Method for the capture of carbon dioxide using oxyfluoride physisorbents
Metal-organic frameworks (MOFs) comprising square arrays of nickel cationic centers linked by N-donor organic ligands and pillared with tungsten oxyfluoride anion are described. In an exemplary MOF, the N-donor organic ligands are pyrazine and the MOF has a pore size of less than about 7 angstroms. Methods of using the MOF to selectively capture carbon dioxide, e.g., from gas compositions comprising nitrogen and/or methane, are also described.
1 . A metal-organic framework (MOF) comprising a plurality of molecular building units having the formula [Ni(L) 2 (WO 2 F 4 )], wherein each L is a bidentate organic ligand comprising two N-donor functional groups.
2 . The MOF of claim 1 , wherein each L comprises one or more N-containing heterocyclic groups.
3 . The MOF of claim 2 , wherein each L is pyrazine and the MOF comprises a plurality of molecular building units having the formula [Ni(pyrazine) 2 (WO 2 F 4 )].
4 . A method of removing carbon dioxide (CO 2 ) from a fluid, the method comprising:
(a) providing a metal-organic framework (MOF), the MOF comprising a plurality of molecular building units having the formula [Ni(L) 2 (WO 2 F 4 )], wherein each L is a bidentate organic ligand comprising two N-donor functional groups;
(b) contacting the MOF with a fluid composition comprising CO 2 and one or more other chemical species; and
(c) selectively capturing the CO 2 from the fluid composition.
5 . The method of claim 4 , wherein the MOF comprises a plurality of molecular building units having the formula [Ni(pyrazine) 2 (WO 2 F 4 )].
6 . The method of claim 4 , wherein the one or more other chemical species comprise nitrogen (N 2 ), water, oxygen (O 2 ), and/or methane (CH 4 ).
7 . The method of claim 4 , wherein the fluid is a gas comprising about 50% by volume CO 2 or less.
8 . The method of claim 7 , wherein the fluid is a gas comprising about 15% by volume CO 2 or less.
9 . The method of claim 8 , wherein the fluid is a gas comprising about 4% by volume CO 2 or less.
10 . The method of claim 4 , where the fluid is air comprising about 400 ppm CO 2 .
11 . The method of claim 4 , wherein capturing the CO 2 occurs selectively over one or more of water, N 2 , O 2 , and CH 4 .
12 . The method of claim 4 , wherein the MOF is regenerated after step (c) via heating and reused to capture additional CO 2 .
13 . The method of claim 4 , wherein the MOF is regenerated after step (c) via vacuum and reused to capture additional CO 2 .
14 . The method of claim 4 , wherein the MOF is regenerated after step (c) via vacuum and heating and reused to capture additional CO 2 .