# US 2025/0144571 A1 · All-nanoporous hybrid membranes comprising zeolites and metal-organic frameworks synthesized therethrough > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2025/0144571 A1 - Document ID: US20250144571A1 - Status: Published application - Kind: A1 - Application number: 19/017,398 - Filed: 2025-01-10 - Published: 2025-05-08 - Earliest claimed: 2020-02-27 - Assignees: Phillips 66 Company; Georgia Tech Research Corporation - Applicants: Phillips 66 Company; Georgia Tech Research Corporation - Inventors: Kiwon EUM; Shaowei YANG; Byunghyun MIN; Chen MA; Jeffrey H. DRESE; Yash TAMHANKAR; Ryan P. LIVELY; Sankar NAIR - Web page: https://patentgrep.com/patent/US20250144571A1 ## CPC - B01D 67/0051: {by controlled crystallisation, e,.g. hydrothermal growth} - B01D 67/00933: {by addition of a layer chemically bonded to the membrane} - B01D 69/12: Composite membranes; Ultra-thin membranes - B01D 69/148: {Organic/inorganic mixed matrix membranes} - B01D 71/0281: {Zeolites} - B01D 71/62: Polycondensates having nitrogen-containing heterocyclic rings in the main chain - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) ## Abstract A method of forming a molecular separation device is provided. The method comprises growing or depositing a silica MFI zeolite coating on a ceramic support. The method further comprises growing a ZIF-8 coating on the silica MFI zeolite coating. Growing the ZIF-8 coating on the silica MFI zeolite comprises applying a first reactant fluid including a metal salt and a second reactant fluid including an imidazole reactant to the silica MFI zeolite coating. Growing the ZIF-8 coating on the silica MFI zeolite further comprises reacting the first and second reactant fluid with the silica MFI zeolite coating to produce the ZIF-8 coating. In certain implementations, at least a portion of the ZIF-8 coating is interspersed with a portion of the silica MFI coating. A molecular separation device including the ZIF-8 coating and the silica MFI zeolite is also disclosed. ## Claims ### Claim 1 A method of forming a molecular separation device, comprising: growing or depositing a silica MFI zeolite coating on a ceramic support, the growing or depositing comprising: coating the ceramic support with a layer of 3D MFI nanoparticles; and coating the layer of 3D MFI nanoparticles with a layer of 2D MFI nanosheets; and growing a ZIF-8 coating on the silica MFI zeolite coating. ### Claim 2 (depends on 1) The method of claim 1, wherein growing the ZIF-8 coating on the silica MFI zeolite coating further comprises applying a first reactant fluid and a second reactant fluid to the silica MFI zeolite coating, and wherein the first reactant fluid comprises a metal salt. ### Claim 3 (depends on 2) The method of claim 2, wherein the second reactant fluid comprises an imidazole reactant. ### Claim 4 (depends on 3) The method of claim 3, wherein the metal salt comprises zinc acetate dihydrate and the imidazole reactant comprises 2-methylimidazole. ### Claim 5 (depends on 2) The method of claim 2, wherein the first reactant fluid and the second reactant fluid are mixed prior to applying the first reactant fluid and the second reactant fluid to the silica MFI zeolite coating. ### Claim 6 (depends on 2) The method of claim 2, wherein growing the ZIF-8 coating on the silica MFI zeolite coating further comprises reacting the first and second reactant fluids on the silica MFI zeolite coating to produce the ZIF-8 coating. ### Claim 7 (depends on 6) The method of claim 6, wherein reacting the first and second reactant fluids further comprises subjecting the first and second reactant fluids to at least one of ambient conditions, heating, or crystallizing by cooling past supersaturation. ### Claim 8 (depends on 1) The method of claim 1, wherein growing or depositing the silica MFI zeolite coating on the ceramic support further comprises subjecting the ceramic support to a dip coating process or a vacuum-assisted filtration process. ### Claim 9 (depends on 1) The method of claim 1, wherein the silica MFI zeolite coating and the ZIF-8 coating form a mixed matrix membrane. ### Claim 10 (depends on 1) The method of claim 1, wherein the 3D MFI nanoparticles have an average diameter in a range from