolved in the solvent precipitates to form a continuous polymer skeleton. This structure-forming component and any remaining solvent can form a separate phase that can promote the formation of additional pore volume in the polymer structure. This structure-forming component and residual solvent can then be removed during the manufacturing process, optionally with an additional drying step.

[0026] When performing solvent-based additive manufacturing (SBAM) using a three-component ink composition without added MOF particles, the composition for the ink can be selected based on a ternary phase diagram for the polymer, solvent, and non-solvent. In particular, for ink compositions suitable for three-dimensional (3D) printing, the phase diagram for the polymer, solvent, and non-solvent will include a binodal line that separates the homogeneous (solution) region from the non-homogeneous region where the polymer forms a separate phase from the solvent and non-solvent. This binodal line in the ternary phase diagram can be determined in any suitable manner, such as using the "cloud point" method. For example, a series of compositions can be formed with intermittently lower ratios of solvent to non-solvent at a constant concentration of polymer to determine a composition (or compositions) that has a "cloudy" state due to the onset of separation into separate polymer and solvent / non-solvent phases. This process can be repeated at a series of polymer concentrations, solvent / non-solvent ratios, or combinations thereof to determine the binodal line. Another method for determining the binodal line is provided by Kosuri et al. (Kosuri, MR, Koros, W. I, Journal of Membrane Science, 2008, 320, 65).

[0027] Instead of using conventional ink compositions, it has been found that 3D printing can be performed by using ink compositions that contain a significant amount of adsorbent in addition to the polymer, solvent, and structure-forming components (non-solvent or polymer). In various embodiments, ink compositions are provided in which the weight ratio of adsorbent particles to polymer is 0.7 or more, or 1.0 or more (i.e., the weight ratio of adsorbent to polymer is 1:1), or 1.5 or more, or 2.0 or more, or 3.0 or more, such as up to 6.0 or even more. Additionally or alternatively, the ink composition can contain 10 wt% or more, or 15 wt% or more, or 20 wt% or more, such as up to 50 wt% or even more, by weight of the ink composition. Additionally or alternatively, the combined weight of polymer and adsorbent in the ink composition can represent 25 wt% or more, or 30 wt% or more, or 40 wt% or more, such as up to 60 wt% or more, by weight of the ink composition. Additionally or alternatively, the ink composition may include 7.0 wt% to 15 wt%, or 10 wt% to 15 wt%, or 12 wt% to 15 wt% of the polymer by weight of the ink composition, and the ink composition may include a sufficient amount of polymer such that phase inversion can occur.

[0028] More generally, the ink composition may comprise 2.0 wt% or more, or 5.0 wt% or more, or 10 wt% or more, or 15 wt% or more, or 20 wt% or more, for example up to 50 wt% or even more, by weight of the ink composition. More generally, the ink composition may comprise 7.0 wt% to 35 wt%, or 10 wt% to 35 wt%, or 12 wt% to 35 wt%, or 7.0 wt% to 15 wt%, or 10 wt% to 15 wt%, or 12 wt% to 15 wt% of polymer by weight of the ink composition.

[0029] In some embodiments where the ink composition includes a non-solvent, the ratio of polymer to non-solvent in the ink composition can be relatively low. Conventionally, it is usually desirable for the polymer content of a three-component ink composition to be comparable to the non-solvent content. For example, a conventional ink composition (not including suspended sorbent particles) may have a weight ratio of polymer to non-solvent of 0.5 (i.e., 1:2) or more, or 0.7 or more, or 1.0 or more, or 1.5 or more, such as up to 20 or even more. In contrast, in some embodiments, the ink composition described herein may have a weight ratio of polymer to non-solvent of less than 0.50, or 0.40 or less, or 0.35 or less, or 0.30 or less, such as a minimum of 0.10 or even less. In other embodiments, the weight ratio of polymer to non-solvent may be 0.8 or less, or 0.5 or less, or 0.40 or less, or 0.35 or less, or 0.30 or less, such as a minimum of 0.10 or even less.

[0030] Additionally or alternatively, in some embodiments where a non-solvent is used, the ink composition may have a relatively low weight ratio of polymer to the combined weight of solvent and non-solvent. Conventionally, for ink compositions that do not include suspended sorbent particles, the weight ratio of polymer to the combined solvent and non-solvent may be 0.25 or more, or 0.3 or more, such as up to 1.0 or even more. In contrast, in some embodiments, the ink compositions described herein may have a weight ratio of polymer to the combined solvent and non-solvent of 0.20 or less, or 0.17 or less, or 0.14 or less, such as a minimum of 0.08 or even less. In other embodiments, the weight ratio of polymer to the combined solvent and non-solvent may be 0.70 or less, or 0.50 or less, or 0.40 or less, or 0.30 or less, or 0.20 or less, or 0.17 or less, or 0.14 or less, such as a minimum of 0.08 or even less.

