ABSTRACT
Abstract
Provided herein are adsorption materials comprising a mixed-metal mixed-organic framework comprising metal ions of two or more distinct metals and a plurality of organic linkers. Each organic linker in the plurality of organic linkers is connected to a metal ion. The adsorption material further comprises a plurality of ligands. In an aspect, each respective ligand in the plurality of ligands is an amine or other Lewis base (electron donor) appended to a metal ion in the two of more distinct elements of the mixed-metal organic framework to provide a mixed-metal mixed-organic framework system.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS AND PRIORITY CLAIM
This Non-Provisional Patent application is a Continuation of U.S. patent application Ser. No. 17/601,610, filed Oct. 5, 2021, titled âMixed-Metal, Mixed-Organic Framework Systems For Selective CO2 Captureâ, which a National Stage of PCT/US2020/029854, filed Apr. 24, 2020, titled âMixed-Metal, Mixed-Organic Framework Systems For Selective CO2 Captureâ, which claims the benefit of priority to U.S. Provisional Patent Application No. 63/839,261 filed Apr. 26, 2019, titled âMixed-Metal, Mixed-Organic Framework Systems For Selective CO2 Captureâ, all of which are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates to systems of modified mixed-metal, mixed-organic frameworks for selective CO 2 capture and methods of using the same.
BACKGROUND OF THE INVENTION
The combustion of fossil fuels results in emission of CO 2 , a large component of anthropogenic contributions to global climate change. In addition to environmental effects, tax penalties and/or incentives related to CO 2 emissions pose a significant financial consideration for infrastructure development, energy production, and manufacturing. The crux of the problem is that the concentration of CO 2 emitted can vary dramatically between applications, and is most commonly diluted with the benign atmospheric gas N 2 . Nevertheless, the quantity of CO 2 emitted is massive. Thus, what is required is a technology capable of selectively removing diluted CO 2 from gas streams, with performance which can be tuned for implementation in diverse applications, and where the CO 2 can be easily and economically recovered for use or storage in turn regenerating the adsorbent technology for reuse.
Prior solutions for CO 2 capture primarily focus on liquid amine solutions, which are expensive to regenerate, cause engineering challenges due to changes in physical properties as CO 2 is adsorbed, and are mildly corrosive. More recently developed technologies include water-lean solutions, which display modest improvements in CO 2 capture performance, but are markedly more expensive than aqueous amines and still suffer from engineering challenges due to changes in physical properties. Solid-phase adsorbents, such as polymers and zeolites, have also been explored for CO 2 capture. The former typically suffer from low selectivity and poor capacity, while the latter are readily de-activated by water, requiring impractical pre-treatment of emissions prior to CO 2 removal.
In addition, prior art metal-organic frameworks have been reported for selective CO 2 capture, prepared from single metal framework materials and functionalized post-synthesis with various diamines. In these systems, while selection of diamine provides some degree to which CO 2 capture performance can be tuned, the limitations in diamine diversity and availability reduces the extent to which the material may be optimized for specific emission streams.
A need exists, therefore, for framework systems that can be adjusted and/or modified so to regulate CO 2 adsorption to a required level and capture CO 2 from different emission streams.
SUMMARY OF THE INVENTION
Provided herein are mixed-metal organic frameworks having an empirical or chemical formula of two or more distinct metallic elements and bridged by a linker. The subject mixed-metal organic frameworks comprise a plurality of disalicylate linkers, where each linker comprises one or more aromatic rings, each aromatic ring comprising a carboxylate functional group and an alcohol functional group, the carboxylate functional group, and the alcohol functional groups are adjacent to one another on each aromatic ring. In addition, each aromatic ring is positioned at a greatest distance from the other.
Further provided are mixed-metal organic frameworks having the formula: M 1 xM 2 (2-x) (A) where M 1 and M 2 are each independently different metal cations, and A is a disalicylate organic linker. In an aspect, M 1 and M 2 are both independently a divalent metal cation. In an aspect, M 1 and M 2 are selected independently from Ca 2+ , Mg 2+ , Fe 2+ , Cr 2+ , V 2+ Mn 2+ , Co 2+ , Ni 2+ , Zn 2+ , Cu 2+ . . . . In an aspect, A is a plurality of disalicylate organic linkers selected independently from a group consisting of:
wherein R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20 are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl; and R 17 is selected from the group consisting of substituted or unsubstituted aryl, vinyl, alkynyl, substituted or unsubstituted heteroaryl, divinyl benzene, and diacetyl benzene.
In an aspect, the mixed metal organic frameworks provide an X-ray diffraction pattern having a unit cell that can be indexed to a hexagonal unit cell. In an aspect, the unit cell is selected from spacegroups 168 to 194 as defined in the International Tables for Crystallography. In an aspect, the present mixed-metal organic frameworks further comprise a metal rod structure described by the Lidin-Andersson helix, as described by Schoedel, Li, Li, O'Keeffe, and Yaghi, Chem Rev. 2016 116, 12466-12535. In an aspect, the mixed-metal organic framework has a hexagonal pore oriented parallel to the metal rod structure. In an aspect, the present mixed-metal organic frameworks display a (3,5,7)-c msi net, according to the approach described by Schoedel, Li, Li, O'Keeffe, and Yaghi, Chem Rev. 2016 116, 12466-12535. In an aspect, The mixed-metal organic framework displays a (3,5,7)-c msg net, according to the approach described by Schoedel, Li, Li, O'Keeffe, and Yaghi, Chem Rev. 2016 116, 12466-12535.
