Fluorinated MOF materials having rectangular channels, method of synthesizing MOF materials and methods of using MOF materials including for CO
View Patent ↗Provided herein are mixed ligand metal organic framework (ML-MOF) materials having rectangular grids characterized by the general formula M a M b F 6-n (O/H 2 O) n (Ligand′) x (Ligand″) y (solvent) z , which are effective for capture of carbon dioxide from a fluid composition.
1 . A mixed ligand metal organic framework (ML-MOF) having rectangular grids characterized by the general formula
M a M b F 6-n (O/H 2 O) n (Ligand′) x (Ligand″) y (solvent) z
wherein O/H 2 O refers to O or H 2 O, M a comprises an element selected from the Periodic Table of the Elements IUPAC Groups 11, 2, 12, 13, 14, 6, 7 or 8-10 (CAS Groups IB, IIA, IIB, IIIA, IVA, IVB, VIB, VIIB, or VIII); M b comprises an element selected from the Periodic Table of the Elements IUPAC Groups 13, 3, 4, 5, 6, 8-10 (CAS Groups IIIA, IIB, IVB, VB, VIB, or VIII); Ligand′ and Ligand″ are of different bond lengths; n=0−4; x=1; y=1; and z=0−4.
2 . A mixed ligand metal organic framework (ML-MOF) having rectangular grids comprising:
a pillar characterized by the formula (M b F 6-n (O/H 2 O) n ), wherein O/H 2 O refers to O or H 2 O, M b comprises an element selected from the Periodic Table of the Elements IUPAC Groups 13, 3, 4, 5, 6, 8-10 (CAS Groups IIIA, IIIB, IVB, VB, VIB, or VIII) and n=0−4; and
a rectangular grid characterized by the formula (M a (Ligand′) x (Ligand″) y ), wherein Ligand′ and Ligand″ are of different bond lengths, M a comprises an element selected from the Periodic Table of the Elements IUPAC Groups 11, 2, 12, 13, 14, 6, 7 or 8-10 (CAS Groups IB, IIA, IIB, IIIA, IVA, IVB, VIB, VIIB, or VIII), x=1 and y=1;
wherein the rectangular grid and pillar associate to form the metal-organic framework.
3 . A method of fabricating a mixed ligand metal organic framework, the method comprising:
combining a hydrofluoric acid solution, a first metal source, a second metal source, and a solvent, sufficient to form a mixture;
reacting the mixture over a period of time sufficient to form a reacted mixture;
processing the reacted mixture to provide a metal organic framework via pillaring of rectangular grids with a pillar,
wherein the pillar is characterized by the formula (M b F 6-n (O/H 2 O) n ), wherein O/H 2 O refers to O or H 2 O, M b comprises an element selected from the Periodic Table of the Elements IUPAC Groups 13, 3, 4, 5, 6, 8-10 (CAS Groups IIA, IIIB, IVB, VB, VIB, or VIII) and n=0−4, and the rectangular grids are characterized by the formula (M a (Ligand′) x (Ligand″) y ), wherein M a comprises an element selected from the Periodic Table of the Elements IUPAC Groups 11, 2, 12, 13, 14, 6, 7 or 8-10 (CAS Groups IB, IIA, IIB, IIIA, IVA, IVB, VIB, VIIB, or VIII), x=1 and y=1, and Ligand′ and Ligand″ are of different bond lengths.
4 . The ML-MOF as in claim 1 , wherein n=1.
5 . The ML-MOF as in claim 1 , wherein M a is selected from the group consisting of Cu 2+ , Zn 2+ , Co 2+ , Ni 2+ , Mn 2+ , Zr 2+ , Fe 2+ , Ca 2+ , Ba 2+ , Pb 2+ , Pt 2+ , Pd 2+ , Ru 2+ , Rh 2+ , Cd 2+ , Mg 2+ , Al 3+ , Fe 2+ , Fe 3+ , Cr 2+ , Cr 3+ , Ru 2+ , Ru 3+ and Co 3+ .
6 . The ML-MOF as in claim 1 , wherein M b is selected from the group consisting of Al 3+ , Fe 2+ , Fe 3+ , Cr 2+ , Cr 3+ , Ti 3+ , V 3+ , V 5+ , Sc 3+ , In 3+ , Nb 5+ and Y 3+ .
7 . The ML-MOF as in claim 1 , wherein the solvent is selected from the group consisting of water, alcohols including ethanol (EtOH), dimethylformamide (DMF) and diethylformamide (DEF).
8 . The ML-MOF as in claim 1 , wherein the solvent comprises water and ethanol (EtOH).
9 . The ML-MOF as in claim 1 , wherein Ligand′ and Ligand″ are each a different organic, poly-functional, N-donor ligand.
10 . The ML-MOF as in claim 1 , wherein Ligand′ and Ligand″ are each a different bi-functional N-donor linker having aromatic or non-aromatic monocyclic or polycyclic groups.
