Metal-organic materials (MOMs) for adsorption of polarizable gases and methods of using MOMs

1. A metal-organic material (MOM), comprising:

[M(L) 2 P] n , wherein [M(L) 2 P] n has a 6-connected 4 8 .6 7 topology net, wherein M 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+ , Cs 2+ , Pb 2+ , Pt 2+ , Pd 2+ , Ru 2+ , Rh 2+ , Cd 2+ , Mg +2 , Al +3 , Fe +3 , Cr 3+ , Ru 3+ and Co 3+ , wherein L is a bifunctional N donor group that serves as a linker, and P is an oxyanion with angular geometry, and wherein n is 1 to 10 18 .

2. The MOM of claim 1 , wherein L is selected from the group consisting of: a dipyridyl-based linker, a pyrazolate-based linker, an imidazolate-based linker, tetrazolate-based linker and a triazolate-based linker.

3. The MOM of claim 1 , wherein P is selected from the group consisting of: CrO 4 2− , MoO 4 2− , WO 4 2− , SO 4 2− , TiO 4 2− , SeO 4 2− , CO 3 2− , SO 3 2− , SiO 3 2− , ZrO 3 2− , Cr 2 O 7 2− , Mo 2 O 7 2− , S 2 O 3 2− , S 2 O 6 2 , S 2 O 8 2− , Ti 3 O 7 2− , PO 4 2− , VO 4 2− , AsO 4 2− , PO 3 3− , BO 3 3− , and AsO 3 3− .

4. The MOM of claim 1 , wherein [M(L) 2 P] n is represented by [M(L) 2 (M′O 4 )] n , wherein [M(g) 2 (M′O 4 )] n wherein M′ 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+ , Cs 2+ , Pb 2+ , Pt 2+ , Pd 2+ , Ru 2+ , Rh 2+ , Cd 2+ , Mg +2 , Al +3 , Fe +3 , Cr 3+ , Ru 3+ , and Co 3+ , and

wherein L is selected from the group consisting of: (1) pyrazine, (2) 4,4′-bipyridine, (3) 4,4′-azo-bis(pyridine), (4) 1,2-bis(4-pyridyl)ethene, (5) 1,2-bis(4-pyridyl)ethane, (6) 1,2-di(pyridine-4-yl)ethane-1,2-diol, (7) 3-[(trimethylsilyl)ethynyl]-4-[2-(4-pyridinyl)ethenyl]pyridine, (8) 1,2-bis(4-pyridyl)ethyne, (9) 1,4-bis(4 pyridyl)benzene, (10) 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine, (11) 4-(9-(pyridin-4-yl)anthracen-10-yl)pyridine, (12) 4,4′-bis(4-pyridyl)biphenyl, (13) N,N′-bis(4-pyridyl)pyromellitic diimide, (14) N,N′-di(pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide, (15) 4,4′-bipyrazolyl, (16) 1,4-bis(1H-pyrazol-4-yl)benzene, (17) 4,4′-buta-1,3-diyne-1,4-diylbis(1H-pyrazole), (18) N,N′-bis(1H-pyrazol-4-yl)pyromellitic diimide, (19) N,N′-bis(1H-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxydiimide, (20) 4,4′-bis(1H-pyrazol-4-yl)biphenyl, (21) N,N′-bis(1H-pyrazol-4-yl)-1,4-benzenedicarboxamide, (22) 4,4′-benzene-1,4-diylbis(1H-pyrazole), (23) Imidazole, (24) 2-methylimidazole, (25) 2-ethylimidazole, (26) 2-nitroimidazole, (27) benzimidazole, (28) purine, (29) 1,4-bis(1-imidazolyl)benzene, (30) 9,10-(1-imidazolyl)anthracene, (30) 4,4′-bis(1-imidazolyl)biphenyl, (32) tetrakis(1-Imidazolyl)borate, (33) 1,2,4-triazol, (34) 4,4′-bis-1,2,4-triazol, (35) 4,4′-azo-1,2,4-triazol, (36) 1,3-bis(1,2,4-triazol-1-yl)-propane, (37) 1,4-bis(1,2,4-triazol-1-yl)-butane, (38) 1,4-bis(1,2,4-triazol-1-ylmethyl)-benzene, and (39) 4,4′-bis(1,2,4-triazol-1-ylmethyl)-1,1′-biphenyl.