[0031] In some alternative embodiments, a wider range of sorbent materials may be incorporated into the ink composition. For example, in some embodiments, the ink composition may have a weight ratio of sorbent to polymer of 0.3-6.0, or 0.5-6.0, or 1.0-6.0, or 1.5-6.0, or 2.0-6.0, or 3.0-6.0. Lower ratios of sorbent material to polymer reduce the benefits of incorporating sorbent material, but also reduce the differences between such ink compositions and traditional three-component ink compositions. In such embodiments, the ink composition may include 3.0 wt% or more, 5.0 wt% or more, or 10 wt% or more, or 15 wt% or more, or 20 wt% or more, for example up to 50 wt% or more, by weight of the ink composition.

[0032] A variety of adsorbent materials can be incorporated into the ink composition for forming structures by 3D printing. Some examples can correspond to metal-organic framework (MOF) materials. Other examples of materials can correspond to zeotype framework materials (including materials with framework atoms other than silicon and aluminum). Still other examples can include, but are not limited to, activated carbon, porous aromatic framework materials, covalent organic framework materials, porous organic polymers, and cage materials. More generally, any type of adsorbent that can be formed into particles can be used in the ink composition as described herein, so long as the adsorbent particles are stable in the solvent and during the creation of structures from the ink composition. The adsorbent particles can have an average particle size of 0.1 μm to 50 μm. Here, the particle size of the adsorbent particles is defined as the diameter of the smallest bounding sphere that can contain the particle.

[0033] Metal-organic frameworks (MOFs) are a relatively new class of porous materials consisting of metal ion / oxide secondary building blocks linked by organically bonding ligands using covalent bonds. MOFs are characterized by low density, high internal surface area, and uniformly sized pores and channels. MOFs are typically crystalline materials. Some types of MOF materials can include zeolitic imidazole frameworks (sometimes called "ZIFs"), unconventional MOFs (sometimes called "UMOFs"), and SIFSIX MOFs.

[0034] Various MOFs have been characterized for their CO2 adsorption capabilities. For example, Mg-MOF-74 is a 2+ As another example, MOF-274 corresponds to a metal-organic framework based on ions and 2,5-dihydroxyterephthalic acid. 2+ As another example, EMM-67 is a metal-organic framework material based on metal ions, which is a combination of Mg 2+ and Mn 2+They represent metal-organic framework materials based on metal ions. MOF-274 and EMM-67 are further enhanced by adding functionalities such as diamines, N,N′-dimethylethylenediamine, or 2-aminomethylpiperidine to produce structures such as EMM-44. Yet another example is MIL-101(Cr), a metal-organic framework consisting of three chromium trigonal nodes and at least 13 oxygen atoms bridged by benzene-dicarboxylate linkages in the MTN (IZA code) topology. Yet another example is EMM-42. EMM-42 is a metal-organic framework with the same secondary building units as MIL-101(Cr), i.e., a trigonal node of three chromium atoms in which some or all of the benzene-dicarboxylate ligands connecting adjacent chromium nodes are replaced by ligands that bind phenylenebisphosphonic acid. Yet another example is HKUST-1, also called MOF-99. The HKUST-1 backbone is formed from dimeric metal units connected by benzene-1,3,5-tricarboxylic acid linker molecules. The paddlewheel unit is a structural motif commonly used to describe the coordination environment of metal centers and is also called the secondary building unit (SBU) of the HKUST-1 structure. The paddlewheel is composed of four benzene-1,3,5-tricarboxylic acid linker molecules bridging two metal centers.

[0035] In this discussion, zeotypes are defined to refer to crystalline materials with a porous framework structure formed by tetrahedral atoms connected by bridging oxygen atoms. Examples of known zeotype structures are described in "Atlas of Zeolite Frameworks" published on behalf of the Structure Committee of the International Zeolite Society, 6th revised edition, Ch. Baerlocher, LB McCusker, DH Olson, eds., Elsevier, New York (2007) and the corresponding website http: / / www.iza-structure.org / databases / . Zeolite refers to a class of zeotypes that contain aluminosilicates of zeotype framework type, but more generally, zeotypes also refer to crystal structures with zeotype frameworks that may also contain oxides of heteroatoms other than silicon and aluminum. Such heteroatoms can generally include any heteroatom known to be suitable for inclusion in a zeotype framework, such as gallium, boron, germanium, phosphorus, zinc, and / or other transition metals that can replace silicon and / or aluminum in the zeotype framework. It is noted that under this definition, zeotypes can include materials such as silicoaluminophosphate (SAPO), silicophosphate (SiPO) or aluminophosphate (AlPO) materials.

