WO2020112899A1 - Multivariate and other metal-organic frameworks, and uses thereof - Google Patents

Multivariate and other metal-organic frameworks, and uses thereof Download PDF

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Publication number
WO2020112899A1
WO2020112899A1 PCT/US2019/063442 US2019063442W WO2020112899A1 WO 2020112899 A1 WO2020112899 A1 WO 2020112899A1 US 2019063442 W US2019063442 W US 2019063442W WO 2020112899 A1 WO2020112899 A1 WO 2020112899A1
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Prior art keywords
mof
water
moieties
organic
organic ligands
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PCT/US2019/063442
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English (en)
French (fr)
Inventor
Omar M. Yaghi
Nikita HANIKEL
Hao LYU
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University of California Berkeley
University of California San Diego UCSD
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University of California Berkeley
University of California San Diego UCSD
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Priority to SG11202105462PA priority Critical patent/SG11202105462PA/en
Priority to JOP/2021/0119A priority patent/JOP20210119A1/ar
Priority to NZ776804A priority patent/NZ776804B2/en
Priority to PH1/2021/551201A priority patent/PH12021551201B1/en
Priority to IL283376A priority patent/IL283376B2/en
Priority to AU2019386080A priority patent/AU2019386080B2/en
Priority to BR112021010139-0A priority patent/BR112021010139B1/pt
Priority to CA3120865A priority patent/CA3120865C/en
Priority to CN201980085904.XA priority patent/CN113272043B/zh
Priority to JP2021529709A priority patent/JP7543266B2/ja
Priority to MX2021006064A priority patent/MX2021006064A/es
Priority to EP19891188.5A priority patent/EP3887022A4/en
Application filed by University of California Berkeley, University of California San Diego UCSD filed Critical University of California Berkeley
Priority to KR1020217019411A priority patent/KR20210105366A/ko
Publication of WO2020112899A1 publication Critical patent/WO2020112899A1/en
Priority to US17/330,402 priority patent/US11998889B2/en
Anticipated expiration legal-status Critical
Priority to ZA2021/03624A priority patent/ZA202103624B/en
Priority to CONC2021/0006739A priority patent/CO2021006739A2/es
Priority to US18/731,344 priority patent/US20240316531A1/en
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/261—Drying gases or vapours by adsorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03B—INSTALLATIONS OR METHODS FOR OBTAINING, COLLECTING, OR DISTRIBUTING WATER
    • E03B3/00—Methods or installations for obtaining or collecting drinking water or tap water
    • E03B3/28—Methods or installations for obtaining or collecting drinking water or tap water from humid air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present disclosure relates generally to water harvesting, and more specifically to systems and methods for harvesting water from surrounding air using various types of metal- organic frameworks.
  • MOFs metal-organic frameworks
  • This invention provides a guideline to fine-tune and improve the water sorption properties by employing metal-organic frameworks constructed from a combination of two or more building blocks, which may generally be referred to as multivariate (MTV) MOFs. 12
  • MTV multivariate
  • This approach will not only drastically expand the variety of water harvesting systems but will also allow for adjustment of the water sorption properties for the respective application.
  • the invention provides multivariate and other metal-organic frameworks (MOFs) for water harvesting and other uses.
  • the multivariate metal-organic frameworks (MTV-MOFs) may have mixed metals in the secondary building units and/or mixed organic ligands.
  • a MOF comprising repeating cores, wherein the cores comprise secondary building units (SBUs) connected to organic ligands.
  • the secondary building units comprise one or more metals or metal-containing complexes.
  • the secondary building units form ID rod-like chains or distinct multinuclear metal clusters.
  • the organic ligands comprise one or more linear ditopic moieties, v-shaped ditopic moieties, trigonal tritopic moieties, square or rectangular tetratopic moieties, or tetrahedral tetratopic moieties.
  • such moieties comprise 5-membered or 6- membered rings substituted with at least two carboxylate groups.
