US20200010337A1 - Metal organic framework with perfluorinated linker - Google Patents
Metal organic framework with perfluorinated linker Download PDFInfo
- Publication number
- US20200010337A1 US20200010337A1 US16/572,781 US201916572781A US2020010337A1 US 20200010337 A1 US20200010337 A1 US 20200010337A1 US 201916572781 A US201916572781 A US 201916572781A US 2020010337 A1 US2020010337 A1 US 2020010337A1
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- United States
- Prior art keywords
- metal
- framework
- perfluorinated
- linker
- metal organic
- Prior art date
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- Abandoned
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 4
- 229910021482 group 13 metal Inorganic materials 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 22
- 239000002351 wastewater Substances 0.000 abstract description 2
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- 239000013078 crystal Substances 0.000 description 9
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WFNRNCNCXRGUKN-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(C(O)=O)C(F)=C1F WFNRNCNCXRGUKN-UHFFFAOYSA-N 0.000 description 6
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- -1 linker compound Chemical class 0.000 description 4
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
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- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BFPYWIDHMRZLRN-SLHNCBLASA-N Ethinyl estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 BFPYWIDHMRZLRN-SLHNCBLASA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229960003405 ciprofloxacin Drugs 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003295 industrial effluent Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- XIPDLDUPKUPXBE-ZUIPHPQLSA-N CC(=O)C1=CN(C2CC2)C2=CC(N3CCNCC3)=C(F)C=C2C1=O.CC1=CC(NS(=O)(=O)C2=CC=C(N)C=C2)=NO1.[H][C@]12CC[C@]3(C)[C@](C)(C#C)CC[C@@]3([H])[C@]1([H])CCC1=CC(O)=CC=C12.[H][C@]12C[C@@]3([H])[C@H](N(C)C)C(O)=C(C(C)=O)C(=O)[C@@]3(O)C(O)=C1C(=O)C1=C(O)C=CC=C1[C@@]2(C)O Chemical compound CC(=O)C1=CN(C2CC2)C2=CC(N3CCNCC3)=C(F)C=C2C1=O.CC1=CC(NS(=O)(=O)C2=CC=C(N)C=C2)=NO1.[H][C@]12CC[C@]3(C)[C@](C)(C#C)CC[C@@]3([H])[C@]1([H])CCC1=CC(O)=CC=C12.[H][C@]12C[C@@]3([H])[C@H](N(C)C)C(O)=C(C(C)=O)C(=O)[C@@]3(O)C(O)=C1C(=O)C1=C(O)C=CC=C1[C@@]2(C)O XIPDLDUPKUPXBE-ZUIPHPQLSA-N 0.000 description 1
- RQHWUHJHDSMJHB-UHFFFAOYSA-N CC1=C(C(=O)O)C(F)=C(F)C(C(=O)O)=C1F Chemical compound CC1=C(C(=O)O)C(F)=C(F)C(C(=O)O)=C1F RQHWUHJHDSMJHB-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000012239 Developmental disease Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
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- 238000009877 rendering Methods 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 1
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 1
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Images
Classifications
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- 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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
-
- 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
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/18—Removal of treatment agents after treatment
Definitions
- the present disclosure relates to metal organic frameworks. Methods for making the frameworks and methods for removing contaminants from water using the frameworks are also disclosed.
- Some drugs are not easily degraded via conventional water treatment methods. For example, reverse osmosis and membrane filtration may not remove parts per million (ppm) levels of contaminants.
- the European Union recently finished the Enzymatic Decontamination Technology (ENDETech) project. This $3.5 million project aimed at developing a commercial technology for the enzymatic degradation of waste pharmaceuticals but did not deliver a commercial product.
- polycyclic aromatic hydrocarbons In addition to pharmaceuticals, other contaminants (e.g., polycyclic aromatic hydrocarbons) may be present in water.
- the contaminants may result from incomplete combustion, industrial effluents, and chemical spills such as the Deepwater Horizon incident. Chronic exposure to polycyclic aromatic hydrocarbons has been linked to carcinogenesis and developmental disorders in humans.
- a more practical alternative would be a non-biologic based alternative that is more reproducible over multiple theaters of deployment. It would be desirable to develop new systems and methods for decontaminating water.