11 . The ML-MOF as in claim 1 , wherein Ligand′ and Ligand″ are each a different polydentate, or poly-functional ligand including bi-functional ligands, tri-functional ligands, or ligands with four or more functional sites, wherein:
one or both of ligand′ and ligand″ comprise N-donor linkers;
one or both of ligand′ and ligand″ comprise different poly-functional ligands;
one or both of ligand′ and ligand″ comprise a plurality of N-donor functional groups;
one or both of ligand′ and ligand″ comprise an aromatic or non-aromatic nitrogen-containing monocyclic or polycyclic group structure; or
ligand′ and ligand″ comprise two different aromatic or non-aromatic nitrogen-containing heterocyclic ligands.
12 . The ML-MOF as in claim 1 , wherein Ligand′ and Ligand″ are different and wherein one or both of Ligand′ and Ligand″ are or contain one or more nitrogen-containing heterocyclic groups selected from the group consisting of pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, triazole, oxadiazole, thiadiazole, quinoline, benzoxazole, benzimidazole, and tautomers thereof.
13 . The ML-MOF as in claim 1 , wherein Ligand′ and Ligand″ are different and wherein one or both of Ligand′ and Ligand″ are selected from the group consisting of: pyrazine, 4,4′-bipyridine, 4-[2-(pyridin-4-yl)ethynyl]pyridine, 4-[2-(pyridin-4-yl)ethenyl]pyridine, 4-[(1E)-2-(pyridin-4-yl)diazen-1-yl]pyridine, 4-[4-(pyridin-4-yl)phenyl]pyridine, 1,2-Bis(4-pyridyl)ethane, 1H-pyrazole-R-1H-pyrazole, 1H-imidazole-R 1H-imidazole, 1H-1,2,3,4-tetrazole-R-1H-1,2,3,4-tetrazole, 1H-1,2,4-triazole-R-1H-1,2,4-triazole, bis(pyridin-4-yl)-1,2,4,5-tetrazine, 4-(2-{4-[2-(pyridin-4-yl)ethynyl]phenyl}ethynyl)pyridine, 4-(2-{4-[2-(pyridin-4-yl)ethenyl]phenyl}ethenyl)pyridine, 4-(4-{2-[4-(pyridin-4-yl)phenyl]ethynyl}phenyl)pyridine, and 4-[4′-(pyridin-4-yl)-[1,1′-biphenyl]-4-yl]pyridine, wherein R is an aliphatic, aromatic or combination of aliphatic/aromatic bridge.
14 . The ML-MOF as in claim 1 , wherein Ligand′ and Ligand″ are different and wherein one or both of Ligand′ and Ligand″ have the general structure H(a)-A-L-B—H(b), wherein:
A and B can be the same or different groups containing donor atoms that bond to M a , H(a) and H(b);
each of the H(a) and H(b) are the same or different heteroatoms selected from the group consisting of N and S; and
L is a link between A and B that is one or more selected from the group consisting of: single, double or triple bonds; alkyl, alkenyl or alkynyl groups with 1-100 C atoms; aromatic or non-aromatic cyclic groups, including phenyl groups; diazene groups; tetrazine; a combination of one or more alkenyl groups and one or more phenyl groups; and a combination of one or more alkynyl groups and one or more phenyl groups.
15 . The ML-MOF as in claim 14 , wherein A and/or B are selected from the group consisting of pyridine, pyrazole, imidazole, tetrazole and triazole.
16 . The ML-MOF as in claim 1 , wherein Ligand′ comprises pyrazine and Ligand″ comprises 4,4-bipyridine.
17 . A method of using the ML-MOF of claim 1 for capturing carbon dioxide from a fluid composition, comprising:
contacting the ML-MOF of claim 1 with a fluid composition including at least carbon dioxide; and
capturing carbon dioxide from the fluid composition.
18 . The ML-MOF as in claim 2 , wherein Ligand′ and Ligand″ are different and wherein one or both of Ligand′ and Ligand″ have the general structure H(a)-A-L-B—H(b), wherein:
A and B can be the same or different groups containing donor atoms that bond to M a , H(a) and H(b);
each of the H(a) and H(b) are the same or different heteroatoms selected from the group consisting of N and S; and
L is a link between A and B that is one or more selected from the group consisting of: single, double or triple bonds; alkyl, alkenyl or alkynyl groups with 1-100 C atoms; aromatic or non-aromatic cyclic groups, including phenyl groups; diazene groups; tetrazine; a combination of one or more alkenyl groups and one or more phenyl groups; and a combination of one or more alkynyl groups and one or more phenyl groups.
19 . The ML-MOF as in claim 18 , wherein A and/or B are selected from the group consisting of pyridine, pyrazole, imidazole, tetrazole and triazole.
20 . The ML-MOF as in claim 2 , wherein Ligand′ comprises pyrazine and Ligand″ comprises 4,4-bipyridine.