  • the invention provides a multivariate metal-organic framework (MTV- MOF) of inorganic metal clusters (secondary building units, SBUs) and a combination of two or more different organic units/ligands (linkers).
  • MTV- MOF multivariate metal-organic framework
  • MOF made up of secondary building units and one type of organic ligand.
  • the organic ligands are linear ditopic, v- shaped ditopic, trigonal tritopic, square or rectangular tetratopic, or tetrahedral tetratopic. In one variation, at least one of the organic ligands is v-shaped as disclosed herein.
  • the secondary building units are metal clusters, or comprise a metal or metal-containing complex. In certain variations, the secondary building units form ID rod-like chains or distinct multinuclear metal clusters.
  • the metal in the secondary building unit is selected from zirconium, nickel, iron, copper, manganese and aluminum, and/or from magnesium, calcium, strontium, barium, titanium, zinc, indium, cadmium, hafnium, lead, cobalt, and chromium.
  • the invention provides a device such as a water harvester, comprising a moisture sorption unit comprising one or more of the MOFs described herein.
  • the invention provides a method of using one or more of the MOFs described herein, comprising containing in, storing in and/or extracting from the composition a predetermined gas or fluid, such as
  • the invention provides a method of using one or more of the MOFs described herein, comprising utilizing the composition for water harvesting or water purification applications.
  • the invention provides a water harvester comprising a moisture sorption unit comprising a MOF of formula Al(OHX2,5-PylDC), wherein 2,5-PylDC is 2,5- pyrroledicarboxylate.
  • the invention provides a method of using the water harvester comprising for water harvesting or water purification applications.
  • the invention encompasses all combination of the particular embodiments recited herein, as if each combination had been laboriously recited.
  • FIGS. 1A and IB depict a non-comprehensive list of compounds that may be used to form organic ligands connected to secondary building units in the MOFs described herein. These linkers can also be combined in systems for water harvesting to expand the realm of MOF materials for water harvesting.
  • FIGS. 2 and 3 depict a structural model of Al(OH)(2,5-PylDC).
  • FIG. 2 shows views along the a-axis and c-axis.
  • FIG. 3 shows an excerpt of the secondary building units of the MOF. Oxygen atoms are located at the vertices of the octahedron, coordinating to an aluminum atom at the center of the octahedron.
  • FIG. 4 depicts a comparison of the powder x-ray diffraction (PXRD) data of the experimentally attained MOF Al(OH)(2,5-PylDC) and its proposed structural model.
  • FIG. 6 depicts a water sorption isotherm of Al(OH)(2,5-PylDC) conducted at 25 °C.
  • FIG. 7 depicts a structural model of Al(OH)(2,4-PylDC): view along the a-axis (left) and c-axis (right). Oxygen atoms are located at the vertices of the octahedron, coordinating to an aluminum atom at the center of the octahedron.
  • FIG. 8 depicts a comparison of the powder x-ray diffraction (PXRD) data of the experimentally attained MOF Al(OH)(2,4-PylDC) and its proposed structural model.
  • FIG. 10 depicts a water sorption isotherm of Al(OH)(2,4-PylDC) conducted at 25 °C.
  • FIG. 11 depicts a structural model of Al(OH)(2,4-TDC): view along the a-axis (left) and c-axis (right). Oxygen atoms are located at the vertices of the octahedron, coordinating to an aluminum atom at the center of the octahedron.
  • FIG. 12 depicts a comparison of the powder x-ray diffraction (PXRD) data of the experimentally attained MOF Al(OH)(2 ,4-TDC) and its proposed structural model.
  • PXRD powder x-ray diffraction
  • FIG. 14 depicts a water sorption isotherm of Al(OH)(2,4-TDC) conducted at 25 °C.
  • FIG. 15 depicts chemical structures of 2,5-furandicarboxylic acid (H 2 (2,5-FDC)) and 2,4-thiophenedicarboxylic acid (H 2 (2,4-TDC)).