In an aspect, the subject mixed-metal organic frameworks express peak maxima in the X-ray diffraction pattern at 30° C. after drying at 250° C. under N 2 for 30 minutes at:
d(â«)
18.65 ± 0.5
10.79 ± 0.5
â9.35 ± 0.5
â7.07 ± 0.5
â6.51 ± 0.5
â6.24 ± 0.5
â5.84 ± 0.5
â5.41 ± 0.5
â5.19 ± 0.5
In an aspect, the express peak maxima in the X-ray diffraction pattern at 30° C. after drying at 250° C. under N 2 for 30 minutes at:
d(â«)
18.65 ± 0.5
10.79 ± 0.5
â7.07 ± 0.5
â5.41 ± 0.5
â5.19 ± 0.5
In an aspect, an A axis of the unit cell and a B axis of the unit cell are each greater than 18 â«, and a c axis is greater than 6 â«.
Further provided herein are mixed-metal mixed-organic framework systems comprising the subject mixed-metal organic framework and a ligand comprising an amine. In an aspect, the ligand is a diamine. In an aspect, the diamine is a cyclic diamine. In an aspect, the diamine is independently selected from:
wherein Z is independently selected from carbon, silicon, germanium, sulfur and selenium; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 , are each independently selected from H, halogen, methyl, halogen substituted methyl and hydroxyl.
In an aspect, the diamine ligand is selected from one of: dimethylethylenediamine (mmen) or 2-(aminomethyl) piperidine (2-ampd). In an aspect, the ligand is a tetramine. In an aspect, the tetramine is selected from one of 3-4-3 tetramine (spermine) or 2-2-2 tetramine.
In an aspect, the mixed-metal organic framework system comprises a secondary ligand, where the secondary ligand is a triamine. In an aspect, the secondary ligand is selected from:
Also provided are methods of synthesizing a mixed-metal organic framework comprising the steps of: contacting a solution comprising two or more sources of two or more distinct metallic elements and an organic linker capable of bridging metal cations and heating the mixture to produce one or more of the present mixed-metal organic frameworks. In an aspect, the two or more distinct metallic elements are independently selected from Ca, Mg, Fe, Cr, V, Mn, Co, Ni, Zn, Cu. In an aspect, the solution comprises an elemental metal or a salt of the metal in which the counter anion comprises a nitrate, acetate, carbonate, oxide, hydroxide, fluoride, chloride, bromide, iodide, phosphate, or acetylacetonate.
Further provided are methods of synthesizing the mixed-metal organic frameworks comprising the steps of contacting the mixed-metal organic framework with a secondary ligand in a gas or liquid medium. In an aspect, the ligand is an amine-containing molecule. In an aspect, the ligand is a diamine. In an aspect, the ligand is a triamine. In an aspect, the ligand is a tetramine.
Provided herein are particles comprising one or more of the subject mixed-metal mixed-organic framework system. Also, provided herein is an adsorbent material comprising the subject mixed-metal mixed-organic framework system. In an aspect, the mixed-metal mixed-organic framework displays a Type-V isotherm profile for CO 2 . Also, provided are methods of adsorbing carbon dioxide is from a carbon-dioxide containing stream by contacting said stream with one or more of the present adsorbents. Further provided are methods of tuning the position of a step of a Type-V CO 2 isotherm comprising the step of varying an amount, or a type, of the metal ions of two or more distinct metals of the mixed-metal organic frameworks or mixed-metal mixed-organic framework systems.
BRIEF DESCRIPTION OF THE DRAWINGS
</para-nu
CROSS-REFERENCE TO RELATED APPLICATIONS AND PRIORITY CLAIM
This Non-Provisional Patent application is a Continuation of U.S. patent application Ser. No. 17/601,610, filed Oct. 5, 2021, titled âMixed-Metal, Mixed-Organic Framework Systems For Selective CO2 Captureâ, which a National Stage of PCT/US2020/029854, filed Apr. 24, 2020, titled âMixed-Metal, Mixed-Organic Framework Systems For Selective CO2 Captureâ, which claims the benefit of priority to U.S. Provisional Patent Application No. 63/839,261 filed Apr. 26, 2019, titled âMixed-Metal, Mixed-Organic Framework Systems For Selective CO2 Captureâ, all of which are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates to systems of modified mixed-metal, mixed-organic frameworks for selective CO 2 capture and methods of using the same.
BACKGROUND OF THE INVENTION
The combustion of fossil fuels results in emission of CO 2 , a large component of anthropogenic contributions to global climate change. In addition to environmental effects, tax penalties and/or incentives related to CO 2 emissions pose a significant financial consideration for infrastructure development, energy production, and manufacturing. The crux of the problem is that the concentration of CO 2 emitted can vary dramatically between applications, and is most commonly diluted with the benign atmospheric gas N 2 . Nevertheless, the quantity of CO 2 emitted is massive. Thus, what is required is a technology capable of selectively removing diluted CO 2 from gas streams, with performance which can be tuned for implementation in diverse applications, and where the CO 2 can be easily and economically recovered for use or storage in turn regenerating the adsorbent technology for reuse.
Prior solutions for CO 2 capture primarily focus on liquid amine solutions, which are expensive to regenerate, cause engineering challenges due to changes in physical properties as CO 2 is adsorbed, and are mildly corrosive. More recently developed technologies include water-lean solutions, which display modest improvements in CO 2 capture performance, but are markedly more expensive than aqueous amines and still suffer from engineering challenges due to changes in physical properties. Solid-phase adsorbents, such as polymers and zeolites, have also been explored for CO 2 capture. The former typically suffer from low selectivity and poor capacity, while the latter are readily de-activated by water, requiring impractical pre-treatment of emissions prior to CO 2 removal.
