Method and system for producing nanoporous structures on a substrate - Patents.com

Abstract

A method of producing a nanoporous structure on a substrate includes additively forming a precursor structure on a substrate from at least one of a metal oxide or a metal cluster compound, exposing the precursor structure to a vapor of an organic linker, and reacting at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker to form a nanoporous structure comprising a metal organic framework.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Patent Application No. 17 / 702,337, filed March 23, 2022, which is incorporated by reference in its entirety. Summary of the Invention [Problem to be solved by the invention]

[0002] Nanoporous coatings have been used in carbon capture and utilization applications. Currently, these nanoporous coatings are produced by solvent-based bulk preparation methods in which a coating precursor is heated in a solvent to form a coating composition, which is then poured onto a substrate to be coated to form a nanoporous coating after the solvent dries. These methods provide very limited control over the deposition of the coating in terms of thickness, spatial distribution, and composition. In addition, these methods may cause corrosion or degradation of the substrate to be coated. Thus, there is a continuing need for improved methods and systems for producing nanoporous structures, such as coatings or articles on substrates for carbon capture and utilization applications.

[0003] A method of producing a nanoporous structure on a substrate includes additively forming a precursor structure on a substrate from at least a metal oxide or a metal cluster compound, exposing the precursor structure to a vapor of an organic linker, and reacting at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker to form a nanoporous structure comprising a metal organic framework.

[0004] An integrated system for producing nanoporous structures on a substrate includes a reactor chamber having a heater effective to heat the reactor chamber and a substrate disposed within the reactor chamber, the reactor chamber having an inlet for introducing vapor of an organic linker into the reactor chamber and an outlet for removing a gas stream from the reactor chamber, a platform disposed within the reactor chamber effective to support and heat the substrate, and an additive manufacturing apparatus disposed within the reactor chamber effective to additively form a precursor structure on the substrate. [Brief description of the drawings]

[0005] The following description should not be considered limiting in any way.With reference to the accompanying drawings, like elements are numbered likewise. [Figure 1] FIG. 1 illustrates a process for producing a nanoporous structure on a substrate according to an embodiment of the present disclosure. [Figure 2A] FIG. 2A shows an article that includes a nanoporous structure disposed on a substrate, where the nanoporous structure has a pattern. [Figure 2B] FIG. 2B illustrates an article that includes a nanoporous structure disposed on a substrate, the nanoporous structure having several portions, the portions having at least one of different shapes, different thicknesses, or different metal-organic frameworks. [Figure 2C] FIG. 2C illustrates an article that includes a nanoporous structure disposed on a substrate, the nanoporous structure having multiple layers, with adjacent layers having at least one of different thicknesses or different metal-organic frameworks. [Diagram 3] FIG. 3 is a schematic diagram of an integrated system for producing a nanoporous structure on a substrate according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] A detailed description of one or more embodiments of the disclosed method and system is provided herein by way of example and not by way of limitation with reference to the figures.

[0007] A method for producing nanoporous structures on a substrate is described. As used herein, nanoporous structures include, but are not limited to, nanoporous coatings. The method includes additively forming a precursor structure on a substrate and then converting the precursor structure to a nanoporous structure via a chemical vapor conversion process achieved by exposing the precursor structure to an organic linker vapor. The method avoids limitations associated with conventional solvent-based methods, such as corrosion, contamination, and lack of control over the deposition process (i.e., thickness, spatial distribution, and composition across the substrate and across layers). Furthermore, the method can be performed in an integrated system incorporating additive deposition and chemical vapor processing in a single chamber, resulting in increased throughput, i.e., lead time savings. Furthermore, the nanoporous structures produced by the method can have finely controlled dimensions, compositions, and properties down to the nanometer and sub-nanometer scale. Because these properties can be controlled, the nanoporous structures can be used to target flue gas streams, i.e., enrichment, gas mixtures, for carbon capture and utilization applications.