  • FIG. 16 depicts a comparison of the powder X-ray diffraction (PXRD) analyses conducted on Al(OH)(2,5-FDC), MTV-MOF Al(OH)(2,5-FDC)o. 5 (2,4-TDC)o and MOF-323.
  • PXRD powder X-ray diffraction
  • FIG. 17 depicts a 'H-nuclear magnetic resonance (NMR) analysis conducted on the linkers H 2 (2,5-FDC) (top) and H 2 (2,4-TDC) (bottom), as well as on the digested ( Le ., treated as described in Example 4 below) MTV-MOF Al(OH)(2,5-FDC)o. 5 (2,4-TDC)o. 5 (center). Numbers indicate the relative signal intensities of the respective peaks determined through integration. [003h FIG. 18 depicts a representative scanning electron microscopy (SEM) micrograph of the MTV-MOF A1(OH)(2,5-FDC)Q.5(2,4-TDC)OJ.
  • SEM scanning electron microscopy
  • FIGS. 19A-E depict various representative scanning electron microscopy (SEM) micrographs and energy dispersive X-ray spectroscopy (EDS) analyses of the MTV-MOF A1(OHX2,5-FDC)O. 5 (2,4-TDC)O. 5 .
  • SEM scanning electron microscopy
  • EDS energy dispersive X-ray spectroscopy
  • FIG. 20 depicts a water sorption analyses on Al(OH)(2,5-FDC), the MTV-MOF A1(OHX2,5-FDC)O.5(2,4-TDC)O. 5 , and MOF-323 at 25 °C (P: partial vapor pressure,
  • FIG. 21 depicts a low pressure region of the water sorption analyses on Al(OH)(2,5-
  • FIG. 22 depicts chemical structures of Isophthalic acid (H2IPA) and 3,5- pyridinedicarboxylic acid (H 2 (3,5-PynDC)).
  • FIG. 23 depicts a comparison of the powder X-ray diffraction (PXRD) analyses conducted on Al(OH)(3,5-PynDC), the MTV-MOF Al(OH)(3,5-PynDC)o. 56 (IPA)o. 44 , and
  • FIG. 24 depicts a 'H-Nuclear magnetic resonance (NMR) analysis conducted on the linkers H 2 (3,5-PynDC) (top) and H2IPA (bottom), as well as on the digested (/.e., treated as described in Example 5 below) MTV-MOF Al(OH)(3,5-PynDC)o. 56 (IPA)o. 44 ⁇ Numbers indicate the relative signal intensities of the respective peaks determined through integration.
  • NMR 'H-Nuclear magnetic resonance
  • FIG. 25 depicts a representative scanning electron microscopy (SEM) micrograph of the MTV-MOF Al(OH)(3,5-PynDC) 0 . 56 (IPA) o.44.
  • FIGS. 26A-E depict representative scanning electron microscopy (SEM) micrographs and energy dispersive X-ray spectroscopy (EDS) analyses of the MTV-MOF Al(OHX3,5-PynDC)o.56(IPA)o.44.
  • SEM scanning electron microscopy
  • EDS energy dispersive X-ray spectroscopy
  • FIG. 27 depicts a water sorption analyses on Al(OH)(3,5-PynDC), the MTV-MOF Al(OHX3,5-PynDC)o. 56 (IPA)o. 44 , and Al(OH)IPA at 25 °C (P: partial vapor pressure,
  • FIG. 28 depicts a low pressure region of the water sorption analyses on Al(OH)(3,5-
  • organic-inorganic hybrid materials in particular metal-organic frameworks (MOFs), constructed from one or more organic building blocks, particularly for water harvesting applications.
  • MOFs are shown to exhibit desirable properties for water harvesting applications under arid conditions.
  • MOFs may be used to adsorb large amounts of atmospheric water at low relative humidity and successive energy- efficient desorption without loss of porosity.