5. The MOM of claim 1 , comprising:

[M(L) 2 P] n , wherein [M(L) 2 P] n has a 6-connected 4 8 .6 7 topology net, wherein M is Co or Ni, wherein L is a bifunctional N donor group that serves as a linker, and P is an oxyanion with angular geometry, and wherein n is 1 to 10 18 ,

wherein [M(L) 2 P] n is represented by [M(L) 2 (M′O 4 )] n , wherein [M(g) 2 (M′O 4 )] n wherein M′ is Mo, W, or Cr, and

wherein L is selected from the group consisting of: (1) pyrazine, (2) 4,4′-bipyridine, (3) 4,4′-azo-bis(pyridine), (4) 1,2-bis(4-pyridyl)ethene, (5) 1,2-bis(4-pyridyl)ethane, (6) 1,2-di(pyridine-4-yl)ethane-1,2-diol, (7) 3-[(trimethylsilyl)ethynyl]-4-[2-(4-pyridinyl)ethenyl]pyridine, (8) 1,2-bis(4-pyridyl)ethyne, (9) 1,4-bis(4 pyridyl)benzene, (10) 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine, (11) 4-(9-(pyridin-4-yl)anthracen-10-yl)pyridine, (12) 4,4′-bis(4-pyridyl)biphenyl, (13) N,N′-bis(4-pyridyl)pyromellitic diimide, (14) N,N′-di(pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide, (15) 4,4′-bipyrazolyl, (16) 1,4-bis(1H-pyrazol-4-yl)benzene, (17) 4,4′-buta-1,3-diyne-1,4-diylbis(1H-pyrazole), (18) N,N′-bis(1H-pyrazol-4-yl)pyromellitic diimide, (19) N,N′-bis(1H-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxydiimide, (20) 4,4′-bis(1H-pyrazol-4-yl)biphenyl, (21) N,N′-bis(1H-pyrazol-4-yl)-1,4-benzenedicarboxamide, (22) 4,4′-benzene-1,4-diylbis(1H-pyrazole), (23) Imidazole, (24) 2-methylimidazole, (25) 2-ethylimidazole, (26) 2-nitroimidazole, (27) benzimidazole, (28) purine, (29) 1,4-bis(1-imidazolyl)benzene, (30) 9,10-(1-imidazolyl)anthracene, (30) 4,4′-bis(1-imidazolyl)biphenyl, (32) tetrakis(1-Imidazolyl)borate, (33) 1,2,4-triazol, (34) 4,4′-bis-1,2,4-triazol, (35) 4,4′-azo-1,2,4-triazol, (36) 1,3-bis(1,2,4-triazol-1-yl)-propane, (37) 1,4-bis(1,2,4-triazol-1-yl)-butane, (38) 1,4-bis(1,2,4-triazol-1-ylmethyl)-benzene, and (39) 4,4′-bis(1,2,4-triazol-1-ylmethyl)-1,1′-biphenyl.

6. The MOM of claim 1 , comprising:

[M(L) 2 P] n , wherein [M(L) 2 P] n has a 6-connected 4 8 .6 7 topology net, wherein M is Co or Ni, wherein L is a bifunctional N donor group that serves as a linker, and P is an oxyanion with angular geometry, and wherein n is 1 to 10 18 ,

wherein [M(L) 2 P] n is represented by [M(L) 2 (M′O 4 )] n , wherein [M(q) 2 (M′O 4 )] n wherein M′ is Mo, W, or Cr, and

wherein L is selected from the group consisting of: (1) pyrazine, (2) 4,4′-bipyridine, (3) 4,4′-azo-bis(pyridine), (4) 1,2-bis(4-pyridyl)ethene, (5) 1,2-bis(4-pyridyl)ethane, (6) 1,2-di(pyridine-4-yl)ethane-1,2-diol, (7) 3-[(trimethylsilyl)ethynyl]-4-[2-(4-pyridinyl)ethenyl]pyridine, (8) 1,2-bis(4-pyridyl)ethyne, (9) 1,4-bis(4 pyridyl)benzene, (10) 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine, (11) 4-(9-(pyridin-4-yl)anthracen-10-yl)pyridine, (12) 4,4′-bis(4-pyridyl)biphenyl, (13) N,N′-bis(4-pyridyl)pyromellitic diimide, (14) N,N′-di(pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide, (15) 4,4′-bipyrazolyl, (16) 1,4-bis(1H-pyrazol-4-yl)benzene, (17) 4,4′-buta-1,3-diyne-1,4-diylbis(1H-pyrazole), (18) N,N′-bis(1H-pyrazol-4-yl)pyromellitic diimide, (19) N,N′-bis(1H-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxydiimide, (20) 4,4′-bis(1H-pyrazol-4-yl)biphenyl, (21) N,N′-bis(1H-pyrazol-4-yl)-1,4-benzenedicarboxamide, (22) 4,4′-benzene-1,4-diylbis(1H-pyrazole), (23) Imidazole, (24) 2-methylimidazole, (25) 2-ethylimidazole, (26) 2-nitroimidazole, (27) benzimidazole, (28) purine, (29) 1,4-bis(1-imidazolyl)benzene, (30) 9,10-(1-imidazolyl)anthracene, (30) 4,4′-bis(1-imidazolyl)biphenyl, (32) tetrakis(1-Imidazolyl)borate, (33) 1,2,4-triazol, (34) 4,4′-bis-1,2,4-triazol, (35) 4,4′-azo-1,2,4-triazol, (36) 1,3-bis(1,2,4-triazol-1-yl)-propane, (37) 1,4-bis(1,2,4-triazol-1-yl)-butane, (38) 1,4-bis(1,2,4-triazol-1-ylmethyl)-benzene, and (39) 4,4′-bis(1,2,4-triazol-1-ylmethyl)-1,1′-biphenyl, and