- the present disclosure relates to metal organic frameworks and methods for making and using the same.
- a metal organic framework including: secondary building units having a metal or metal cluster or polymeric infinite-chain; and a perfluorinated linker (e.g., a perfluorinated arene linker, a perfluorinated heteroarene linker, etc.).
- a perfluorinated linker e.g., a perfluorinated arene linker, a perfluorinated heteroarene linker, etc.
- the metal may be a group 13 metal and may be selected from the group consisting of aluminum, gallium, and indium.
- the metal is selected from the group consisting of copper, zinc, hafnium, and zirconium.
- the perfluorinated arene linker is
- An exemplary method for treating water containing a contaminant includes contacting the water with the metal organic framework.
- the contaminant is an arene or a heteroarene.
- the contaminant may be a pharmaceutical compound such as tetracycline, ciprofloxacin, or 17 ⁇ -ethynylestradiol.
- the method further includes removing the metal organic framework containing the contaminant from the water.
- FIG. 1 illustrates the formation of a metal organic framework in accordance with some embodiments of the present disclosure.
- FIG. 2 illustrates a reaction for forming a metal organic framework in accordance with some embodiments of the present disclosure.
- FIG. 3 illustrates a metal organic framework in accordance with some embodiments of the present disclosure.
- FIG. 4 illustrates an expanded view of a portion of a metal organic framework in accordance with some embodiments of the present disclosure.
- FIGS. 5A and 5B are schematic illustrations of a decontamination method in accordance with some embodiments of the present disclosure.
- FIGS. 6A and 6B illustrate ⁇ - ⁇ stacking.
- the term “comprising” may include the embodiments “consisting of” and “consisting essentially of.”
- the terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases that require the presence of the named ingredients/steps and permit the presence of other ingredients/steps.
- compositions, mixtures, or processes as “consisting of” and “consisting essentially of” the enumerated ingredients/steps, which allows the presence of only the named ingredients/steps, along with any impurities that might result therefrom, and excludes other ingredients/steps.
- approximating language may be applied to modify any quantitative representation that may vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” and “substantially,” may not be limited to the precise value specified, in some cases. The modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints.
- Metal organic frameworks are materials in which metal-to-organic ligand interactions yield coordination networks.
- the frameworks include metal-containing secondary building units and organic linkers.
- the metal-containing secondary building units may consist of single metal ions or may be clusters that include metals and other elements.
- the secondary building unit may also be referred to as an inorganic node.
- FIG. 1 illustrates a metal organic framework 100 in accordance with some embodiments of the present disclosure.
- the metal organic framework 100 includes secondary building units 110 and linkers 120 .
- the secondary building units 110 contain a metal (e.g., a group 13 metal).
- the secondary building units 110 consist of a metal ion.
- the secondary building units 110 are clusters.
- the linkers 120 are perfluorinated linkers (e.g., perfluorinated arene linkers, perfluorinated heteroarene linkers, etc.).
- the linker of the present disclosure is referred to as “perfluorinated” because it contains no C—H bonds, only C—F bonds.
- the linker 120 is selected from
- only one linker compound is included. In other embodiments, multiple linker compounds are included.
- alkyne spacers allows for easy linker synthesis via Sonogashira couplings and for potential modulation/oligomer extension in which each linker can be dimerized or trimerized in order to create longer linkers prior to framework synthesis.
- the clusters may include the general formula M(L) (Y) wherein M is a metal and may be selected from Zr, In, Ga, or Al; L may be selected from carboxyl groups, hydroxyl groups, or amine groups; and Y may be selected from H 2 O, OH, halogens, or amines. L and Y may also be bridging or non-bridging ligands and can bind a single metal atom with a hapticity ranging from about 1 to about 5.
- Non-limiting examples include [M( ⁇ -O 2 CR) 2 ( ⁇ -OH)]—, trimeric [M 3 O(O 2 CR) 6 (H 2 O) 3 ] + and derivatives thereof, wherein M is a metal.
- a secondary building unit is a metal paddlewheel of M 2 (O 2 CR) 4 , wherein M is a metal.
- M is a metal.
