Rapid and enhanced activation of microporous coordination polymers by flowing supercritical CO
Flowing supercritical CO 2 is used to activate metal organic framework materials (MOF). MOFs are activated directly from N,N-dimethylformamide (DMF) thus avoiding exchange with a volatile solvent. Most MCPs display increased surface areas directly after treatment although those with coordinatively unsaturated metal centers benefit from additional heating.
1. A method for treating a solvent-containing metal organic framework material (MOF) to increase its internal surface area or porosity, comprising introducing a composition consisting of CO 2 into a vessel containing the solvent-containing MOF, while venting the CO 2 and maintaining supercritical conditions for carbon dioxide in the vessel.
2. The method of claim 1 wherein the solvent is not miscible in supercritical CO 2 .
3. The method of claim 1 where the solvent is the solvent of synthesis of the MOF.
4. The method of claim 3 , wherein the solvent is selected from the group consisting of diethylformamide and dimethylformamide.
5. The method of claim 3 wherein the material is treated directly after synthesis without exchanging the solvent of synthesis.
6. The method of claim 1 comprising venting the CO 2 while maintaining sufficient pressure for liquid CO 2 to be present in the vessel.
7. The method of claim 1 wherein introducing CO 2 into the vessel comprises adding gaseous CO 2 at a pressure at which it forms liquid CO 2 , continuing to add CO 2 until the vessel is full of liquid CO 2 , and then raising the temperature and/or pressure to achieve supercritical conditions for CO 2 .
8. The method of claim 1 further comprising venting the CO 2 while maintaining conditions for liquid CO 2 in the vessel.
9. A method according to claim 1 , wherein the MOF material is made by reacting a metal cation with an organic linker selected from:
4,4′,4″-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE),
biphenyl-4,4′-dicarboxylate (BPDC),
benzene-1,3,5-tris(1H-tetrazole) (BTT),
4,4′-bipyridine,
2-Methylimidazole, and
Imidazole.
10. A method according to claim 9 , wherein the metal is selected from Zn 2+ , Cu 2+ , Mg 2+ , Ni 2+ , Co 2+ , and Mn 2+ .
11. A method of making a porous material, comprising:
a) combining a metal salt and an organic linker in a solvent or solvents of reaction in which both are soluble,
b) exposing the combined metal salt and organic linker to conditions under which they react to form a porous material comprising a metal-organic framework,
c) obtaining crystals of the porous material from the reaction mixture of step b), wherein the crystals comprise the metal-organic framework material and occluded solvent of reaction, and
d) exposing the crystals to a composition consisting of flowing supercritical carbon dioxide to remove occluded solvent from the crystals and provide an activated material.
12. A method according to claim 11 , wherein the linker comprises two or more carboxyl groups attached to an aromatic ring of the linker.
13. A method according to claim 11 , wherein the linker comprises two or more nitrogen-containing aromatic rings.
14. A method according to claim 11 , wherein the occluded solvent is not miscible in supercritical carbon dioxide.
15. A method according to claim 11 , further comprising exchanging the reaction solvent with a second solvent before exposing the material to flowing supercritical carbon dioxide.
16. A method according to claim 11 , wherein the solvent or solvents of reaction are not exchanged with another solvent prior to exposure to flowing supercritical carbon dioxide.
17. A method according to claim 11 , wherein the metal salt comprises a salt of Zn 2+ ,Cu 2+ , Mn 2+ , or Mg 2+ .
18. A method according to claim 11 , wherein the linker is selected from the group consisting of
4,4′,4″-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE),
biphenyl-4,4′-dicarboxylate (BPDC),
benzene-1,3,5-tris(1H-tetrazole) (BTT),
4,4′-bipyridine,
2-Methylimidazole, and
Imidazole.
19. A method of making and activating a porous material comprising a metal organic framework (MOF), comprising
reacting a metal cation selected from Zn 2+ , Cu 2+ , Mg 2+ , Ni 2+ , Co 2+ , Mn 2+ with an organic linker composition in a solvent to form a MOF material having occluded solvent of synthesis,
optionally exposing the MOF material to a second solvent to exchange out the solvent of synthesis, and
drying the MOF material by exposing the MOF material containing either the solvent of synthesis or the second solvent to conditions of flowing supercritical carbon dioxide to make the activated porous material.
20. A method for the treatment of a solvent-containing metal organic framework material (MOF) to increase its internal surface area or porosity, comprising introducing CO 2 into a vessel containing the solvent-containing MOF, and venting the CO 2 while maintaining conditions for liquid carbon dioxide in the vessel.