[0008] 1, a method for producing a nanoporous structure (15) on a substrate (11) includes additively forming a precursor structure (16) from at least one of a metal oxide or a metal cluster compound on the substrate (11) (19), exposing the precursor structure (16) to a vapor of an organic linker (10), and reacting at least one of the metal oxide or the metal cluster compound in the precursor structure (16) with the organic linker (10) to form a nanoporous structure (15) including a metal-organic framework (18). The method may further include generating and delivering a vapor of the organic linker (10) to the precursor structure (16). Preferably, the vapor of the organic linker (10) is generated in a system separate from the one in which the vapor contacts the precursor structure so that the temperature for generating the vapor and the temperature for reacting the organic linker with the metal oxide or metal cluster compound can be independently controlled.

[0009] The metal oxide used to prepare the precursor structure may include at least one of zinc oxide, aluminum oxide, magnesium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, calcium oxide, barium oxide, cerium oxide, manganese oxide, gallium oxide, or cadmium oxide. The metal cluster compound used to prepare the precursor structure may include at least one of titanium-based cluster compounds or zirconium-based cluster compounds. As used herein, titanium-based cluster compounds or zirconium-based cluster compounds refer to cluster compounds that include titanium or zirconium as the main metal.

[0010] The metal oxide and metal cluster compounds may be in the form of fine particles. The particle size of the metal oxide and metal cluster compounds is not particularly limited. Advantageously, the metal oxide and metal cluster compounds may have an average particle size of about 10 nanometers (nm) to about 100 micrometers (μm), preferably about 10 nm to about 10 μm, about 10 nm to about 1 μm, or about 10 nm to about 500 nm. The average particle size of the metal oxide and metal cluster compounds is, for example, the median particle size (D50) measured using a laser particle size distribution analyzer.

[0011] The substrate on which the nanoporous structure is disposed is not particularly limited and may include metallic, ceramic, polymeric, or composite substrates. The substrate selected will depend on the nature of the targeted carbon capture and utilization system.

[0012] In the method disclosed herein, the precursor structure is additively formed on the substrate from at least one of metal oxide or metal cluster compounds. By using additive manufacturing, the precursor structure can be designed based on an optimized flow, taking into account the characteristics of the target (flue) gas, for example, for carbon dioxide capture and utilization applications. Additively forming the precursor structure can be performed via an aerosol jet process, a binder jet process, or a material jet process.

[0013] When using an aerosol injection process to make the precursor structure, a composition including at least one of the metal oxide or metal cluster compounds and optionally a solvent is loaded into an aerosol injection device, and then the metal oxide / metal cluster compound is atomized using either ultrasonic or pneumatic processes. The atomized metal oxide or metal cluster compound in the composition can then be captured by an inert carrier gas to form an aerosol. The aerosol can be directed to a nozzle where it is focused and collimated as it exits the nozzle. The focused aerosol stream is directed toward the substrate to be coated such that the atomized metal oxide or metal cluster compound is deposited on the substrate. The deposited metal oxide or metal cluster compound can be annealed or sintered at a temperature of about 250 to about 2000°C or about 450°C to about 2000°C and a pressure of about 1 mbar to about 1 bar to form the precursor structure.

[0014] Exemplary aerosol injection devices that can be used are manufactured by Optomec, Inc. and are described, for example, in U.S. Patent Nos. 7,108,894 and 7,938,341. Commercially available aerosol injection devices include the Optomec AEROSOL JET 300 series systems.

[0015] The precursor structure can also be additively formed via a binder jetting process. During the binder jetting process, a layer of powder containing at least one of a metal oxide or a metal cluster compound is deposited on the substrate to be coated. A liquid binder is then selectively sprayed onto the powder layer according to a preset pattern. The liquid binder may include an organic binder and optionally a solvent for the organic binder. After application to the powder, the binder is solidified or dried. Additional powder and additional binder are deposited to form the next layer. This process is repeated under which a green structure is formed. The green structure is then sintered to form the precursor structure. The sintering temperature may be about 150 to about 2000°C, preferably about 450 to about 2000°C. Sintering may be performed at a pressure of about 1 mbar to about 1 bar. During sintering, the binder may be burned off.