In addition, prior art metal-organic frameworks have been reported for selective CO 2 capture, prepared from single metal framework materials and functionalized post-synthesis with various diamines. In these systems, while selection of diamine provides some degree to which CO 2 capture performance can be tuned, the limitations in diamine diversity and availability reduces the extent to which the material may be optimized for specific emission streams.
A need exists, therefore, for framework systems that can be adjusted and/or modified so to regulate CO 2 adsorption to a required level and capture CO 2 from different emission streams.
SUMMARY OF THE INVENTION
Provided herein are mixed-metal organic frameworks having an empirical or chemical formula of two or more distinct metallic elements and bridged by a linker. The subject mixed-metal organic frameworks comprise a plurality of disalicylate linkers, where each linker comprises one or more aromatic rings, each aromatic ring comprising a carboxylate functional group and an alcohol functional group, the carboxylate functional group, and the alcohol functional groups are adjacent to one another on each aromatic ring. In addition, each aromatic ring is positioned at a greatest distance from the other.
Further provided are mixed-metal organic frameworks having the formula: M 1 xM 2 (2-x) (A) where M 1 and M 2 are each independently different metal cations, and A is a disalicylate organic linker. In an aspect, M 1 and M 2 are both independently a divalent metal cation. In an aspect, M 1 and M 2 are selected independently from Ca 2+ , Mg 2+ , Fe 2+ , Cr 2+ , V 2+ Mn 2+ , Co 2+ , Ni 2+ , Zn 2+ , Cu 2+ . . . . In an aspect, A is a plurality of disalicylate organic linkers selected independently from a group consisting of:
wherein R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20 are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl; and R 17 is selected from the group consisting of substituted or unsubstituted aryl, vinyl, alkynyl, substituted or unsubstituted heteroaryl, divinyl benzene, and diacetyl benzene.
In an aspect, the mixed metal organic frameworks provide an X-ray diffraction pattern having a unit cell that can be indexed to a hexagonal unit cell. In an aspect, the unit cell is selected from spacegroups 168 to 194 as defined in the International Tables for Crystallography. In an aspect, the present mixed-metal organic frameworks further comprise a metal rod structure described by the Lidin-Andersson helix, as described by Schoedel, Li, Li, O'Keeffe, and Yaghi, Chem Rev. 2016 116, 12466-12535. In an aspect, the mixed-metal organic framework has a hexagonal pore oriented parallel to the metal rod structure. In an aspect, the present mixed-metal organic frameworks display a (3,5,7)-c msi net, according to the approach described by Schoedel, Li, Li, O'Keeffe, and Yaghi, Chem Rev. 2016 116, 12466-12535. In an aspect, The mixed-metal organic framework displays a (3,5,7)-c msg net, according to the approach described by Schoedel, Li, Li, O'Keeffe, and Yaghi, Chem Rev. 2016 116, 12466-12535.
In an aspect, the subject mixed-metal organic frameworks express peak maxima in the X-ray diffraction pattern at 30° C. after drying at 250° C. under N 2 for 30 minutes at:
d(â«)
18.65 ± 0.5
10.79 ± 0.5
â9.35 ± 0.5
â7.07 ± 0.5
â6.51 ± 0.5
â6.24 ± 0.5
â5.84 ± 0.5
â5.41 ± 0.5
â5.19 ± 0.5
In an aspect, the express peak maxima in the X-ray diffraction pattern at 30° C. after drying at 250° C. under N 2 for 30 minutes at:
d(â«)
18.65 ± 0.5
10.79 ± 0.5
â7.07 ± 0.5
â5.41 ± 0.5
â5.19 ± 0.5
In an aspect, an A axis of the unit cell and a B axis of the unit cell are each greater than 18 â«, and a c axis is greater than 6 â«.
Further provided herein are mixed-metal mixed-organic framework systems comprising the subject mixed-metal organic framework and a ligand comprising an amine. In an aspect, the ligand is a diamine. In an aspect, the diamine is a cyclic diamine. In an aspect, the diamine is independently selected from:
wherein Z is independently selected from carbon, silicon, germanium, sulfur and selenium; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 , are each independently selected from H, halogen, methyl, halogen substituted methyl and hydroxyl.
In an aspect, the diamine ligand is selected from one of: dimethylethylenediamine (mmen) or 2-(aminomethyl) piperidine (2-ampd). In an aspect, the ligand is a tetramine. In an aspect, the tetramine is selected from one of 3-4-3 tetramine (spermine) or 2-2-2 tetramine.
In an aspect, the mixed-metal organic framework system comprises a secondary ligand, where the secondary ligand is a triamine. In an aspect, the secondary ligand is selected from:
Also provided are methods of synthesizing a mixed-metal organic framework comprising the steps of: contacting a solution comprising two or more sources of two or more distinct metallic elements and an organic linker capable of bridging metal cations and heating the mixture to produce one or more of the present mixed-metal organic frameworks. In an aspect, the two or more distinct metallic elements are independently selected from Ca, Mg, Fe, Cr, V, Mn, Co, Ni, Zn, Cu. In an aspect, the solution comprises an elemental metal or a salt of the metal in which the counter anion comprises a nitrate, acetate, carbonate, oxide, hydroxide, fluoride, chloride, bromide, iodide, phosphate, or acetylacetonate.