[0036] The ink composition may also include a polymer to form a polymeric structure during 3D printing. Some examples of polymers that can be incorporated into the ink composition are polymers of intrinsic microporosity. Polymers of intrinsic microporosity (PIMs) are new materials of interest for critical gas separations. Spiro centers integrated into the polymer backbone prevent efficient packing and create micropores in the polymer. The micropores can be advantageous for forming contactor structures because they allow process gases flowing through channels in the contactor structure to access different parts of the contactor volume.

[0037] Other types of porous polymers may be used to form the ink composition. In some embodiments, the polymers in the ink composition can include, but are not limited to, cellulose acetate, polyimines (e.g., Matrimid 5218), polyamide-imides (e.g., Torlon®), polyethersulfone (PES), derivatives of PIM-1 (e.g., amidoximated PIM-1), and other polymers that have inherent steric frustration that affects microporosity.

[0038] In some aspects, the solvent may be tetrahydrofuran, acetone, and / or N-methylpyrrolidone. More generally, the solvent may be a solvent that has a high solubility for the polymer in the ink composition. There are many ways to determine the level of solubility of the polymer in the volatile solvent compound. For example, in some aspects, the Hildebrand solubility parameter of the polymer and the volatile solvent compound may be measured. In some embodiments, the Hildebrand solubility parameter of the polymer and the volatile solvent compound is 3.6 MPa or less. l / 2The following differences are possible: One skilled in the art will appreciate that such embodiments provide a volatile solvent compound capable of melting the polymer to produce a substantially homogeneous solution. In some embodiments, the potential solvent can include, but is not limited to, acetaldehyde, acetic acid, acetone, acetonitrile, butanediol, butoxyethanol, diethylenetriamine, dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), dioxane, ethanol, ethylamine, ethylene glycol, formic acid, furfuryl alcohol, glycerol, methanol, methyldiethanolamine, N-methyl-2-pyrrolidone (NMP), propanol, propanediol, propanoic acid, propylene glycol, pyridine, tetrahydrofuran (THF), triethylene glycol, hydrogen peroxide, nitric acid, sulfuric acid, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, chloroform, diethyl ether, dichloromethane, or combinations thereof.

[0039] In the embodiment in which the ink composition includes a non-solvent as a structure-forming component, the non-solvent can be a compound that has low or minimal solubility for the polymer in the ink composition. There are many ways to determine the level of solubility of the polymer in the non-solvent compound. In some embodiments, the non-solvent can be selected by first measuring the Hansen solubility parameters of the polymer and the non-solvent compound. For example, the polymer and the non-solvent can be selected such that the relative energy difference calculated from the Hansen solubility parameters of the polymer and the non-solvent compound can be 1 or more. Those skilled in the art will understand that such an embodiment will provide a non-solvent compound that cannot melt the polymer.

[0040] In some embodiments, the non-solvent may correspond to toluene, dimethylacetamide, or a combination thereof. In some embodiments, the non-solvent may be N-methyl-2-pyrrolidone (NMP). In some embodiments, the non-solvent may be and / or include water. In other embodiments, the non-solvent may be substantially free of water (less than 0.1 wt%), which allows for the use of water-sensitive MOFs in the ink composition. HKUST-1 is an example of a water-sensitive MOF. In some embodiments, the non-solvent may be an alcohol, such as methanol, ethanol, isopropanol, or n-propanol. In some embodiments, the non-solvent may correspond to a mixture of non-solvents. In some embodiments, a mixture of non-solvents and pore-forming components may be added to the ink composition. It should be noted that under conditions that will exist after depositing the ink composition, the evaporation rate of the solvent may be faster than the evaporation rate of the non-solvent, because otherwise phase inversion to form the polymer structure cannot occur.

[0041] Additionally or alternatively, a pore-forming component may be included as a structure-forming component. LiNO3 is one example of a pore-forming component that may be used in the ink composition. Polyvinylpyrrolidone (PVP) is another example of a pore-forming component. The pore-forming component may be added in a relatively small amount, for example, an amount corresponding to 0.1 wt% to 20 wt%, or 0.1 wt% to 10 wt%, or 0.1 wt% to 5.0 wt%, or 1.0 wt% to 20 wt%, or 1.0 wt% to 10 wt% of the ink composition.