[0016] The precursor structures can also be formed via a material jetting process, sometimes referred to as continuous jetting or drop-on-demand jetting. Metal oxide and metal cluster compounds jetted onto the substrate to be coated can be sintered or annealed to form the precursor structures.

[0017] The precursor structure produced by the methods described herein may have a thickness of about 10 nm to about 10 micrometers, about 100 nm to about 1 micrometer, or about 800 nm to about 10 micrometers. As used herein, the thickness of the precursor structure may be measured in a direction perpendicular to the substrate. After the precursor structure is formed, but before the precursor structure is exposed to the organic linker vapor, powder may optionally be removed from the precursor structure to remove loose particles from the surface of the precursor structure.

[0018] The precursor structure is then exposed to a vapor of an organic linker. The organic linker may include at least one of a carboxylate or an imidazolate. Examples of organic linkers include 2-methylimidazolate, 2-ethylimidazolate, 1-benzyl-1H-imidazolate, benzene-1,4-dicarboxylate, trans-1,4-cyclohexanedicarboxylate, 1,3,5-benzenetricarboxylate, and benzene-1,2,4,5-tetracarboxylate. Other known organic linkers may be used. More than one organic linker may be used. In an embodiment, the vapor of two or more organic linkers reacts with at least one of the metal oxide or metal cluster compounds in the precursor structure to form a nanoporous structure (15) including a metal-organic framework (18).

[0019] The metal oxide or metal cluster compound can be reacted with the organic linker at a temperature of about 80° C. to about 185° C., preferably about 80° C. to about 100° C., and a pressure of about 0.001 bar to about 10 bar, preferably about 0.001 bar to about 1 bar, to form a nanoporous structure comprising a metal-organic network.

[0020] After the reaction, the nanoporous structure can be activated by heating the nanoporous structure under subatmospheric pressure of about 0.0001 bar to about 0.01 bar, preferably about 0.0001 bar to about 0.001 bar, at a temperature of about 100 to about 200° C., preferably about 120° C. to about 150° C. During activation, excess organic linker that is deposited on the nanoporous structure and inside the pores of the nanoporous structure but does not react with either the metal oxide or the metal cluster compound can be removed.

[0021] The nanoporous structure formed may have a thickness of about 10 nm to about 500 nm or about 1 μm to about 100 μm. The thickness of the nanoporous structure may be measured in a direction perpendicular to the substrate. The nanoporous structure comprises a metal-organic framework. In particular, the nanoporous structure has a solid crystalline network comprising inorganic nodes (17) connected by organic moieties (12), the inorganic nodes being formed from at least one of metal oxide or metal cluster compounds, the organic moieties being formed from organic linkers. The pore diameter of the potential voids in the crystalline network may be in the range of about 5 to about 20 Å, with the pore wall area being approximately the thickness of a single molecule. This crystalline lattice has a large internal specific surface area (up to about >7000 m2). 2 / g) which can be used in integration and energy technology applications.

[0022] Using the methods disclosed herein, the localization, shape, thickness, and composition of nanoporous structures can be controlled; these characteristics cannot be achieved using traditional solvent-based or bulk preparation methods.

[0023] By way of illustration, conventional methods can produce continuous films or structures on a substrate. The methods disclosed herein can produce not only continuous coatings, but also discontinuous nanoporous structures or nanoporous structures with a predetermined pattern. FIG. 2A shows an article (20) including a nanoporous structure (25) disposed on a substrate (11), the nanoporous structure (25) having a predetermined pattern. The pattern can be designed to achieve a "functional effect" for various applications. Such articles (20) can be produced by the methods described herein, but cannot be produced by conventional methods.