Further provided are methods of synthesizing the mixed-metal organic frameworks comprising the steps of contacting the mixed-metal organic framework with a secondary ligand in a gas or liquid medium. In an aspect, the ligand is an amine-containing molecule. In an aspect, the ligand is a diamine. In an aspect, the ligand is a triamine. In an aspect, the ligand is a tetramine.
Provided herein are particles comprising one or more of the subject mixed-metal mixed-organic framework system. Also, provided herein is an adsorbent material comprising the subject mixed-metal mixed-organic framework system. In an aspect, the mixed-metal mixed-organic framework displays a Type-V isotherm profile for CO 2 . Also, provided are methods of adsorbing carbon dioxide is from a carbon-dioxide containing stream by contacting said stream with one or more of the present adsorbents. Further provided are methods of tuning the position of a step of a Type-V CO 2 isotherm comprising the step of varying an amount, or a type, of the metal ions of two or more distinct metals of the mixed-metal organic frameworks or mixed-metal mixed-organic framework systems.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a powder x-ray diffraction pattern of a representative mixed-metal MOF-274 framework system.
FIGS. 2 A, 2 B, 2 C, 2 D and 2 E depict representative data collected by energy-dissipative x-ray spectroscopy (âEDSâ).
FIG. 3 is normalized x-ray absorption spectroscopy data for Ni 1 Mg 1 -MOF-274 (50% Ni), collected at the Ni K-edge. It is critical to note that the feature around 2.5 â« decreases as the Mg: Ni ratio increases.
FIG. 4 is a comparison of the scattering paths that reveal Mg is a weaker backscatterer than Ni.
FIG. 5 is a representative fitted extended x-ray absorption fine structure (EXAFS) spectrum for a Ni 1 Mg 1 -MOF-274 (50% Ni) framework system.
FIG. 6 is a representative powder x-ray diffraction pattern of mixed-metal framework system EMM-44 (the 2-ampd-appended mixed-metal MOF-274 framework system).
FIG. 7 is a representative 1H NMR of mixed-metal mixed-organic framework system EMM-44, following digestion with DCI in DMSO-d 6 .
FIG. 8 are CO 2 isotherms for Mn 0.1 Mg 1.9 -EMM-44 (5% Mn), Mn 0.2 Mg 1.8 -EMM-44 (10% Mn), Mn 0.5 Mg 1.5 -EMM-44 (25% Mn) and Mn 1 Mg 1 -EMM44 (50% Mn) MOF-274, displaying an unusual and highly desired type-V isotherm.
FIG. 9 is CO 2 isotherm for Mn 0.1 Mg 1.9 -EMM-44 (5% Mn), Mn 0.2 Mg 1.8 -EMM-44 (10% Mn), Mn 0.5 Mg 1.5 -EMM-44 (25% Mn) and Mn 1 Mg 1 -EMM44 (50% Mn) MOF-274 plotted on a log scale to more fully display the characteristic low-pressure step in the Type-V isotherm.
FIG. 10 . shows a position of the CO 2 -isotherm midpoint versus Mn loading for Mn x Mg 2-x -EMM-44.
FIG. 11 illustrates the structure of a diamine-appended metal organic framework EMM-44.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Provided herein are mixed-metal organic frameworks comprising metal ions of two or more distinct elements and a plurality of organic linkers, where each organic linker is connected to one of the metal ions of two or more distinct elements. Further provided are mixed-metal mixed-organic framework systems comprising a mixed-metal mixed-organic framework and a ligand. The mixed-metal mixed-organic framework comprises metal ions of two or more distinct elements and a plurality of organic linkers, where the organic linker is connected to one of the metal ions of two or more distinct elements.
In an aspect, the mixed-metal organic framework comprises two or more distinct elements independently selected from the group of Mg, Ca, V, Mn, Cr, Fe, Co, Ni, Cu and Zn. In an aspect, each of the two or more distinct elements is Mg, Mn, Ni, or Zn. In an aspect, the mixed-metal organic framework comprises a ligand selected from the group of diamine, cyclic diamine, triamine, and/or tetramine. In an aspect, the ligand is an organic diamine. In an aspect, the ligand is amine 2-(aminomethyl) piperidine (â2-ampdâ). In an aspect, the mixed-metal mixed-organic framework system displays a Type-V step CO 2 isotherm profile upon exposure to carbon dioxide. In an aspect, the Type-V step is adjusted through metal selection and/or ratio of metals incorporated into the mixed-metal framework.
Also, provided is an adsorbent material comprising the mixed-metal mixed-organic framework system described herein. Further provided are methods of removing carbon dioxide from a feed comprising the step of passing the feed over the mixed-metal mixed-organic framework system. In addition, methods of adjusting a position of a step of a Type-V isotherm comprising the step of varying one or more of the metal ions of two or more distinct elements of the mixed-metal mixed-organic framework system.
In an aspect, provided herein is a mixed-metal organic framework of general structural Formula I
M 1 xM 2 (2-x) (A)ââI
wherein M 1 is a metal or salt thereof, and M 2 is a metal or salt thereof, but M 1 is not M 2 ; X is a value from 0.01 to 1.99; and A is a plurality of organic linkers.
Further, in an aspect, provided is a mixed-metal mixed-organic framework system of general structural Formula II
M 1 x M 2 (2-x) (A)(B)ââII
wherein M 1 is independently selected from Mg, Ca, V, Mn, Cr, Fe, Co, Ni, Cu and Zn; M 2 is independently selected from Mg, Ca, V, Mn, Cr, Fe, Co, Ni, Cu and Zn, and M 1 is not M 2 ; X is a value from 0.01 to 1.99; A is an organic linker; and B is a ligand.