- the metal is copper, zinc, or zirconium.
- M 6 is a metal.
- the metal is zirconium or hafnium.
- the metal organic framework includes a secondary building unit and from about 4 to about 12 organic linkers.
- FIGS. 2 and 3 which are described in more detail below, are examples of nodes with [In( ⁇ -O 2 CR) 2 ( ⁇ -OH)] ⁇ secondary building units.
- FIG. 2 illustrates a reaction for forming a metal organic framework in accordance with some embodiments of the present disclosure.
- the reactants are 2,3,5,6-tetrafluoroterephthalic acid and indium (III) chloride.
- other reactants may also be used as long as the linker is perfluorinated and the secondary building units contain a metal.
- the metal is copper, zinc, hafnium, zirconium, aluminum, gallium, or indium.
- the carboxyl groups in 2,3,5,6-tetrafluoroterephthalic acid are replaced with hydroxyl groups or amine groups.
- Non-limiting examples of amines include heterocyclic amines, triazoles, and free amines.
- the indium in indium (III) chloride is replaced with a different metal and/or the chloride is replaced with a different halide or ligand.
- FIG. 3 illustrates a perspective view of a metal organic framework in accordance with some embodiments of the present disclosure.
- FIG. 4 illustrates an expanded view of a portion of a metal organic framework in accordance with some embodiments of the present disclosure.
- FIGS. 5A and 5B illustrate a method 230 for decontaminating water in accordance with some embodiments of the present disclosure.
- the method 230 includes providing 231 a metal organic framework 200 to wastewater 240 containing contaminants 245 .
- the method 230 further includes removing (e.g., filtering out) 232 the metal organic framework 200 with contaminants 245 to produce clean water 250 .
- the removal may be a batch process or a continuous process.
- the metal organic framework can be added to a fixed volume of contaminated water. After a period of time, the metal organic framework can be removed (e.g., via filtration) with at least a portion of the contaminants contained therein. Depending on solution concentration loading, contaminant removal may take from about an hour up to several days. For example, a 2 mL solution containing about 10,000 ppm tetracycline can be decontaminated down to about 9,200 ppm after 5 days using about 50 mg of the metal organic framework. However, the initial contamination concentration may generally be lower (e.g., from about 1 ppm to about 2 ppm).
- the metal organic framework can be supplied to a stream of contaminated water and removed after a fixed period of time.
- the metal organic framework containing the contaminants can be recycled.
- the recycling may include removing the contaminants from the metal organic framework, thereby rendering the metal organic framework suitable for another removal step.
- the recycling may be performed in the field or in a laboratory setting.
- the recycling may include washing with solvent, heating in the solid state, heating in a solvent, or some combination thereof.
- the contaminant may be removed through a series of solvent washing steps.
- the solvent may be ethanol.
- FIGS. 6A and 6B illustrate ⁇ - ⁇ stacking between benzene and hexafluorobenzene.
- the contaminant is an arene compound.
- an electron-poor linker e.g., a perfluorinated arene
- an electron-rich contaminant e.g., an arene compound
- ⁇ - ⁇ stacking refers to a noncovalent attractive force between two aromatic rings.
- the contaminant may be a pharmaceutical compound.
- the pharmaceutical compound removed from the water is selected from
- the decontamination and water treatment methods of the present disclosure are not limited to embodiments wherein the contaminants are pharmaceutical compounds.
- the contaminants have resulted from incomplete combustion, industrial effluent, or a chemical spill.
- the systems and methods of the present disclosure may be used to remove polycyclic aromatic hydrocarbons, benzene, naphthalene, anthracene, pyrene, and/or combinations thereof and/or their derivatives.
- the systems and methods are used to treat water contaminated with at least one pharmaceutical compound and at least of polycyclic aromatic hydrogen.
- Indium (III) chloride and 2,3,5,6-tetrafluoroterephthalic acid were reacted to form a metal organic framework.