[0042] Table 1 shows examples of combinations of polymers, solvents, and non-solvent or pore-forming components (i.e., structure-forming components) that can be used to form ink compositions for solvent-based additive manufacturing. The final column of Table 1 shows certain solvents that may cause problems when used in combination with the listed polymers to form ink compositions for solvent-based additive manufacturing (SBAM). Note that although LiNO3 is included in the "non-solvent" column of Table 1, it actually represents a pore-forming component. [Table 1]

[0043] An example of a printer for forming structures with an ink composition can be a direct ink-write printer. For example, in some aspects, the printer can include an ink holding vessel, an ink nozzle configured to be attached to the ink holding vessel, a vapor nozzle, and a movable stage for the substrate. In some aspects, the movable stage can be configured to be removably attached to the substrate. The distance between the ink nozzle and the movable stage can include a gap substantially enclosed by the control volume shell. For example, the control volume shell can include a cylindrical shell having an opening to accommodate the vapor nozzle. The control volume shell can have any hollow shape to substantially enclose the ink nozzle and the gap. The hollow shapes include, but are not limited to, cylindrical, conical, rectangular, frusto-conical, elliptical, or any combination thereof. In some alternative aspects, additional solvent can be dispersed as vapor into the control volume shell during layer formation to help manage the amount of evaporation immediately after the layer of ink composition is deposited.

[0044] In some embodiments, the bed or surface on which the ink composition is deposited to form the 3D structure can be a heated bed or surface. The use of a heated bed or surface can assist in the evaporation of the solvent and cause phase inversion to form the polymer structure. In some embodiments, the bed or surface on which the ink composition is deposited to form the 3D printed structure can be heated to a temperature of 40°C to 80°C. [Characterization of polymer structures produced by 3D printing]

[0045] The polymer structures produced by 3D printing of the ink compositions as described herein can have unexpectedly low surface areas based on nitrogen adsorption isotherms. The polymer structures produced by 3D printing correspond to particles of adsorbent supported, dispersed and / or otherwise incorporated in a continuous polymer structure. Conventionally, the surface area of ​​such adsorbent-polymer mixtures would be expected to correspond substantially to a weighted average of the two components. However, it has been found that the surface area of ​​the resulting polymer structures can be at least 5.0%, or at least 8.0%, or at least 10% lower than conventionally expected values ​​(relative to the predicted values), for example, with a minimum surface area of ​​the polymer structures being 30% lower than the predicted values, or even less.

[0046] Additionally or alternatively, the polymeric structures produced by 3D printing of the ink compositions as described herein may have a reduced pore volume. Conventionally, the pore volume of such adsorbent-polymer mixtures is predicted to correspond to a weighted average of the two components. However, it has been found that the pore volume of the resulting polymeric structures may be at least 5.0%, or at least 8.0%, or at least 10% less than conventionally predicted values ​​(relative to predicted values), for example, with a minimum pore volume of the polymeric structures being 30% less than predicted values, or even less.

[0047] In this discussion, the surface area and pore volume of the polymeric structural materials formed by SBAM can be determined by measuring N2 adsorption isotherms according to ASTM D3663 (BET surface area) and ASTM D4641 (N2 pore volume), respectively. Where specified, pore volume may be determined according to ASTM D4284 (Hg porosimetry for pore volume).

[0048] In some embodiments, the surface area of ​​the polymeric structural material (including the encapsulated adsorbent) is greater than 50 m 2 / g or more, or 100m 2 / g or more, or 200m 2 / g or more, or 500m 2 / g or more, for example up to 3000m 2 / g, or in some cases even higher. It should be noted that such surface areas and / or pore volumes include surface area and pore volume contributions from both the polymer and the MOF. In some embodiments, the polymer structure has a pore volume (determined by nitrogen physisorption) of 0.5 cm 3 / g~1.3cm 3 / g and / or a pore volume (as determined by mercury porosimetry) of 1.0 cm 3 / g~3.0cm 3 / g. [Incorporation of diamine-loaded adsorbents into 3D-printed structures]

[0049] Certain MOFs, such as MOF-274 or EMM-67, when doped with diamines, exhibit favorable Type V CO2 isotherms, which may offer advantages over the Type I isotherms exhibited by most adsorbents, as they provide near-ideal performance with minimal temperature swings.

[0050] In some circumstances, the diamine can be removed from the amine-added MOF by soaking the diamine-added MOF in a particular solvent. Due to the nature of the 3D printing process, the MOF incorporated in the ink composition can be exposed to a number of solvents, which can remove at least a portion, and in some cases, substantially all, of any amine added to the MOF. The removal of the diamine from the MOF adsorbent incorporated in the polymeric structural material during 3D printing can be reduced, minimized, and / or mitigated in various ways. In some aspects, the solvent and non-solvent for the ink composition can be selected to reduce or minimize the removal of the added diamine. An example of an ink composition that can reduce or minimize such stripping of the added diamine can include a solvent / non-solvent pair that includes hexane, cyclohexane, and / or toluene. Additionally or alternatively, after forming a structure from the polymeric structural material, additional diamine can be added to the MOF adsorbent incorporated in the polymeric structural material using a gas phase process.