Before the present methods and devices are disclosed and described, it is to be understood that unless otherwise indicated this invention is not limited to specific compounds, components, compositions, reactants, reaction conditions, ligands, catalyst structures, metallocene structures, or the like, as such may vary, unless otherwise specified. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.
For the purposes of this disclosure, the following definitions will apply:
As used herein, the terms âaâ and âtheâ as used herein are understood to encompass the plural as well as the singular.
As used herein, the term âheteroatomâ includes oxygen (O), nitrogen (N), sulfur(S) and silicon (Si), boron (B) and phosphorous (P).
The term âarylâ means, unless otherwise stated, a polyunsaturated, aromatic substituent that can be a single ring or multiple rings fused together or linked covalently. In an aspect, the substituent has from 1 to 11 rings, or more specifically, 1 to 3 rings. The term âheteroarylâ refers to aryl substituent groups (or rings) that contain from one to four heteroatoms selected from N, O and S, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized. An exemplary heteroaryl group is a six-membered azine, e.g., pyridinyl, diazinyl and triazinyl. A heteroaryl group can be attached to the remainder of the molecule through a heteroatom. Non-limiting examples of aryl and heteroaryl groups include phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4-imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-benzothiazolyl, purinyl, 2-benzimidazolyl, 5-indolyl, 1-isoquinolyl, 5-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 3-quinolyl, and 6-quinolyl. Substituents for each of the above noted aryl and heteroaryl ring systems are selected from the group of acceptable substituents described below.
As used herein, the terms âalkyl,â âaryl,â and âheteroarylâ can optionally include both substituted and unsubstituted forms of the indicated species. Substituents for the aryl and heteroaryl groups are generically referred to as âaryl group substituents.â The substituents are selected from, for example: groups attached to the heteroaryl or heteroarene nucleus through carbon or a heteroatom (e.g., P, N, O, S, Si, or B) including, without limitation, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl, âORâ², âO, âNRâ², âNâORâ², âNRâ²Râ³, âSRâ², -halogen, âSiRâ²Râ³Râ³, âOC(O)Râ², âC(O)Râ², --CO.sub.2Râ², âCONRâ²Râ³, âOC(O)NRâ²Râ³, âNRâ³C(O)Râ², âNRâ²âC(O) NRâ³Râ³, âNRâ³C(O).sub.2Râ², âNRâC(NRâ²Râ³Râ³).dbd.NRâ³, âNRâC(NRâ²Râ³)âNRâ³, âS(O)Râ², âS(O)Râ², âS(O)NRâ²Râ³, âNRSORâ², âCN and, âRâ², --, âCH(Ph), fluoro(C 1 -C 4 ) alkoxy, and fluoro (C 1 -C 4 ) alkyl, in a number ranging from zero to the total number of open valences on the aromatic ring system. Each of the above-named groups is attached to the aryl or heteroaryl nucleus directly or through a heteroatom (e.g., P, N, O, S, Si, or B); and where Râ², Râ³, Râ²â³ and Râ³ are preferably independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. When a compound of the invention includes more than one R group, for example, each of the R groups is independently selected as are each Râ², Râ³, Râ²â³ and Râ³ groups when more than one of these groups is present.
The term âalkyl,â by itself or as part of another substituent, means, unless otherwise stated, a straight or branched chain, or cyclic hydrocarbon radical, or combination thereof, which may be fully saturated, mono- or polyunsaturated and can include di-, tri- and multivalent radicals, having the number of carbon atoms designated (i.e. C 1 -C 10 means one to ten carbons). Examples of saturated hydrocarbon radicals include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, cyclohexyl, (cyclohexyl)methyl, cyclopropylmethyl, homologs and isomers of, for example, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like. An unsaturated alkyl group is one having one or more double bonds or triple bonds. Examples of unsaturated alkyl groups include, but are not limited to, vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and the higher homologs and isomers. The term âalkyl,â unless otherwise noted, is also meant to optionally include those derivatives of alkyl defined in more detail below, such as âheteroalkyl.â
The term âheteroalkyl,â by itself or in combination with another term, means, unless otherwise stated, a stable straight or branched chain, or cyclic hydrocarbon radical, or combinations thereof, consisting of the stated number of carbon atoms and at least one heteroatom selected from the group consisting of O, N, Si and S, and wherein the nitrogen and sulfur atoms may optionally be oxidized and the nitrogen heteroatom may optionally be quaternized. The heteroatom(s) O, N and S and Si may be placed at any interior position of the heteroalkyl group or at the position at which the alkyl group is attached to the remainder of the molecule. Examples include, but are not limited to, âCH 2 âCH 2 âOâCH 3 , âCH 2 âCH. 2 âNHâCH 3 , âCH 2 âCH 2 âN(CH 3 )âCH 3 , âCH 2 âSâCH 2 âCH 3 , âCH 2 âCH 2 , âS(O)âCH 3 , âCH 2 âCH 2 âS(O) 2 âCH 3 , âCHâCHâOâCH 3 , âSi(CH 3 ) 3 , âCH 2 âCHâNâOCH 3 , and âCHâCHâN(CH 3 )âCH 3 . Up to two heteroatoms may be consecutive, such as, for example, âCH 2 âNHâOCH 3 and âCH 2 âOâSi(CH 3 ) 3 . Similarly, the term âheteroalkyleneâ by itself or as part of another substituent means a divalent radical derived from heteroalkyl, as exemplified, but not limited by, âCH 2 âCH 2 âSâCH 2 âCH 2 âand âCH 2 âSâCH 2 âCH 2 âNHâCH 2 â. For heteroalkylene groups, heteroatoms can also occupy either or both chain termini (e.g., alkyleneoxy, alkylenedioxy, alkyleneamino, alkylenediamino, and the like). Still further, for alkylene and heteroalkylene linking groups, no orientation of the linking group is implied by the direction in which the formula of the linking group is written. For example, the formula âCO 2 Râ²ârepresents both âC(O)ORâ² and âOC(O)Râ².