- DMF N,N-dimethylformamide
- 2-propanol 85.50 mL
- deionized water 4.75 mL
- 2,3,5,6-tetrafluoroterephthalic acid 0.595 g, 2.50 mmol, 1.00 equiv
- InCl 3 (1.10 g, 5.00 mmol, 2.00 equiv
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
A metal organic framework includes metal-containing secondary building units and perfluorinated linkers (e.g., pefluorinated arene linkers, perfluorinated heteroarene linkers, etc.). The metal may be copper, zinc, hafnium, zirconium, aluminum, gallium, or indium. A method for removing contaminants from wastewater may utilize the metal organic framework. The contaminants may include arenes.
Description
- This application is a continuation of U.S. application Ser. No. 15/410,813, filed Jan. 20, 2017, which claims the benefit of U.S. Provisional Application Ser. No. 62/280,769, filed Jan. 20, 2016, and the entireties of both of these prior applications are hereby expressly incorporated by reference herein.
- The present disclosure relates to metal organic frameworks. Methods for making the frameworks and methods for removing contaminants from water using the frameworks are also disclosed.
- According to the World Health Organization, pharmaceutical contamination of drinking water is an emerging problem. By some estimates, almost 25% of the world's rivers and lakes are contaminated. Although current contaminant levels are generally below therapeutic thresholds, the effects of prolonged exposure at low dosages are unknown. Pharmaceutical contamination could potentially affect aquatic life in addition to humans.
- Some drugs (e.g., tetracycline, ciprofloxacin, and 17α-ethynylestradiol) are not easily degraded via conventional water treatment methods. For example, reverse osmosis and membrane filtration may not remove parts per million (ppm) levels of contaminants. The European Union recently finished the Enzymatic Decontamination Technology (ENDETech) project. This $3.5 million project aimed at developing a commercial technology for the enzymatic degradation of waste pharmaceuticals but did not deliver a commercial product.
- In addition to pharmaceuticals, other contaminants (e.g., polycyclic aromatic hydrocarbons) may be present in water. The contaminants may result from incomplete combustion, industrial effluents, and chemical spills such as the Deepwater Horizon incident. Chronic exposure to polycyclic aromatic hydrocarbons has been linked to carcinogenesis and developmental disorders in humans.
- Common water treatment techniques (traditionally designed for parasite and microbe removal) such as the activated sludge process are capable of removing some of these contaminants from water streams. However, batch and site disparities in sludge quality are notorious and have led to mixed results in water purification. Furthermore, approaches such as the activated sludge method, although feasible on a plant scale, may not be feasible for deployment to individual users in the field or during site specific catastrophic events.
- A more practical alternative would be a non-biologic based alternative that is more reproducible over multiple theaters of deployment. It would be desirable to develop new systems and methods for decontaminating water.
- The present disclosure relates to metal organic frameworks and methods for making and using the same.
- Disclosed, in various embodiments, is a metal organic framework including: secondary building units having a metal or metal cluster or polymeric infinite-chain; and a perfluorinated linker (e.g., a perfluorinated arene linker, a perfluorinated heteroarene linker, etc.).
- The metal may be a group 13 metal and may be selected from the group consisting of aluminum, gallium, and indium.
- In other embodiments, the metal is selected from the group consisting of copper, zinc, hafnium, and zirconium.
- In some embodiments, the perfluorinated arene linker is
- 2,3,5,6-tetrafluoroterephthalic acid.
- Methods for using the metal organic frameworks are also disclosed. An exemplary method for treating water containing a contaminant includes contacting the water with the metal organic framework.
- In some embodiments, the contaminant is an arene or a heteroarene.
- The contaminant may be a pharmaceutical compound such as tetracycline, ciprofloxacin, or 17α-ethynylestradiol.
- In some embodiments, the method further includes removing the metal organic framework containing the contaminant from the water.
- These and other non-limiting characteristics are more particularly described below.
- The following is a brief description of the drawings, which are presented for the purposes of illustrating the exemplary embodiments disclosed herein and not for the purposes of limiting the same.