[0051] In some aspects, the added diamine of the diamine-added MOF (such as EMM-44) can be substantially maintained in the polymeric structural material formed by 3D printing based on the selection of ingredients in the ink composition. In particular, an ink composition can be formed that includes the diamine-added MOF and a) a solvent / non-solvent combination or b) a polymer, solvent, and solvent combination that can reduce or minimize the loss of the added diamine during the printing process. More generally, the solvent and non-solvent can be selected from non-polar aprotic solvents (such as hexane, toluene, and / or cyclohexane) or polar aprotic solvents that do not have a Lewis base lone pair that can contribute to a Lewis acid metal site (such as tetrahydrofuran and / or dimethyl sulfoxide). Solvents that have a high tendency to cause the removal of the added diamine can include nitrogen-containing polar aprotic solvents such as N-methylpyrrolidone and dimethylformamide. Polar protic solvents such as water, methanol, and / or ethanol may also have a high tendency to cause the removal of the added diamine.

[0052] Additionally or alternatively, in some embodiments, it is possible to increase the amount of diamine-loaded MOFs in the 3D printed structure by adding the diamine to MOFs that have sites available for diamine loading using a gas phase process after printing. After forming the structure with a polymeric structural material that incorporates MOFs as adsorbents, the diamine can be loaded by contacting the entire system with a diamine-containing solution. An example of a solution is 15 vol% to 25 vol% 2-aminomethylpiperidine in a solvent such as toluene. Other examples of diamines that can be loaded in this way include, but are not limited to, N,N'-dimethylethylenediamine, spermine, and triethylenetetramine. The solvent used for the diamine loading can be a non-polar hydrocarbon and / or aromatic solvent (e.g., toluene, hexane), but surprisingly, methanol can also be used. Methanol can be used even though it is said to tend to strip the diamine from the MOF when it is part of the ink composition for 3D printing. Loading the amine using methanol can act to remove residual solvent from the structure formed by the 3D printing process. Example 1 - Ink composition and 3D printed fibers (PIM-1)

[0053] A series of ink compositions were prepared using two different MOF materials with selectivity for CO2 adsorption. The first series of compositions was prepared using MOF corresponding to HKUST-1. To prepare a well-dispersed printing ink composition containing HKUST-1, the MOF was first dispersed in a solvent mixture and sonicated for 1 h. Tetrahydrofuran (THF, ACS grade, Alfa Aesar) was selected as the solvent, and dimethylacetamide (DMAc, ACS grade, Alfa Aesar) was selected as the non-solvent. The sonication could effectively prevent particle aggregation. The MOF suspension was then transferred into a 3D printer ink cartridge. After that, dried PIM-1 fine powder was added to the MOF suspension. The cartridge containing the mixture was sealed and placed in a rotary oven at 80 °C for 12 h to dissolve the polymer and generate a uniform dispersion. After cooling, the ink was immediately used for solution-based additive manufacturing.

[0054] To test these suspension-type ink compositions, the ink compositions were 3D printed onto single fibers by SBAM. The ink compositions containing HKUST-1 were printed under an atmosphere containing a solvent (THF) to minimize evaporation until the ink was deposited on the substrate during printing of the single fiber. The solvent was then allowed to evaporate, resulting in the formation of a wet polymer structure with mixed solvent / non-solvent moieties. After 3D printing, the wet composite was vacuum dried at 100°C for 12 hours to remove some residual solvent and non-solvent.

[0055] Table 2 shows the ink compositions used to print the various fibers. For comparison, some control fibers were also printed. In Table 2, the first row corresponds to the control fibers with only PIM-1, the second row corresponds to the values ​​for neat HKUST-1 particles, the third row corresponds to the ink composition with HKUST-1 nanoparticles suspended in a solution of PIM-1 in THF and DMAC. The weight ratio of HKUST-1 to PIM-1 in this last row was 4:1. [Table 2]

[0056] After forming the dried fibers, the surface area and porosity of the resulting dried samples were characterized by nitrogen physisorption at 77 K. Figure 1 shows the physisorption isotherms in addition to the values ​​shown in Table 2. Additional pore volume values ​​were also obtained using mercury porosimetry, as shown in Table 2.

[0057] The surface area and pore volume of the HKUST-1 / PIM-1 sample were lower than expected. As shown in Table 2, the surface area of ​​HKUST-1 alone was 1650 m 2 The resulting polymer structure had a surface area of ​​approximately 1465 m based on a 4:1 ratio of HKUST-1 to polymer. 2 / g. In contrast, the measured surface area is 1208 m 2 / g, which is 18% lower than would be predicted based on the ratio of HKUST-1 to PIM-1 in the resulting polymer structure. Similarly, the measured pore volume was approximately 20% lower than would be predicted.