As used herein, the term âligandâ means a molecule containing one or more substituent groups capable of functioning as a Lewis base (electron donor). In an aspect, the ligand can be oxygen, phosphorus or sulfur. In an aspect, the ligand can be an amine or amines containing 1 to 10 amine groups.
The terms âhaloâ or âhalogen,â by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.
The symbol âRâ is a general abbreviation that represents a substituent group that is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted heterocycloalkyl groups.
As used herein, the term âPeriodic Tableâ means the Periodic Table of the Elements of the International Union of Pure and Applied Chemistry (IUPAC), dated December 2015.
As used herein, an âisothermâ refers to the adsorption of an adsorbate as function of concentration while the temperature of the system is held constant. In an aspect, the adsorbate is CO 2 and concentration can be measured as CO 2 pressure. As described herein, isotherms can be performed with porous materials and using various mathematical models applied to calculate the apparent surface area. S. Brunauer, P.H. Emmett, and E. Teller. J. Am. Chem. Soc. 1938, 60, 309-319; K. Walton and R. Q. Snurr, J. Am. Chem. Soc. 2007, 129, 8552-8556; I. Langmuir, J. Am. Chem. Soc. 1916, 38, 2221.
As used herein, the term âstepâ in an isotherm is defined by a sigmoidal absorption profile, otherwise known as a Type-V isotherm. S. J. Gregg and K.S.W. Sing, Adsorption, Surface Area and Porosity, 2 nd Ed. Academic Press Inc., New York, NY, 1982, Ch V. The step can be generally defined by a positive second derivative in the isotherm, followed by an inflection point and a subsequent negative second derivative in the isotherm. The step occurs when adsorbent binding sites become accessible only at certain gas partial pressures, such as when CO 2 inserts into a metal-amine bond, or alternatively, when a dynamic framework pore is opened.
The term âsalt(s)â includes salts of the compounds prepared by the neutralization of acids or bases, depending on the particular ligands or substituents found on the compounds described herein. When compounds of the present invention contain relatively acidic functionalities, base addition salts can be obtained by contacting the neutral form of such compounds with a sufficient amount of the desired base, either neat or in a suitable inert solvent. Examples of base addition salts include sodium, potassium, calcium, ammonium, organic amino, or magnesium salt, or a similar salt. Examples of acid addition salts include those derived from inorganic acids like hydrochloric, hydrobromic, nitric, carbonic, monohydrogencarbonic, phosphoric, monohydrogenphosphoric, dihydrogenphosphoric, sulfuric, monohydrogensulfuric, hydriodic, or phosphorous acids, and the like, as well as the salts derived from relatively nontoxic organic acids like acetic, propionic, isobutyric, butyric, maleic, malic, malonic, benzoic, succinic, suberic, fumaric, lactic, mandelic, phthalic, benzenesulfonic, p-tolylsulfonic, citric, tartaric, methanesulfonic, and the like. Certain specific compounds of the present disclosure contain both basic and acidic functionalities that allow the compounds to be converted into either base or acid addition salts. Hydrates of the salts are also included.
It is understood that, in any compound described herein having one or more chiral centers, if an absolute stereochemistry is not expressly indicated, then each center may independently be of R-configuration or S-configuration or a mixture thereof. Thus, the compounds provided herein may be enantiomerically pure or be stereoisomeric mixtures. In addition, it is understood that, in any compound described herein having one or more double bond(s) generating geometrical isomers that can be defined as E or Z, each double bond may independently be E or Z or a mixture thereof. Likewise, it is understood that, in any compound described, all tautomeric forms are also intended to be included.
In addition, the compounds provided herein may also contain unnatural proportions of atomic isotopes at one or more of the atoms that constitute such compounds. For example, the compounds may be radiolabeled with radioactive isotopes, such as for example tritium (3H), iodine-125 ( 125 I) or carbon-14 ( 14 C). All isotopic variations of the subject compounds, whether radioactive or not, are intended to be encompassed within the scope of present disclosure.
Provided herein is a mixed-metal organic framework comprising a plurality of metal ions of two or more distinct elements and a plurality of organic linkers, where each linker is connected to at least one metal ion of the plurality of metal ions of two or more distinct elements. Also, provided herein is a mixed-metal mixed-organic framework system comprising a mixed-metal organic framework and a ligand, wherein the mixed-metal organic framework comprises a plurality of metal ions of two or more distinct elements, and a plurality of organic linkers, the linker being connected to one of the metal ions.
In an aspect, the mixed-metal organic framework presented herein has the general Formula I:
M 1 x M 2 (2-x) (A)ââI
wherein M 1 is a metal and M 2 is a metal, but M 1 is not M 2 ; X is a value from 0.01 to 1.99; and A is an organic linker as described herein.