-
FIG. 1 illustrates the formation of a metal organic framework in accordance with some embodiments of the present disclosure. -
FIG. 2 illustrates a reaction for forming a metal organic framework in accordance with some embodiments of the present disclosure. -
FIG. 3 illustrates a metal organic framework in accordance with some embodiments of the present disclosure. -
FIG. 4 illustrates an expanded view of a portion of a metal organic framework in accordance with some embodiments of the present disclosure. -
FIGS. 5A and 5B are schematic illustrations of a decontamination method in accordance with some embodiments of the present disclosure. -
FIGS. 6A and 6B illustrate π-π stacking. - A more complete understanding of the devices and methods disclosed herein can be obtained by reference to the accompanying drawings. These figures are merely schematic representations based on convenience and the ease of demonstrating the existing art and/or the present development, and are, therefore, not intended to indicate relative size and dimensions of the assemblies or components thereof.
- Although specific terms are used in the following description for the sake of clarity, these terms are intended to refer only to the particular structure of the embodiments selected for illustration in the drawings, and are not intended to define or limit the scope of the disclosure. In the drawings and the following description below, it is to be understood that like numeric designations refer to components of like function. In the following specification and the claims which follow, reference will be made to a number of terms, which shall be defined to have the following meanings.
- The singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.
- As used in the specification and in the claims, the term “comprising” may include the embodiments “consisting of” and “consisting essentially of.” The terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases that require the presence of the named ingredients/steps and permit the presence of other ingredients/steps. However, such description should be construed as also describing compositions, mixtures, or processes as “consisting of” and “consisting essentially of” the enumerated ingredients/steps, which allows the presence of only the named ingredients/steps, along with any impurities that might result therefrom, and excludes other ingredients/steps.
- Unless indicated to the contrary, the numerical values in the specification should be understood to include numerical values which are the same when reduced to the same number of significant figures and numerical values which differ from the stated value by less than the experimental error of the conventional measurement technique of the type used to determine the particular value.
- All ranges disclosed herein are inclusive of the recited endpoint and independently combinable. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value; they are sufficiently imprecise to include values approximating these ranges and/or values.
- As used herein, approximating language may be applied to modify any quantitative representation that may vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” and “substantially,” may not be limited to the precise value specified, in some cases. The modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints.
- For the recitation of numeric ranges herein, each intervening number there between with the same degree of precision is explicitly contemplated.
- Metal organic frameworks are materials in which metal-to-organic ligand interactions yield coordination networks. The frameworks include metal-containing secondary building units and organic linkers. The metal-containing secondary building units may consist of single metal ions or may be clusters that include metals and other elements. The secondary building unit may also be referred to as an inorganic node.
-
FIG. 1 illustrates a metalorganic framework 100 in accordance with some embodiments of the present disclosure. The metalorganic framework 100 includessecondary building units 110 andlinkers 120. Thesecondary building units 110 contain a metal (e.g., a group 13 metal). In some embodiments, thesecondary building units 110 consist of a metal ion. In other embodiments, thesecondary building units 110 are clusters. Thelinkers 120 are perfluorinated linkers (e.g., perfluorinated arene linkers, perfluorinated heteroarene linkers, etc.). The linker of the present disclosure is referred to as “perfluorinated” because it contains no C—H bonds, only C—F bonds. - In some embodiments, the
linker 120 is selected from - In some embodiments, only one linker compound is included. In other embodiments, multiple linker compounds are included.
- The use of alkyne spacers allows for easy linker synthesis via Sonogashira couplings and for potential modulation/oligomer extension in which each linker can be dimerized or trimerized in order to create longer linkers prior to framework synthesis.
- When the
secondary building units 110 are clusters, the clusters may include the general formula M(L) (Y) wherein M is a metal and may be selected from Zr, In, Ga, or Al; L may be selected from carboxyl groups, hydroxyl groups, or amine groups; and Y may be selected from H2O, OH, halogens, or amines. L and Y may also be bridging or non-bridging ligands and can bind a single metal atom with a hapticity ranging from about 1 to about 5. Non-limiting examples include [M(μ-O2CR)2(μ-OH)]—, trimeric [M3O(O2CR)6(H2O)3]+ and derivatives thereof, wherein M is a metal. - Another example of a secondary building unit is a metal paddlewheel of M2(O2CR)4, wherein M is a metal. In some embodiments, the metal is copper, zinc, or zirconium.
- Another example of a secondary building unit is a M6)6, wherein M is a metal. In some embodiments, the metal is zirconium or hafnium.
