Green methods for preparing highly CO2 selective and H2S tolerant metal organic frameworks

1. A method of preparing a metal-organic framework, comprising:

grinding a metal node precursor with a ligand precursor to form a mixture of precursors, wherein the ligand precursor includes one or more of pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, oxadiazole, thiadiazole, quinoline, benzoxazole, benzimidazole, 1,4-Diazabicyclo[2.2.2]octane, 1,2-bis(4-pyridyl)acetylene, and tautomers thereof;

wetting the mixture of precursors with one or more drops of water; and

heating the wetted mixture to an activation temperature to obtain a metal-organic framework.

2. The method of claim 1 , wherein the metal node precursor includes a metal selected from the group consisting of Ni, Cu, Zn, Fe, and Co.

3. The method of claim 1 , wherein the metal node precursor includes M-SiF 6 , wherein M includes a metal selected from the group consisting of Ni, Cu, Zn, Fe, and Co.

4. The method of claim 1 , wherein the ligand precursor is present in stoichiometric excess of the metal node precursor.

5. The method of claim 1 , wherein the activation temperature includes temperatures up to about 45° C.

6. The method of claim 1 , wherein the activation temperature includes temperatures up to about 120° C.

7. The method of claim 1 , wherein the metal-organic framework is a two-dimensional metal organic framework.

8. The method of claim 1 , wherein the metal-organic framework is a three-dimensional metal-organic framework.

9. The method of claim 1 , wherein the metal node precursor is a solid metal node precursor and the ligand precursor is a solid ligand precursor.

10. A method comprising contacting a metal-organic framework according to claim 1 with a fluid composition comprising CO 2 , and sorbing the CO 2 from the fluid composition using the metal-organic framework.

11. The method of claim 10 , wherein the fluid composition further comprises one or more of H 2 S, N 2 , O 2 , CH 4 , and H 2 .

12. A method comprising contacting a metal-organic framework according to claim 1 with a fluid composition comprising H 2 S, and sorbing the H 2 S from the fluid composition using the metal-organic framework.

13. The method of claim 12 , wherein the fluid composition further comprises one or more of CO 2 , N 2 , O 2 , CH 4 , and H 2 .

14. A method of preparing a metal-organic framework, comprising:

mixing a metal node precursor with a ligand precursor to form a mixture, wherein the metal node precursor includes CoSiF 6

adding water to the mixture; and

heating the mixture to an activation temperature to obtain a metal-organic framework.

15. The method of claim 14 , wherein the ligand precursor includes one or more of pyridine, 4,4′-Bipyridin, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, triazole, oxadiazole, thiadiazole, quinoline, benzoxazole, benzimidazole, 1,4-Diazabicyclo[2.2.2]octane, 1,2-bis(4-pyridyl)acetylene, and tautomers thereof.

16. The method of claim 14 , wherein the ligand precursor is present in stoichiometric excess of the metal node precursor.

17. A method of preparing a metal-organic framework, comprising:

mixing a metal node precursor with a ligand precursor to form a mixture, wherein the metal node precursor includes FeSiF 6 ;

adding water to the mixture; and

heating the mixture to an activation temperature to obtain a metal organic framework.

18. The method of claim 17 , wherein the ligand precursor includes one or more of pyridine, 4,4′-Bipyridin, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, triazole, oxadiazole, thiadiazole, quinoline, benzoxazole, benzimidazole, 1,4-Diazabicyclo[2.2.2]octane, 1,2-bis(4-pyridyl)acetylene, and tautomers thereof.

19. The method of claim 17 , wherein the ligand precursor is present in stoichiometric excess of the metal node precursor.