[0058] Figures 1 and 2 show nitrogen physical adsorption isotherms collected during characterization to obtain surface area and pore volume for various samples. Figures 1 and 2 show N2 adsorption isotherms for the HKUST-1 sample. As shown in Figures 1 and 2, the adsorption per gram of the composite polymeric material with 80 wt% HKUST-1 and 20 wt% PIM-1 was about 80% of the adsorption per gram of the HKUST-1 material. Given that the polymeric material contains 80 wt% MOF, this indicates that the adsorption capacity of the adsorbent material is substantially maintained. Despite the reduction in the surface area and pore volume of the adsorbent in the composite polymeric material, the adsorption capacity of the adsorbent material is maintained. Conventionally, one would have predicted that the adsorption per gram of the composite polymeric material would be reduced by 20% based on the amount of adsorbent in the composite material. Conventionally, one would have predicted an additional 15% to 20% reduction in adsorption due to one or more of the following factors: The factors are a) reduced surface area and / or pore volume in the composite material, b) potentially poor pore interconnectivity (although this is mitigated if the 3D printed material is well formed), c) insertion of the polymer into the pores of the adsorbent, filling the accessible pore volume, and / or d) coating, blocking, or otherwise blocking the pore openings, denying access to the otherwise unblocked pore structure of the adsorbent. In contrast, only a reduction with the amount of adsorbent in the composite material was clearly observed. It should be noted that the polymeric material also has some baseline adsorption capacity, but this contribution is expected to be small due to the low weight fraction of polymer in the composite polymeric material. Example 2 - Ink composition and 3D printed fibers (PES)

[0059] A second series of ink compositions was made by creating a solution consisting of approximately 20.6 wt% polyethersulfone (PES), 2.3 wt% polyvinylpyrrolidone (PVP), 68.5% dimethylacetamide (DMAc), and 8.6% water (H2O). A series of solutions were created such that the total amount of EMM-67 and PES in the solution was 25 wt% to 75 wt% of the weight of the solution. The following is an example of preparing an ink composition with a target weight of 10 g of polymer, solvent, non-solvent, and pore former, and 50 wt% EMM-67 in the final structure. 2.06 g of EMM-67 was added to a mixture of 6.85 g DMAc and 0.86 g H2O. The mixture was sonicated in a sonication bath for 12 hours to disperse the EMM-67 particles. This mixture was then added with 2.06 g of PES and 0.23 g of PVP and placed in a glass vial on a heated roller (approximately 50° C.) where polymer dissolution occurred. Once this mixture (corresponding to the ink composition) was homogenous (after 1-3 days), the ink composition was placed in a stainless steel cartridge and printed in a modified Creality 3D printer.

[0060] A third and fourth series of compositions were produced using polyethersulfone as the polymer and a diamine-added MOF known as EMM-44 as part of the ink composition, with the caveat that for both the second and third series of ink compositions, due to the nature of the ink formulation and subsequent printing process, at least a portion of the added diamine is stripped from EMM-44, so that at least a portion of the MOF incorporated into the resulting structural material corresponds to EMM-67, rather than EMM-44.

[0061] For the third series of compositions, ink compositions were formed by first forming a solution consisting of approximately 15 wt% polyethersulfone (PES), 65.6 wt% dimethylacetamide (DMAc), and 19.4 wt% lithium nitrate (LiNO3), and a series of solutions were then formed by adding EMM-44 to form solutions in which the total amount of EMM-44 and PES in the solution was between 25 wt% and 75 wt% of the solution weight.

[0062] The following is an example of a procedure for forming a homogenous ink composition. In this example, the target final weight of the ink composition was to form an ink composition containing 100 g of polymer, solvent, and structure forming components (in the form of LiNO3, a pore forming component), although any other suitable amount of ink composition may be formed. The weight of EMM-44 in the ink composition corresponds to the weight added to 100 g of polymer, solvent, and structure forming components. In this example, the goal was to create an ink composition containing approximately 25 wt% EMM-44.

[0063] To form the ink composition (having approximately 100 g of polymer, solvent, and structure-forming components), an initial mixture was prepared corresponding to 20 wt% of solvent, non-solvent, and polymer. In this example, this initial mixture corresponds to 3 g of PES, 14.7 g of DMAc, and 4.7 g of LiNO3. The initial mixture was placed in a glass bottle on a heated roller (approximately 50°C) until the solution was homogenous (1-4 days). The dispersion solution was then prepared by mixing the remaining 80 wt% of LiNO3 and DMAc. This corresponds to 56.2 g of DMAc and 18.8 g of LiNO3. In this step, an additional amount of DMAc was added to provide a solvent that would enter the pores of the EMM-44. Alternating shear mixing and ultrasonication was performed until the LiNO3 was dissolved in the DMAc. Then, EMM-44 was added, and alternating shear mixing and ultrasonication was performed again until the EMM-44 particles were dispersed. The initial mixture was then added to the solution to form a mixture with the remaining portion of the polymer, and heated (approximately 60° C.) and shear mixed for 6 hours to initiate dissolution of the polymer. The mixture was then placed in a glass bottle on a heated roller (approximately 50° C.) where dissolution of the remaining polymer occurred. Once the mixture (corresponding to the ink composition) was homogenous (after 1-3 days), the ink composition was placed in a stainless steel cartridge and heated (approximately 60° C.) to degas the dope, and then printed in a modified Creality 3D printer. Note that the ink composition was printed without a solvent atmosphere.