- In some embodiments, the metal organic framework includes a secondary building unit and from about 4 to about 12 organic linkers.
-
FIGS. 2 and 3 , which are described in more detail below, are examples of nodes with [In(μ-O2CR)2(μ-OH)]∞ secondary building units. -
FIG. 2 illustrates a reaction for forming a metal organic framework in accordance with some embodiments of the present disclosure. The reactants are 2,3,5,6-tetrafluoroterephthalic acid and indium (III) chloride. However, other reactants may also be used as long as the linker is perfluorinated and the secondary building units contain a metal. In some embodiments, the metal is copper, zinc, hafnium, zirconium, aluminum, gallium, or indium. - In some embodiments, the carboxyl groups in 2,3,5,6-tetrafluoroterephthalic acid are replaced with hydroxyl groups or amine groups. Non-limiting examples of amines include heterocyclic amines, triazoles, and free amines.
- In some embodiments, the indium in indium (III) chloride is replaced with a different metal and/or the chloride is replaced with a different halide or ligand.
-
FIG. 3 illustrates a perspective view of a metal organic framework in accordance with some embodiments of the present disclosure. -
FIG. 4 illustrates an expanded view of a portion of a metal organic framework in accordance with some embodiments of the present disclosure. -
FIGS. 5A and 5B illustrate amethod 230 for decontaminating water in accordance with some embodiments of the present disclosure. Themethod 230 includes providing 231 a metalorganic framework 200 towastewater 240 containingcontaminants 245. Themethod 230 further includes removing (e.g., filtering out) 232 the metalorganic framework 200 withcontaminants 245 to produceclean water 250. The removal may be a batch process or a continuous process. - In the batch process, the metal organic framework can be added to a fixed volume of contaminated water. After a period of time, the metal organic framework can be removed (e.g., via filtration) with at least a portion of the contaminants contained therein. Depending on solution concentration loading, contaminant removal may take from about an hour up to several days. For example, a 2 mL solution containing about 10,000 ppm tetracycline can be decontaminated down to about 9,200 ppm after 5 days using about 50 mg of the metal organic framework. However, the initial contamination concentration may generally be lower (e.g., from about 1 ppm to about 2 ppm).
- In the continuous process, the metal organic framework can be supplied to a stream of contaminated water and removed after a fixed period of time.
- Optionally, the metal organic framework containing the contaminants can be recycled. The recycling may include removing the contaminants from the metal organic framework, thereby rendering the metal organic framework suitable for another removal step. The recycling may be performed in the field or in a laboratory setting. The recycling may include washing with solvent, heating in the solid state, heating in a solvent, or some combination thereof. In some embodiments, the contaminant may be removed through a series of solvent washing steps. The solvent may be ethanol.
-
FIGS. 6A and 6B illustrate π-π stacking between benzene and hexafluorobenzene. In some embodiments, the contaminant is an arene compound. Without wishing to be bound by theory, it is believed that π-π interactions between an electron-poor linker (e.g., a perfluorinated arene) and an electron-rich contaminant (e.g., an arene compound) will facilitate removal of the contaminant from a contaminated water source. π-π stacking (which may also be referred to as aromatic stacking or aromatic-aromatic interaction) refers to a noncovalent attractive force between two aromatic rings. - The contaminant may be a pharmaceutical compound. In some embodiments, the pharmaceutical compound removed from the water is selected from
- sulfamethoxazole.
- However, the decontamination and water treatment methods of the present disclosure are not limited to embodiments wherein the contaminants are pharmaceutical compounds. In some embodiments, the contaminants have resulted from incomplete combustion, industrial effluent, or a chemical spill.
- The systems and methods of the present disclosure may be used to remove polycyclic aromatic hydrocarbons, benzene, naphthalene, anthracene, pyrene, and/or combinations thereof and/or their derivatives.
- In some embodiments, the systems and methods are used to treat water contaminated with at least one pharmaceutical compound and at least of polycyclic aromatic hydrogen.
- The following examples are provided to illustrate the devices and methods of the present disclosure. The examples are merely illustrative and are not intended to limit the disclosure to the materials, conditions, or process parameters set forth therein.