In an aspect, X is a value from 0.01 to 1.99. In an aspect, X is a value from 0.1 to 1. In an aspect, X is a value selected from the group consisting of 0.05, 0.1, 0.5 and 1. Further, while X and 2-X represent the relative ratio of M 1 to M 2 , it should be understood that any particular stoichiometry is not implied in Formula I, Formula IA, Formula II or Formula III described herein. As such, the mixed-metal organic frameworks of the Formula I, IA, II or III are not limited to a particular relative ratio of M 1 to M 2 . It is further understood that the metals are typically provided in ionic form and available valency will vary depending on the metal selected.
The metal of Formula I, IA, II and III described herein can be one of the elements of Period 4 Groups IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB of the Periodic Table and Period 3 Group IIA including Mg, Ca, V, Mn, Cr, Fe, Co, Ni, Cu and Zn. Furthermore, the mixed-metal organic framework comprises two more distinct elements as well as different combination of metals, theoretically represented as M 1 x M 2 y . . . . M n z (A)(B) 2 |x+y+ . . . +z=2 and M 1 â M 2 â . . . â M n .
In an aspect, M 1 is selected from Mg, V, Ca, Mn, Cr, Fe, Co, Ni, Cu and Zn; and M 2 is selected from Mg, V, Ca, Mn, Cr, Fe, Co, Ni, Cu and Zn, provided that M 1 is not M 2 . In an aspect, M 1 is selected from the group consisting of Mg, Mn, Ni and Zn; and M 2 is selected from the group consisting of Mg, Mn, Ni and Zn; provided M 1 is not M 2 . In an aspect, M 1 is Mg and M 2 is Mn. In an aspect, M 1 is Mg and M 2 is Ni. In an aspect, M 1 is Zn and M 2 is Ni. It is further understood that the metals are typically provided in an ionic form and the valency will vary depending on the metal selected. Further, the metals can be provided as a salt or in salt form.
In addition, the metal can be a monovalent metal that would make A the protonated form of the linker H-A. For example, the metal can be Na + or one from Group I. Also, the metal can be one of two or more divalent cations (âdivalent metalsâ) or trivalent cations (âtrivalent metalsâ). In an aspect, the mixed metal mixed organic framework includes metals which are at oxidation states other than +2 can (i.e., more than just divalent, trivalent tetravalent,). The framework can have metals comprising a mixture of different oxidation states. Exemplary mixtures include Fe (II) and Fe (III), Cu (II) and Cu (I) and/or Mn (II) and Mn (III). More specifically, trivalent metals are metals having a +3 oxidation state. Some metals used to form the mixed-metal organic framework, specifically Fe and Mn, can adopt +2 (divalent) or +3 (trivalent) oxidation states under relatively gentle conditions. Chem. Mater, 2017, 29, 6181. Likewise, Cu (II) can form Cu (I) under gentle conditions. As such, any minor change to the oxidation state of any of the metals and/or selective change in the oxidation state of a metal can be used to modify the present mixed-metal organic frameworks. Furthermore, any combination of different molecular fragments C 1 , C 2 , . . . . C n may exist. Finally, all of the above variations can be combined, for example, multiple metals (two or more distinct metals) with multiple valences and multiple charge-balancing molecular fragments.
Suitable organic linkers (also referred to herein as âlinkersâ) can be determined from the structure of the mixed-metal organic framework and the symmetry operations that relate the portions of the organic linker that bind to the metal node of the mixed-metal organic framework. A ligand which is chemically or structurally different, yet allows the metal node-binding regions to be related by a C 2 axis of symmetry, will form a mixed-metal organic framework of an identical topology. In an aspect, the organic linker can be formed by two phenyl rings joined at carbon 1,1â², with carboxylic acids on carbons 3, 3â², and alcohols on carbons 4,4â². Switching the position of the carboxylic acids and the alcohols (e.g., âpc-H 4 DOBPDCâ or âpc-MOF-274â described below) does not change the topology of the mixed-metal organic framework.
In an aspect, useful linkers include:
where R 1 is connected to R 1 â² and R 2 is connected to R 2 .â³
Examples of such linkers include:
where R is any molecular fragment.
Examples of suitable organic linkers include para-carboxylate (âpc-linkerâ) such as 4,4â²-dioxidobiphenyl-3,3â²-dicarboxylate (DOBPDC); 4,4â³-dioxido-[1,1â²: 4â²,1â³-terphenyl]-3,3â³-dicarboxylate (DOTPDC); and dioxidobiphenyl-4,4â²-dicarboxylate (para-carboxylate-DOBPDC also referred to as PC-DOBPDC) as well as the following compounds:
In an aspect, the organic linker has the formula:
where R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20 are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl.
In an aspect, the organic linker has the formula:
where, R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl.
In an aspect, the organic linker has the formula:
where R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are each independently selected from H, halogen, hydroxyl, methyl, or halogen substituted methyl, and R 17 is selected from substituted or unsubstituted aryl, vinyl, alkynyl, and substituted or unsubstituted heteroaryl.
In an aspect, the organic linker has the formula:
where R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are each independently selected from H, halogen, hydroxyl, methyl, or halogen substituted methyl.
where R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are each independently selected from H, halogen, hydroxyl, methyl, or halogen substituted methyl, and R 17 is selected from substituted or unsubstituted aryl, vinyl, alkynyl, and substituted or unsubstituted heteroaryl.
In an aspect, the organic linker includes multiple bridged aryl species such as molecules having two (or more) phenyl rings or two phenyl rings joined by a vinyl or alkynyl group.