[0024] The nanoporous structure prepared according to the method of the present disclosure may have a first portion and a second portion, the first portion and the second portion having at least one of different thicknesses, different shapes, or different metal-organic frameworks. As used herein, different metal-organic frameworks may include metal-organic frameworks with different organic linkers, metal-organic frameworks with different inorganic nodes, or metal-organic frameworks with different pore diameters, different pore wall areas, or different internal specific surface areas. The different metal-organic frameworks may have more than one difference.

[0025] 2B shows an article (30) prepared according to the method of the present disclosure, comprising a nanoporous structure disposed on a substrate (11), the nanoporous structure comprising a first nanoporous structure (35A), a second nanoporous structure (35B), and a third nanoporous structure (35C), the first, second, and third nanoporous structures may have at least one of different shapes, different thicknesses, or different metal-organic frameworks.

[0026] The methods described herein also allow for the fabrication of nanoporous structures on a substrate having a layered structure in which at least two layers have at least one of different thicknesses, different geometries, or different metal-organic frameworks. For example, the nanoporous structure may be an AB-AB-AB stack for binary systems. The nanoporous structure may be an ABC-ABC-ABC stack for ternary systems. Other configurations are possible. Such articles can be advantageously used in membrane separation processes, carbon capture for multicomponent off-gas streams, etc.

[0027] An article having a layered nanoporous structure on a substrate can be prepared by forming a first nanoporous structure on a substrate as described herein, incrementally forming a second precursor structure on the first nanoporous structure from at least one of a second metal oxide or a second metal cluster compound, exposing the second precursor structure to a vapor of a second organic linker, and reacting at least one of the second metal oxide or second metal cluster compound in the second precursor structure with the second organic linker to form a second nanoporous structure comprising a second metal organic framework disposed on the first nanoporous structure. This process can be repeated to deposit more layers having controlled thicknesses and / or compositions.

[0028] Alternatively, an article having a layered nanoporous structure on a substrate can be prepared by additively forming a first precursor layer on the substrate, additively forming a second precursor layer on the first precursor layer, and additively forming additional precursor layers if desired to provide a stack of precursor layers, where the metal oxide / metal cluster compounds used to make each precursor layer can be the same or different, and exposing the stack of precursor layers to a vapor of an organic linker to react the metal oxide / metal cluster compounds in the precursor stack with the organic linker to form the article. Each layer of the nanoporous structure can have the same or different metal-organic frameworks.

[0029] FIG. 2C shows an article (40) having a nanoporous structure disposed on a substrate (11), the nanoporous structure having a first layer (45A), a second layer (45B), a third layer (45C), and a fourth layer (45D), wherein adjacent layers of the nanoporous structure have at least one of different thicknesses, different shapes, or different metal-organic frameworks.

[0030] Advantageously, in a system for producing nanoporous nanostructures, the chemical vapor conversion system is integrated into an additive manufacturing system, such that the precursor structure and the nanoporous structure can be formed in a single reactor chamber.

[0031] As a specific example, a method for producing a nanoporous structure includes additively forming a precursor structure on a substrate from at least one of a metal oxide or a metal cluster compound in a reactor chamber equipped with a heater via an aerosol jet process, a binder jet process, or a material jet process; introducing a vapor of the organic linker, optionally with a carrier gas, into the reactor chamber; exposing the precursor structure to the vapor of the organic linker in the reactor chamber; reacting at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker in the reactor chamber at a temperature of about 80° C. to about 100° C. to form a nanoporous structure comprising a metal organic framework; and heating the nanoporous structure at a temperature of about 120° C. to about 150° C. and a subatmospheric pressure of about 0.0001 bar to about 0.001 bar to activate the nanoporous structure.

[0032] Referring to FIG. 2, an integrated system (550) for producing nanoporous structures includes a reactor chamber (700) with a heater (100) effective to heat the reactor chamber (700). The heater (100) can also heat a substrate disposed within the reactor chamber (700). The integrated system may have more than one heater to ensure uniform heating of the interior of the reactor chamber. The heaters can be individually controlled. Thus, each chamber wall may have a different temperature, if desired. This configuration allows for more control over the additive formation process and chemical conversion rates.