- Indium (III) chloride and 2,3,5,6-tetrafluoroterephthalic acid were reacted to form a metal organic framework. To a pre-mixed solution of N,N-dimethylformamide (DMF) (4.75 mL), 2-propanol (85.50 mL), and deionized water (4.75 mL) was added 2,3,5,6-tetrafluoroterephthalic acid (0.595 g, 2.50 mmol, 1.00 equiv) and InCl3 (1.10 g, 5.00 mmol, 2.00 equiv) in that order. The resulting solution was sonicated for 6-7 minutes until complete dissolution was observed. The solution sat in a hood for 30 minutes covered with Parafilm, which was determined to produce larger crystals than no wait period. The clear solution was then filtered through a GE-brand 25 mm PVDF syringe filter in 5 mL portions into 20 mL scintillation vials. The scintillation vials were sealed with Teflon-lined caps and placed in an 80° C. oven for 72 h. The vials were removed from the oven and allowed to cool to room temperature. The colorless crystals were combined into one 4 mL vial by drawing up both crystals and mother liquor using a pipette. The mother liquor was decanted away from the crystals which were then washed with DMF (3×2 mL). Crystals of the framework material washed with DMF (3×2 mL) were dried under vacuum at room temperature for a minimum of 18 h.
- To a 4 mL vial containing 2.00 mL deuterium oxide was added tetracycline HCl (0.020 g, 0.042 mmol, 1.00 equiv). The solution was manually shaken until dissolution was observed. Dried framework material (0.0500 g) was then added to the golden yellow solution. The vial was placed on a Thermo Scientific MaxQ 2000 shaker (˜100 RPM) for five days. The doping liquid was then removed via pipette and set aside for NMR analysis. The yellow crystals were rinsed with deuterium oxide (3×2 mL); the second rinse portion was used to transfer the crystals to a new 4 mL vial, and the crystals soaked in the third portion overnight. All washings were combined and analyzed via 1H NMR using tetrahydrofuran (3.4 μL, 0.042 mmol, 1.0 equiv) as a standard. Separately the yellow crystals were digested using a 1:1 mixture by volume of DCI:CD3OD (3.00 mL). The resulting solution was then analyzed using 1H NMR spectroscopy using dichloromethane (2.7 μL, 0.042 mmol, 1.0 equiv) as a standard. NMR analysis indicated approximately ˜8% of the starting tetracycline was incorporated into the MOF framework.
- The present disclosure has been described with reference to exemplary embodiments. Obviously, modifications and alternations will occur to others upon reading and understanding the preceding detailed description. It is intended that the present disclosure be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (20)
1. A metal organic framework comprising:
a secondary building unit comprising a metal; and
a perfluorinated linker.
2. The framework of claim 1 , wherein the metal is selected from the group consisting of copper, zinc, hafnium, zirconium, aluminum, gallium, and indium.
3. The framework of claim 1 , wherein the metal is a group 13 metal.
4. The framework of claim 3 , wherein the group 13 metal is selected from the group consisting of aluminum, gallium, and indium.
5. The framework of claim 1 , wherein the perfluorinated linker is a perfluorinated arene linker.
6. The framework of claim 1 , wherein the perfluorinated linker is a perfluorinated heteroarene linker.
8. The framework of claim 1 , wherein the secondary building unit consists of a group 13 metal ion.
9. The framework of claim 1 , wherein the secondary building units are clusters.
10. The framework of claim 1 , wherein the metal is copper.
11. The framework of claim 1 , wherein the metal is zinc.
12. The framework of claim 1 , wherein the metal is hafnium.
13. The framework of claim 1 , wherein the metal is zirconium.
14. The framework of claim 1 , wherein the metal is aluminum.
15. The framework of claim 1 , wherein the metal is gallium.
16. The framework of claim 1 , wherein the metal is indium.
18. The framework of claim 17 , wherein the metal is selected from the group consisting of copper, zinc, hafnium, zirconium, aluminum, gallium, and indium.
19. The framework of claim 17 , wherein the secondary building unit consists of a group 13 metal ion.
20. A metal organic framework comprising:
a secondary building unit comprising a metal; and
a perfluorinated arene or heteroarene linker.
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