  • This invention identifies reported as well as new MOFs which are particularly suitable for water harvesting under arid conditions.
  • the invention provides technology to tune and improve the water harvesting properties by employing multivariate (MTV) MOFs.
  • MTV multivariate
  • Such metal-organic frameworks may be constructed from a combination of two or more organic units/ligands.
  • MOF-based water harvesting devices The harvested water can be used for human consumption or irrigation of crops.
  • the tuning of water sorption properties by employment of the MOFs described herein can be used in other water sorption based applications, such as in heat pumps, dehumidifiers, adsorption refrigerators, solar cooling systems, dryers, organic light emitting devices and secondary battery devices.
  • the following description describes various types of MOFs, including single-linker
  • MOFs and MTV-MOFs for water sorption applications, in particular water harvesting.
  • a MOF comprising repeating cores, wherein the cores comprise secondary building units connected to organic ligands.
  • the organic ligands comprise one or more linear ditopic moieties, v-shaped ditopic moieties, trigonal tritopic moieties, square or rectangular tetratopic moieties, or tetrahedral tetratopic moieties. In one variation, the organic ligands comprise v- shaped ditopic moieties.
  • such moieties comprise 5-membered or 6- membered rings substituted with at least two caiboxylate groups. In one variation, such moieties comprise 5-membered or 6-membered rings substituted with two carboxylate groups.
  • organic ligands comprise one or more moieties of Formula
  • X 1 is NH, O or S, and each of R a and R b is independently H or
  • X 3 is NH, O or S, and each of R a and R e is independently H or
  • X 2 is NH, O or S, and R c is H or alkyl
  • X 1 is NH, O or S, and R a is H or alkyl
  • X 2 is NH or O
  • R e is H or alkyl
  • X 1 is NH or O
  • R B is H or alkyl
  • X 1 is NH or O
  • R e is H or alkyl
  • X 1 is NH or O.
  • organic ligands comprise one or more moieties of Formula
  • R d , R e and R f is independently H or alkyl
  • Y 1 and Y 4 are N, and the remaining of Y 4 and Y 1 is CH, or both Y 1 and Y 4 are N, and each of R d and R e are independently H or alkyl; and wherein Y 1 is CH or N.
  • R a , R b , R e , R d , R e and R f are each H.
  • each organic ligand comprises in another variation of the foregoing, each secondary building unit comprises aluminum hydroxide.
  • the MOF is MOF-313.
  • each organic ligand comprises in another variation of the foregoing, each secondary building unit comprises aluminum hydroxide.
  • the MOF is MOF-314.
  • each organic ligand comprises In another
  • each secondary building unit comprises aluminum hydroxide.
  • the MOF is MOF-323.
  • the organic ligands comprise and
  • the M comprises aluminum hydroxide.
  • the M comprises aluminum hydroxide.
  • the M comprises aluminum hydroxide.
  • the organic ligands comprise
  • the MTV-MOF comprises aluminum hydroxide.
  • the MTV-MOF is Al(OH)(3,5- PynDC)(IPA).
  • the MTV-MOF is wherein m
  • the MTV-MOF is Al(OH)(3,5-PynDC)o. 56 (IPA)o. 44 ⁇
  • FIGS. 1A and IB provides a non-comprehensive list of compounds that may be used to form organic ligands connected to secondary building units in the MOFs described herein. These linkers can also be combined in systems for water harvesting to expand the realm of MOF materials for water harvesting dramatically.
  • the secondary building units comprise one or more metals or metal-containing complexes.
  • the secondary building units form ID rod-like chains or distinct multinuclear metal clusters.
  • each secondary building unit comprises one metal or metal-containing complex.
  • each secondary building unit comprises zirconium, nickel, iron, copper, manganese, aluminum, magnesium, calcium, strontium, barium, titanium, zinc, indium, cadmium, hafnium, lead, cobalt, or chromium, or a complex thereof. In one variation, each secondary building unit comprises aluminum or an aluminum-containing complex.