[0064] Ink compositions were prepared using similar procedures with varying combined weights of PES and EMM-44 (approximately 25 wt% to 75 wt% combined weight relative to the weight of the ink composition). The ink compositions were then used to form structures by 3D printing. A method for 3D printing at least some of these structures includes forming the 3D printed structures on a heated bed to promote evaporation of the solvent. After the structures were formed by 3D printing, a post-printing process was used to remove at least a portion of the LiNO3 from the resulting structures. In this example, the post-printing LiNO3 removal was accomplished by soaking the resulting structures in water for three days. The water was changed once per day. After the third day, the structures were soaked in methanol for one hour. The methanol was changed every 20 minutes.

[0065] A fourth series of ink compositions was also formed using PES and EMM-44; however, different solvents and different shaping components were used. In part due to these differences, the resulting 3D printed structures had relatively small surface areas. Thus, while 3D printed structures were successfully formed from inks based on this third series of ink compositions, the resulting 3D printed structures were not nearly as suitable for use in applications involving the adsorption of components from process fluids. This was due to the fact that the BET surface area of ​​the inks was less than 30 m. 2 / g or less than 10m 2 / g, e.g., as low as 0.1m 2 / g, or in some cases less.

[0066] For the fourth series of ink compositions, the ink compositions included EMM-44 as the adsorbent, PES as the polymer, n-methylpyrrolidone (NMP) as the solvent, and methanol (MeOH) as the non-solvent. An example of preparing the ink composition was adding 6 g of EMM-44 to a mixture of NMP (120 g) and MeOH (30 g), followed by ultrasonication for approximately 4 hours to ensure dispersion of the EMM-44 particles. Then, 60 g of PES was dissolved in the resulting EMM-44 / NMP / MeOH solution and left on a roller overnight. An additional 25 g of PES was gradually added over a period of 3 days. The resulting ink composition was transferred into a stainless steel tube for mounting in a modified Creality 3D printer. The ink composition was printed without a solvent atmosphere. It should be noted that due to the presence of methanol in the ink composition, the added diamine of EMM-44 may have been removed, so that at least some of the MOF particles in the ink composition may have been changed to Mg-MOF-274. Further embodiments

[0067] EMBODIMENT 1 1. A solvent-based additive manufacturing ink composition comprising: 2.0 wt % or more of an adsorbent material based on the weight of the ink composition; 35 wt% or less of a polymer; A solvent for the polymer; and a structure-forming component, An ink composition, wherein the ratio of the weight of the polymer to the combined weight of the solvent and non-solvent is 0.7 or less.

[0068] EMBODIMENT 2 i) the ink composition comprises 10 wt % or more of the adsorbent material; ii) the ratio of the weight of the adsorbent to the weight of the polymer is 1.0 or greater; iii) the ink composition comprises 15 wt % or less of the polymer; iv) the ratio of the weight of the polymer to the combined weight of the solvent and the structure-forming component is 0.20 or less; v) a combination of two or more of i) to iv) is provided; or vi) The ink composition of embodiment 1, wherein a combination of three or more of i)-iv) is provided.

[0069] EMBODIMENT 3 the structure-forming component comprises a non-solvent, and the ratio of the weight of the polymer to the weight of the non-solvent is 0.80 or less; or the structure-forming component comprises a pore-forming component; or The ink composition of any one of the preceding embodiments, wherein these combinations are provided.

[0070] EMBODIMENT 4 2. The ink composition of any one of the preceding embodiments, wherein the ink composition is substantially free of water.

[0071] EMBODIMENT 5 2. The ink composition of any one of the preceding embodiments, wherein the ink composition comprises a suspension of particles of the adsorbent material in a solution comprising the polymer, the solvent, and the structure-forming component.

[0072] EMBODIMENT 6 the weight ratio of the adsorbent material to the polymer is 2.0 or greater; or the ink composition comprises 20 wt % or more of the sorbent material; or The ink composition of any one of the preceding embodiments, wherein these combinations are provided.