In an aspect, provided herein the mixed-metal organic framework of structural Formula IA:
M 1 x M 2 (2-x) (A)ââIA
wherein M 1 is a metal independently selected from Mg, Ca, V, Mn, Cr, Fe, Co, Ni, Cu or Zn, or salt thereof; M 2 is a metal independently selected from Mg, Ca, V, Mn, Cr, Fe, Co, Ni, Cu or Zn or salt thereof, but M 1 is not M 2 ; X is a value from 0.01 to 1.99; and A is an organic linker as described herein.
As described herein, the mixed-metal mixed-organic frameworks are porous crystalline materials formed of two or more distinct metal cations, clusters, or chains joined by two or more multitopic (polytopic) organic linkers.
The present mixed-metal organic framework can be appended with amine molecule, referred to herein as âligand,â that enables a step-shaped isotherm. The step-shaped isotherm occurs upon the insertion of the CO 2 into the metal-amine coordination bond, in turn creating a negative charge to localize on the oxygen of the CO 2 . Diamines (molecules containing two amines) enable an amine to be bound to the metal, and a second amine to be positioned down the channel of the mixed-metal organic framework. Upon insertion of CO 2 , the second amine accepts a proton, and t
CLAIMS
Claims ( 20 )
We claim:
1 . A mixed-metal organic framework system, comprising:
a mixed-metal organic framework of the formula: M 1 x M 2 y M 3 z (A) where M 1 , M 2 , and M 3 are each independently different metal cations, x+y+z=2, and A is a disalicylate organic linker, wherein M 1 , M 2 , and M 3 are selected independently from Ca 2+ , Mg 2+ , Fe 2+ , Cr 2+ , V 2+ , Mn 2+ , Co 2+ , Ni 2+ , Zn 2+ , Cu 2+ ; and a ligand that is an amine.
2 . The mixed-metal organic framework of claim 1 , wherein the mixed-metal organic framework comprises a plurality of disalicylate linkers A, wherein each linker comprises one or more aromatic rings, each aromatic ring comprising a carboxylate functional group and an alcohol functional group, the carboxylate functional group and the alcohol functional groups are adjacent to one another on each aromatic ring, and each aromatic ring is positioned at a greatest distance from the other.
3 . The mixed-metal organic framework of claim 1 , wherein M 1 , M 2 , and M 3 are each independently a divalent metal cation.
4 . The mixed-metal organic framework of claim 1 , wherein A is a plurality of linkers selected independently from a group consisting of:
wherein R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R 20 are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl; and
R 17 is selected from the group consisting of substituted or unsubstituted aryl, vinyl, alkynyl, substituted or unsubstituted heteroaryl, divinyl benzene, and diacetyl benzene.
5 . The mixed-metal organic framework of claim 1 , wherein the mixed metal organic framework provides an X-ray diffraction pattern that can be indexed to a hexagonal unit cell.
6 . The metal-organic framework of claim 5 , wherein an a axis of the unit cell and a b axis of the unit cell are each greater than 18 â«, and a c axis is greater than 6 â«.
7 . The mixed-metal organic framework of claim 5 , where the unit cell is selected from spacegroups 168 to 194.
8 . The mixed-metal organic framework of claim 1 , further comprising a metal rod structure.
9 . The mixed-metal organic framework of claim 8 having a hexagonal pore oriented parallel to the metal rod structure.
10 . The mixed-metal organic framework of claim 1 , wherein the mixed-metal organic framework displays a (3,5,7)-c msi net, or wherein the mixed-metal organic framework displays a (3,5,7)-c msg net.
11 . The mixed-metal organic framework of claim 1 , wherein the mixed-metal organic framework expresses peak maxima in the X-ray diffraction pattern at 30° C. after drying at 250° C. under N 2 for 30 minutes at:
d(â«)
18.65 ± 0.5
10.79 ± 0.5
â9.35 ± 0.5
â7.07 ± 0.5
â6.51 ± 0.5
â6.24 ± 0.5
â5.84 ± 0.5
â5.41 ± 0.5
â5.19 ± 0.5
12 . The metal-organic framework system of claim 1 , wherein the ligand is a diamine.
13 . The metal-organic framework system of claim 12 , wherein the diamine is independently selected from:
wherein Z is independently selected from carbon, silicon, germanium, sulfur and selenium; and
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 , are each independently selected from H, halogen, methyl, halogen substituted methyl and hydroxyl.
14 . The mixed-metal organic framework system of claim 12 , wherein the diamine ligand is selected from one of: dimethylethylenediamone (mmen) or 2-(aminomethyl) piperidine 2-ampd.
15 . The mixed-metal organic framework system of claim 1 , wherein the ligand is a tetramine.
16 . The mixed-metal organic framework system of claim 15 , wherein the tetramine is selected from one of 3-4-3 tetramine (spermine) or 2-2-2 tetramine.
17 . The mixed-metal organic framework system of claim 1 , further comprising a ligand wherein the ligand is a triamine.
18 . The metal-mixed organic framework system of claim 17 , wherein the ligand is selected from:
19 . A method of synthesizing the mixed-metal organic framework of claim 1 comprising the steps of:
1) contacting a solution comprising 2 or more sources of 2 or more distinct metallic elements and an organic linker capable of bridging metal cations, the metallic elements being selected independently from Ca, Mg, Fe, Cr, V, Mn, Co, Ni, Zn, Cu, and
2) heating the mixture to produce the mixed-metal organic framework of any of the preceding claims .
20 . The method of claim 19 , wherein the solution comprises an elemental metal or a salt of the metal in which the counter anion comprises a nitrate, acetate, carbonate, oxide, hydroxide, fluoride, chloride, bromide, iodide, phosphate, or acetylacetonate.
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