about 50 nm to about 200 nm. ### Claim 11 A method of forming a molecular separation device, comprising: growing or depositing a porous, nanocrystalline material comprising a zeolite on a ceramic support, the growing or depositing comprising: coating the ceramic support with a layer of 3D MFI nanoparticles; and coating the layer of 3D MFI nanoparticles with a layer of 2D MFI nanosheets; and growing a porous, polycrystalline material comprising a metal-organic framework (MOF) on the porous, nanocrystalline material comprising the zeolite. ### Claim 12 (depends on 11) The method of claim 11, wherein growing the porous, polycrystalline material further comprises: applying a first reactant fluid comprising a metal salt to the porous, nanocrystalline material; converting the first reactant fluid to a metal-containing film; applying a second reactant fluid comprising an imidazole reactant to the ceramic support with the porous, nanocrystalline material; and reacting the imidazole reactant with the metal-containing film to convert the metal-containing film into the porous, polycrystalline material. ### Claim 13 (depends on 11) The method of claim 11, wherein the zeolite comprises a pure-silica MFI zeolite. ### Claim 14 (depends on 11) The method of claim 11, wherein the MOF is a zeolitic imidazolate framework (ZIF). ### Claim 15 (depends on 14) The method of claim 14, wherein the ZIF is selected from ZIF-8, ZIF-90, or a hybrid, mixed-linker ZIF. ### Claim 16 (depends on 11) The method of claim 11, wherein converting the first reactant fluid to the metal-containing film is by solvent evaporation which further comprises subjecting the first reactant fluid to at least one of ambient conditions, heating, or crystallizing by cooling past supersaturation. ### Claim 17 (depends on 11) The method of claim 11, wherein growing or depositing the porous, nanocrystalline material comprising the zeolite on the ceramic support further comprises subjecting the ceramic support to a dip coating process or a vacuum-assisted filtration process. ### Claim 18 (depends on 11) The method of claim 11, wherein the 3D MFI nanoparticles have an average diameter in a range from about 50 nm to about 200 nm. ### Claim 19 A molecular separation device, comprising: a porous, polycrystalline membrane material comprising a metal-organic framework (MOF); and a porous, nanocrystalline material comprising a zeolite on a ceramic support, wherein the zeolite comprises a layer of 3D MFI nanoparticles and a layer of 2D MFI nanosheets; wherein the porous, nanocrystalline material is dispersed within at least a portion of the porous, polycrystalline membrane material; wherein the porous, nanocrystalline material provides a plurality of nanoporous structures; and wherein the molecular separation device has a propylene permeability of greater than 100 barrer and a propylene to propane selectivity of greater than 100. ### Claim 20 (depends on 19) The device of claim 19, wherein the MOF comprises a zeolitic imidazolate framework (ZIF) and the zeolite comprises a pure-silica MFI zeolite. ### Claim 21 (depends on 19) The device of claim 19, wherein the 3D MFI nanoparticles have an average diameter in a range from about 50 nm to about 200 nm. ### Claim 22 (depends on 19) The device of claim 19, wherein the zeolite comprises the layer of 3D MFI nanoparticles coated on the ceramic support and the layer of 2D MFI nanosheets coated on the layer of 3D MFI nanoparticles. ### Claim 23 (depends on 19) The device of claim 19, wherein the zeolite comprises the layer of 2D MFI nanosheets coated on the ceramic support and the layer of 3D MFI nanoparticles coated on the layer of 2D MFI nanosheets. ### Claim 24 (depends on 19) The device of claim 19, wherein the porous, polycrystalline membrane material is grown by: applying a first reactant fluid comprising a metal salt to the porous, nanocrystalline material; converting the first reactant fluid to a metal-containing film; applying a second reactant fluid comprising an imidazole reactant to the ceramic support with the porous, nanocrystalline material; and reacting the imidazole reactant with the metal-containing film to convert the metal-containing film into the porous, polycrystalline membrane material.