[0073] EMBODIMENT 7 2. The ink composition of any one of the preceding embodiments, wherein the adsorbent material comprises a metal organic framework material, a zeotype framework material, activated carbon, a covalent organic framework, a porous aromatic framework, a porous organic polymer, or a combination thereof, and the adsorbent material optionally comprises an adsorbent selective for CO2 adsorption.

[0074] EMBODIMENT 8 2. The ink composition of any one of the preceding embodiments, wherein the adsorbent material comprises MOF-274, HKUST-1, EMM-67, EMM-44, or a combination thereof.

[0075] EMBODIMENT 9 2. The ink composition of any one of the preceding embodiments, wherein the polymer comprises a polymer of inherent microporosity, cellulose acetate, polyethersulfone, or a combination thereof.

[0076] EMBODIMENT 10 10. A method of forming a 3D printed polymer structure, comprising printing the ink composition of any one of embodiments 1 to 9, and evaporating a portion of the solvent to form a continuous polymer structure.

[0077] EMBODIMENT 11 The surface area of ​​the continuous polymer structure is 50 m 2 / g or more, or The continuous polymer structure has a pore volume of 0.50 cm as determined by nitrogen physisorption. 3 / g or more, or Combinations of these are provided according to the method of embodiment 10.

[0078] EMBODIMENT 12 12. The method of claim 10 or 11, wherein the surface area of ​​the continuous polymer structure is at least 10% less than the weighted average of the surface area of ​​the adsorbent material and the surface area of ​​the polymer.

[0079] EMBODIMENT 13 13. A continuous polymeric structure formed by 3D printing of an ink composition according to the method of any one of embodiments 10 to 12.

[0080] While the present invention has been described and illustrated with reference to specific embodiments, those skilled in the art will recognize that the present invention is useful in variations not necessarily illustrated herein, and therefore, reference should be made solely to the appended claims in order to determine the true scope of the present invention.

Claims

1. 1. A solvent-based additive manufacturing ink composition comprising: 2.0 wt % or more of an adsorbent material based on the weight of the ink composition; 35 wt % or less of a polymer; A solvent for the polymer; and a structure-forming component, An ink composition, wherein the ratio of the weight of the polymer to the combined weight of the solvent and non-solvent is 0.7 or less.

2. i) the ink composition comprises 10 wt % or more of the adsorbent material; ii) the ratio of the weight of the adsorbent to the weight of the polymer is 1.0 or greater; iii) the ink composition contains 15 wt % or less of the polymer; iv) the ratio of the weight of the polymer to the combined weight of the solvent and the structure-forming component is 0.20 or less; v) a combination of two or more of i) to iv) is provided; or The ink composition of claim 1 , wherein a combination of three or more of i) through iv) is provided.

3. the structure-forming component comprises a non-solvent, and the ratio of the weight of the polymer to the weight of the non-solvent is 0.80 or less; or the structure-forming component comprises a pore-forming component; or The ink composition of claim 1 wherein a combination of these is provided.

4. The ink composition of claim 1 , wherein the ink composition is substantially free of water.

5. The ink composition of claim 1 , wherein the ink composition comprises a suspension of particles of the adsorbent material in a solution comprising the polymer, the solvent, and the structure-forming component.

6. the weight ratio of the adsorbent material to the polymer is 2.0 or greater; or the ink composition comprises 20 wt % or more of the adsorbent material; or The ink composition of claim 1 wherein a combination of these is provided.

7. The sorbent material comprises a metal organic framework material, a zeotype framework material, activated carbon, a covalent organic framework, a porous aromatic framework, a porous organic polymer, or a combination thereof, and the sorbent material optionally comprises a CO ２ The ink composition of claim 1 comprising an adsorbent having selectivity for adsorption.

8. The ink composition of claim 1 , wherein the adsorbent material comprises MOF-274, HKUST-1, EMM-67, EMM-44, or a combination thereof.

9. The ink composition of claim 1 , wherein the polymer comprises a polymer of inherent microporosity, cellulose acetate, polyethersulfone, or a combination thereof.

10. 10. A method of forming a 3D printed polymer structure, comprising printing the ink composition of any one of claims 1 to 9 and evaporating a portion of the solvent to form a continuous polymer structure.

11. The surface area of ​​the continuous polymer structure is 50 m ２ / g or more, or The continuous polymer structure has a pore volume of 0.50 cm as determined by nitrogen physisorption. ３ / g or more, or The method of claim 10 wherein a combination of these is provided.

12. 11. The method of claim 10, wherein the surface area of ​​the continuous polymer structure is at least 10% less than the weighted average of the surface area of ​​the adsorbent material and the surface area of ​​the polymer.

13. 11. A continuous polymeric structure formed by 3D printing of an ink composition according to the method of claim 10.

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