  • MOFs described herein could enable shifting of the P/PQ value at which a steep step is observed in the water vapor sorption isotherm. Further, the total water uptake of a MOF with voluminous ligands can be improved by“doping” it with less bulky ligands due to the resulting increase in the pore volume of the MTV-system. Also, linkers otherwise not forming a MOF can be included in a MTV-MOF, thus expanding the realm of water harvesting materials enormously.
  • the secondary building units are connected to the organic ligands through the oxygen atoms of the carboxylate groups in the organic ligands via a cis- edge-shared octahedra geometry or a trans-edge-shared octahedra geometry.
  • the method comprises combining one or more of the compounds set forth in FIGS. 1A and IB with a metal solution under basic conditions, at elevated temperatures.
  • the metal solution comprises any of the metals described herein for the MOFs.
  • the compounds in FIGS. 1A and IB and the metal solution are combined with a basic solution, such as sodium hydroxide.
  • a solid is obtained from the reaction mixture, and isolated.
  • the isolated product can then be characterized using any suitable methods or techniques known in the art, including, for example, by x-ray diffraction (e.g., powder x-ray diffraction).
  • a method of water harvesting comprising: adsorbing water from ambient atmosphere using a water-harvesting system, wherein the water-harvesting system comprises one or more of the MOFs described herein; desorbing vapor from the one or more MOFs; and collecting water from the vapor.
  • a water-harvesting system comprising an adsorbent layer comprising one or more of the MOFs described herein.
  • the MOFs used are MTV-MOFs.
  • the water-harvesting system is a passive device, in which sunlight-driven desorption of water leads to saturation in a closed environment which, consequently, leads to water condensation.
  • the water-harvesting system is an active device, in which a condenser is needed to collect the water.
  • the condenser may be, for example, adjacent to the adsorbent layer in the water-harvesting system.
  • a composition comprising a multivariate metal-organic framework (MTV -MOF) of inorganic metal clusters (secondary building units, SBUs) and a combination of two or more different organic units (linkers).
  • MTV -MOF multivariate metal-organic framework
  • SBUs secondary building units
  • linkers two or more different organic units
  • linkers are selected from v-shaped, trigonal or tritopic linkers; or square/rectangular-shaped tetratopic linkers; or tetrahedral tetratopic linkers.
  • composition of embodiment 1 wherein at least one of the linkers is a v-shaped linker disclosed herein.
  • composition of embodiment 1, wherein the metal clusters are infinite ID rod-like chains or distinct multinuclear metal clusters.
  • a device such as a water harvester, comprising a moisture sorption unit comprising the composition of any one of embodiments 1 to 5.
  • a method of using the composition of any one of embodiments 1 to 6, comprising containing in, storing in and/or extracting from the composition a predetermined gas or fluid, such as CO2, H2O, H 2 , CH4, C2H4, C2H2, etc.
  • a predetermined gas or fluid such as CO2, H2O, H 2 , CH4, C2H4, C2H2, etc.
  • a water harvester comprising a moisture sorption unit comprising a MOF of formula
  • a metal-organic framework comprising repeating cores, wherein the cores comprise secondary building units connected to organic ligands, wherein the secondary building units comprise one or more metals or metal-containing complexes, wherein the organic ligands comprise one or more linear ditopic moieties, v-shaped ditopic moieties, trigonal tritopic moieties, square or rectangular tetratopic moieties, or tetrahedral tetratopic moieties, wherein the moieties comprise 5-membered or 6-membered rings substituted with at least two caiboxylate groups, and wherein the secondary building units are connected to the organic ligands through the oxygen atoms of the caiboxylate groups in the organic ligands.