[0033] The reactor chamber (700) may have an inlet (200) for introducing the organic linker vapor and optionally a carrier gas into the reactor chamber (700) and an outlet (300) for removing the gas stream from the reactor chamber (700). The organic linker vapor may be generated in a vapor generation system, for example, a chamber 800, which is in fluid communication with the reactor chamber (700). The vapor generation system may have a heater (not shown). The temperature of the vapor generation system may be different from the temperature of the reactor chamber. The gas stream that is removed may include by-products and a gaseous carrier, if used. The outlet (300) of the reactor chamber (700) may be connected to a pump.

[0034] The integrated system (550) also includes a platform (400) disposed within the reactor chamber (700). The platform (400) may be movable and is effective to support a substrate (450) on which the nanoporous structure is disposed. Optionally, the movable platform (400) also includes a heater (150). The platform may have more than one heater to ensure uniform heating of the substrate. The heater (150) allows the substrate to be heated to a temperature different from the chamber temperature. The additional heaters (150) may allow further control over the additive formation process and chemical conversion rates.

[0035] The integrated system (550) may also include an additive manufacturing device (600) disposed within the reactor chamber (700). The additive manufacturing device (600) is effective to additively form precursor structures on a substrate. Any known additive manufacturing device may be used and may include an aerosol jetting device, a binder jetting device, or a material jetting device. Optionally, the integrated system (550) also includes a roller (500) for spreading the jetted powder on the substrate to be coated.

[0036] Several embodiments of the foregoing disclosure are described below.

[0037] Embodiment 1. A method of producing a nanoporous structure on a substrate comprising additively forming a precursor structure on a substrate from at least one of a metal oxide or a metal cluster compound, exposing the precursor structure to a vapor of an organic linker, and reacting at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker to form a nanoporous structure comprising a metal organic framework.

[0038] Embodiment 2. The method of embodiment 1, comprising additively forming the precursor structure via an aerosol jetting process, a binder jetting process, or a material jetting process.

[0039] Embodiment 3. The method of embodiment 1 or 2, wherein the precursor structure is formed from a metal oxide, the metal oxide comprising at least one of zinc oxide, aluminum oxide, magnesium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, calcium oxide, barium oxide, cerium oxide, manganese oxide, gallium oxide, or cadmium oxide.

[0040] Embodiment 4. The method of any one of embodiments 1-3, wherein the precursor structure is formed from the metal cluster compound, the metal cluster compound comprising at least one of a titanium-based cluster compound or a zirconium-based cluster compound.

[0041] Embodiment 5. The method of any one of embodiments 1 to 4, wherein the metal oxide and the metal cluster compound have a particle size of about 10 nm to about 100 μm.

[0042] Embodiment 6. The method of any one of embodiments 1 to 5, wherein the precursor structure has a thickness of about 10 nm to about 10 micrometers.

[0043] Embodiment 7. The method of any one of embodiments 1-6, further comprising removing powder from the precursor structure to remove loose particles from the precursor structure prior to exposing the precursor structure to the vapor of the organic linker.

[0044] Embodiment 8. The method of any one of embodiments 1 to 7, wherein the organic linker comprises at least one of a carboxylate or an imidazolate.

[0045] Embodiment 9. The method of any one of embodiments 1 to 8, comprising reacting at least one of the metal oxide or metal cluster compounds in the precursor structure with the organic linker at a temperature of about 80° C. to about 100° C. to form the nanoporous structure.

[0046] Embodiment 10. The method of any one of embodiments 1 to 9, comprising reacting at least one of the metal oxide or metal cluster compounds in the precursor structure with the organic linker at a pressure of about 0.001 bar to about 1 bar to form the nanoporous structure.