wherein the MOM is selected from the group consisting of: [Co(bpe) 2 (CrO 4 )], [Ni(bpe) 2 (CrO 4 )] n , [Ni(bpa) 2 (CrO 4 )] n , [Ni(zbp) 2 (CrO 4 )] n , [Ni(bpb) 2 (CrO 4 )] n , [Co(bpe) 2 (MoO 4 )] n , [Ni(bpe) 2 (MoO 4 )] n , [Ni(bpa) 2 (MoO 4 )] n , [Ni(zbp) 2 (MoO 4 )] n , [Ni(bpb) 2 (MoO 4 )] n , [Co(bpe) 2 (WO 4 )] n , [Ni(bpe) 2 (WO 4 )] n , [Co(bpa) 2 (WO 4 )] n , and [Ni(bpa) 2 (WO 4 )] n .

7. The MOM of claim 1 , comprising:

[M(L) 2 P] n , wherein [M(L) 2 P] n has a 6-connected 4 8 .6 7 topology net, wherein M 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+ , Cs 2+ , Pb 2+ , Pt 2+ , Pd 2+ , Ru 2+ , Rh 2+ , Cd 2+ , Mg +2 , Al +3 , Fe +3 , Cr 3+ , Ru 3+ and Co 3+, wherein L is a bifunctional N donor group that serves as a linker, and P is an oxyanion with angular geometry, and wherein n is 1 to 10 18 , and

wherein L is selected from: 1,2-bis(4-pyridyl)ethene (bpe), 1,2-bis(4-pyridyl)ethane (bpa), 4,4′-azopyridine (zbp), or 1,4-bis(4-pyridyl)benzene (bpb).

8. A method of capturing a polarizable gas in a gas, comprising:

exposing the gas to a [M(L) 2 P] n , wherein [M(L) 2 P] n has a 6-connected 4 8 .6 7 topology net, wherein M 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+ , Cs 2+ , Pb 2+ , Pt 2+ , Pd 2+ , Ru 2+ , Rh 2+ , Cd 2+ , Mg +2 , Al +3 , Fe +3 , Cr 3+ , Ru 3+ and Co 3+ , wherein L is a bifunctional N donor group that serves as a linker, and P is an oxyanion with angular geometry, wherein n is 1 to 10 18 ; and capturing the polarizable gas in the [M(L) 2 P] n , wherein the polarizable gas is removed from the gas after the exposure to the MOM to form a modified gas.

9. The method of claim 8 , wherein the polarizable gas is CO 2 , wherein the gas includes at least one of the following gases: N 2 , H 2 , and CH 4 , wherein the [M(L) 2 P] n has a greater relative affinity for CO 2 over each one of N 2 , H 2 , and CH 4 .

10. A method of separating components in a gas, comprising:

exposing a gas including a first component and a second component to a metal-organic material (MOM), wherein the MOM includes a [M(L) 2 P] n , wherein [M(L) 2 P] n has a 6-connected 4 8 .6 7 topology net, wherein M 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+ , Cs 2+ , Pb 2+ , Pt 2+ , Pd 2+ , Ru 2+ , Rh 2+ , Cd 2+ , Mg +2 , Al +3 , Fe +3 , Cr 3+ , Ru 3+ and Co 3+ , wherein L is a bifunctional N donor group that serves as a linker, and P is an oxyanion with angular geometry, wherein n is 1 to 10 18 , wherein the MOM has a greater relative affinity for the first component over a second component; and capturing the first component in the MOM.

11. The method of claim 10 , wherein the first component is CO 2 and the second component is N 2 .

12. The method of claim 10 , wherein the first component is CO 2 and the second component is H 2 .

13. The method of claim 10 , wherein the first component is CO 2 and the second component is CH 4 .