  • the cores comprise secondary building units connected to organic ligands, wherein the secondary building units comprise one or more metals or metal-containing complexes, wherein the organic ligands comprise one or more linear ditopic moieties, v-shaped ditopic moieties, t
  • X 1 is NH, O or S, and each of R 8 and R b is independently H or
  • X 3 is NH, O or S, and each of R 8 and R e is independently H or
  • X 2 is NH, O or S, and R e is H or alkyl
  • X 1 is NH, O or S, and R 8 is H or alkyl
  • X 3 is NH, O or S, and R 8 is H or alkyl; wherein X 1 is NH, O or S;
  • Y 1 , Y 2 and Y 3 are independently CH or N;
  • X 3 is NH, O or S
  • Y 1 and Y 2 are independently CH or N.
  • R d , R e and R f is independently H or alkyl
  • Y 1 and Y 4 are N, and the remaining of Y 4 and Y 1 is CH, or both Y 1 and Y 4 are N, and each of R d and R e are independently H or alkyl;
  • Y 1 is CH or N.
  • each organic ligand comprises one moiety of Formula (I)-(CP), and the MOF is a single-linker metal-organic framework.
  • each organic ligand comprises one moiety of Formula (I)-(VII), and the MOF is a single-linker metal-organic framework.
  • each organic ligand comprises:
  • each secondary building unit comprises aluminum hydroxide.
  • each secondary building unit comprises aluminum hydroxide.
  • each secondary building unit comprises aluminum hydroxide.
  • MTV-MOF multivariate metal- organic framework
  • each secondary building unit comprises aluminum hydroxide.
  • each secondary building unit comprises aluminum hydroxide.
  • each secondary building unit comprises aluminum hydroxide.
  • each secondary building unit comprises zirconium, nickel, iron, copper, manganese, aluminum, magnesium, calcium, strontium, barium, titanium, zinc, indium, cadmium, hafnium, lead, cobalt, or chromium, or a complex thereof.
  • each secondary building unit comprises aluminum or an aluminum-containing complex.
  • a method of water harvesting comprising:
  • adsorbing water from ambient atmosphere using a water-harvesting system wherein the water-harvesting system comprises one or more MOFs of any one of embodiments 11 to 50; desorbing vapor from the one or more MOFs; and
  • a water harvesting system comprising an adsorbent layer comprising one or more
  • MOFs of any one of embodiments 11 to 50 are provided.
  • a method of using the MOF of any one of embodiments 11 to 50 comprising containing in, storing in and/or extracting from the MOF a predetermined gas or fluid.
  • FIG. 11 The structure (FIG. 11) of the synthesized MOF was verified based on powder x-ray diffraction (PXRD) analysis (FIG. 12).
  • the structure was shown to be constructed from ID rodlike SBUs connected by 2,4-thiophenedicarboxylate linker ligands.
  • Al(OH)(2,5-FDC) (also known as MIL- 160) was synthesized by dissolving 3 ⁇ 4(2,5-FDC)
  • Al(OH)(3,5-PynDC) 70 mg was obtained.
  • Al(OH)IPA also known as CAU- 10.

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  • Curing Cements, Concrete, And Artificial Stone (AREA)
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US12054922B2 (en) 2019-09-30 2024-08-06 Water Harvesting, Inc. Refrigerator integrated with an atmospheric water harvesting unit, and methods of using thereof
US12390760B2 (en) 2020-02-14 2025-08-19 Water Harvesting, Inc. Atmospheric water harvester with high efficiency, and methods of using thereof
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US11536010B2 (en) 2021-01-19 2022-12-27 Water Harvesting, Inc. Atmospheric water harvester with climate-adjustable adsorbant properties
US11781295B2 (en) 2021-01-19 2023-10-10 Water Harvesting, Inc. Atmospheric water harvester with climate-adjustable adsorbant properties
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US12472464B2 (en) 2023-01-19 2025-11-18 Water Harvesting, Inc. Atmospheric water harvester having subcooler heat exchanger
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