[0047] Embodiment 11. The method of any one of embodiments 1-10, wherein the additive forming, exposing, and reacting are performed in a single reactor chamber.

[0048] Embodiment 12. The method of any one of embodiments 1 to 11, wherein the metal-organic framework is a crystalline network comprising inorganic nodes linked by organic moieties, the inorganic nodes being formed from at least one of the metal oxide or the metal cluster compound, the organic moieties being formed from the organic linker, and the crystalline network having voids with pore diameters of about 5 to about 20 angstroms.

[0049] Embodiment 13. The method of any one of embodiments 1 to 12, further comprising exposing the nanoporous structure to a temperature of about 120° C. to about 150° C. and a subatmospheric pressure of about 0.0001 bar to about 0.001 bar to activate the nanoporous structure.

[0050] Embodiment 14. The method of any of embodiments 1-13, comprising additively forming the precursor structure on the substrate from at least one of the metal oxide or the metal cluster compound in a reactor chamber equipped with a heater via an aerosol jetting process, a binder jetting process, or a material jetting process; introducing a vapor of the organic linker into the reactor chamber; exposing the precursor structure to the vapor of the organic linker in the reactor chamber; reacting at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker in the reactor chamber at a temperature of about 80° C. to about 100° C. to form a nanoporous structure comprising a metal organic framework; and exposing the nanoporous structure to a temperature of about 120° C. to about 150° C. and a subatmospheric pressure of about 0.0001 bar to about 0.001 bar to activate the nanoporous structure.

[0051] Embodiment 15. The method of any one of embodiments 1 to 14, wherein the vapor of the organic linker is introduced into the reactor chamber with a gaseous carrier.

[0052] Embodiment 16. The method of any one of embodiments 1 to 15, wherein the nanoporous structure is discontinuous and has a predetermined pattern.

[0053] Embodiment 17. The method of any one of embodiments 1 to 16, wherein the nanoporous structure has a first portion and a second portion, the first portion and the second portion having at least one of different thicknesses, different shapes, or different metal-organic frameworks.

[0054] Embodiment 18. The method of any of embodiments 1-17, further comprising: additionally forming a second precursor structure from at least one of a second metal oxide or a second metal cluster compound on the nanoporous structure; exposing the second precursor structure to vapor of a second organic linker; and reacting at least one of the second metal oxide or second metal cluster compound in the second precursor structure with the second organic linker to form a second nanoporous structure comprising a second metal organic framework disposed on the nanoporous structure, wherein the nanoporous structure and the second nanoporous structure have at least one of different thicknesses, different shapes, or different metal-organic frameworks.

[0055] Embodiment 19. An integrated system for producing a nanoporous structure on a substrate, comprising: a reactor chamber having a heater effective to heat the reactor chamber and a substrate disposed within the reactor chamber, the reactor chamber having an inlet for introducing vapor of an organic linker into the reactor chamber and an outlet for removing a gas flow from the reactor chamber; a platform disposed within the reactor chamber, the platform effective to support and optionally heat the substrate; and an additive manufacturing apparatus disposed within the reactor chamber, the additive manufacturing apparatus effective to additively form a precursor structure on the substrate.

[0056] Embodiment 20. The integrated system of embodiment 19, wherein the additive manufacturing device is an aerosol jetting device, a binder jetting device, or a material jetting device.

[0057] Embodiment 21. The integrated system of embodiment 19 or 20, wherein the outlet of the reactor chamber is connected to a pump.

[0058] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. As used herein, a "combination" is inclusive of blends, mixtures, alloys, reaction products, and the like. All references are incorporated herein by reference in their entirety.

[0059] Use of the terms "a" and "an" and "the" and similar referents should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. "Or" means "and / or." The modifier "about" used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity).

Claims

1. 1. A method for producing a nanoporous structure on a substrate, comprising: Additively forming a precursor structure on the substrate from at least one of a metal oxide or a metal cluster compound; exposing the precursor structure to a vapor of an organic linker; reacting at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker to form the nanoporous structure comprising a metal organic framework; A method comprising:

2. The method of claim 1 , comprising additively forming the precursor structure via an aerosol jetting process, a binder jetting process, or a material jetting process.

3. 10. The method of claim 1 , wherein the precursor structure is formed from a metal oxide, the metal oxide comprising at least one of zinc oxide, aluminum oxide, magnesium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, calcium oxide, barium oxide, cerium oxide, manganese oxide, gallium oxide, or cadmium oxide.

4. 10. The method of claim 1, wherein the precursor structure is formed from the metal cluster compound, the metal cluster compound comprising at least one of a titanium-based cluster compound or a zirconium-based cluster compound.

5. 10. The method of claim 1, further comprising removing powder from the precursor structure to remove loose particles from the precursor structure prior to exposing the precursor structure to the vapor of the organic linker.

6. The method of claim 1 , wherein the organic linker comprises at least one of a carboxylate or an imidazolate.

7. 2. The method of claim 1, comprising reacting at least one of the metal oxide or metal cluster compound in the precursor structure with the organic linker at a temperature of about 80° C. to about 100° C. to form the nanoporous structure.

8. The method of claim 1 , wherein the additive forming, the exposing, and the reacting are performed in a single reactor chamber.

9. 13. The method of claim 1, further characterized by exposing the nanoporous structure to a temperature of about 120° C. to about 150° C. and a subatmospheric pressure of about 0.0001 bar to about 0.001 bar to activate the nanoporous structure.

10. additively forming the precursor structure on the substrate from at least one of the metal oxide or the metal cluster compound via an aerosol jetting process, a binder jetting process, or a material jetting process in a reactor chamber equipped with a heater; introducing the vapor of the organic linker into the reactor chamber; exposing the precursor structure to the vapor of the organic linker in the reactor chamber; reacting at least one of the metal oxide or the metal cluster compound in the precursor structure with the organic linker in the reactor chamber at a temperature of about 80° C. to about 100° C. to form the nanoporous structure comprising the metal-organic framework; and exposing the nanoporous structure to a temperature of about 120° C. to about 150° C. and a subatmospheric pressure of about 0.0001 bar to about 0.001 bar to activate the nanoporous structure.

11. The method of any one of claims 1 to 9, wherein the nanoporous structure is discontinuous and has a predetermined pattern.

12. 10. The method of any one of claims 1 to 9, wherein the nanoporous structure has a first portion and a second portion, the first portion and the second portion having at least one of different thicknesses, different shapes, or different metal-organic frameworks.

13. additionally forming a second precursor structure on the nanoporous structure from at least one of a second metal oxide or a second metal cluster compound; exposing the second precursor structure to a vapor of a second organic linker; reacting at least one of the second metal oxide or the second metal cluster compound in the second precursor structure with the second organic linker to form a second nanoporous structure comprising a second metal organic framework disposed on the nanoporous structure; The method of any one of claims 1 to 9, wherein the nanoporous structure and the second nanoporous structure have at least one of different thicknesses, different shapes, or different metal-organic frameworks.

14. 1. An integrated system (550) for producing a nanoporous structure on a substrate, comprising: a reactor chamber (700) comprising a heater (100) effective to heat said reactor chamber (700) and a substrate (450) disposed within said reactor chamber (700), said reactor chamber having an inlet (200) for introducing vapor of an organic linker into said reactor chamber (700) and an outlet (300) for removing a gas stream from said reactor chamber (700); a platform (400) disposed within said reactor chamber (700), said platform (400) effective to support and optionally heat said substrate (450); an additive manufacturing apparatus (600) disposed within the reactor chamber (700), the additive manufacturing apparatus (600) effective to additively form a precursor structure on the substrate (450); An integrated system comprising:

15. 15. The integrated system of claim 14, wherein the additive manufacturing device is an aerosol jetting device, a binder jetting device, or a material jetting device.

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