Overcoming two carbon dioxide adsorption steps in diamine-appended metal-organic frameworks
Primary, secondary (1º,2º) alkylethylenediamine- and alkylpropylenediamine-appended variants of metal-organic framework are provided for CO 2 capture applications. Increasing the size of the alkyl group on the secondary amine enhances the stability to diamine volatilization from the metal sites. Two-step adsorption/desorption profiles are overcome by minimizing steric interactions between adjacent ammonium carbamate chains. For instance, the isoreticularly expanded framework Mg 2 (dotpdc) (dotpdc 4− =4,4″-dioxido-[1,1′:4′,1″-terphenyl]-3,3″-dicarboxylate), yields diamine-appended adsorbents displaying a single CO 2 adsorption step. Further, use of the isomeric framework Mg-IRMOF-74-II or Mg 2 (pc-dobpdc) (pc-dobpdc 4− =3,3-dioxidobiphenyl-4,4-dicarboxylate, pc=para-carboxylate) also leads to a single CO 2 adsorption step with bulky diamines. By relieving steric interactions between adjacent ammonium carbamate chains, these frameworks enable step-shaped CO 2 adsorption, decreased water co-adsorption, and increased stability to diamine loss. Variants of Mg 2 (dotpdc) and Mg 2 (pc-dobpdc) functionalized with large diamines such as N-(n-heptyl)ethylenediamine have utility as adsorbents for carbon capture applications.
1. An adsorption material, comprising:
a metal-organic framework comprising a plurality of metal ions and a plurality of polytopic organic linkers, wherein each polytopic organic linker in the plurality of polytopic organic linkers is connected to at least two metal ions of the plurality of metal ions; and
a plurality of ligands, wherein each respective ligand in the plurality of ligands is amine appended to at least one metal ion in the plurality of metal ions of the metal-organic framework, each respective ligand in the plurality of ligands comprising:
wherein,
X is a metal ion of the metal-organic framework,
Z is carbon, silicon, germanium, sulfur, or selenium,
Q is carbon, silicon, germanium, sulfur, or selenium,
R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , and R 8 are each independently selected from H, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocycloalkyl, and
R 6 is substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocycloalkyl, wherein R6 comprises at least three non-hydrogen atoms,
each polytopic organic linker in the plurality of polytopic organic linkers has the formula:
and wherein,
R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl.
2. The adsorption material of claim 1 , wherein each metal ion (X) in the plurality of metal ions is Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, or Zn.
3. The adsorption material of claim 1 , wherein R 6 is substituted or unsubstituted alkyl having between three and ten carbon atoms.
4. The adsorption material of claim 1 , wherein R 6 is an n-alkane with between three and ten carbon atoms.
5. The adsorption material of claim 4 , wherein R 6 is propyl, butyl, pentyl, hexyl, or heptyl.
6. The adsorption material of claim 1 , wherein R 6 is a branched-chain alkane.
7. The adsorption material of claim 1 , wherein R 6 is a substituted or unsubstituted heterocycloalkyl.
8. The adsorption material of claim 1 , wherein R 6 is a cycloalkane.
9. The adsorption material of claim 1 , wherein R 6 is substituted or unsubstituted cyclopropane, cyclobutane, cylopentane, or cyclohexane.
10. The adsorption material of claim 1 , wherein R 1 is hydrogen.
11. The adsorption material of claim 1 , wherein
each respective ligand in the plurality of ligands comprises:
R 2 , R 3 , R 4 , and R 5 are each hydrogen, and
Z and Q are each carbon.
12. The adsorption material of claim 1 , wherein each metal ion (X) in the plurality of metal ions is Mg.
13. The adsorption material of claim 1 , wherein each ligand in the plurality of ligands is N-(n-heptyl)ethylenediamine.
14. The adsorption material of claim 1 , wherein the polytopic organic linker is 3,3′-dioxidobiphenyl-4,4′-dicarboxylate (para-carboxylate-dobpdc 4− ).
15. The adsorption material of claim 1 , wherein the adsorption material exhibits a single CO 2 adsorption step upon CO 2 adsorption.
16. The adsorption material of claim 1 , wherein the adsorption material exhibits a single CO 2 desorption step upon CO 2 desorption.
17. The adsorption material of claim 1 , wherein the adsorption material has a 77 K N 2 Brunauer-Emmett-Teller (BET) surface area of at least 3050 m 2 /g.
18. The adsorption material of claim 1 , wherein the adsorption material has a Langmuir surface area of at least 5800 m 2 /g.
19. The adsorption material of claim 1 , wherein the crystallographic density of the adsorption material is between 0.4 g/cm 3 and 1.2 g/cm 3 .
20. The adsorption material of claim 1 , wherein
each respective ligand in the plurality of ligands comprises:
R 6 has a molecular weight of 44 g/mol or greater.
21. The adsorption material of claim 1 , wherein
each respective ligand in the plurality of ligands comprises:
R 6 has a molecular weight of 58 g/mol or greater.
22. The adsorption material of claim 1 , wherein
each respective ligand in the plurality of ligands comprises:
R 6 has a molecular weight of 72 g/mol or greater.
23. The adsorption material of claim 1 , wherein
each respective ligand in the plurality of ligands comprises:
R 6 has a molecular weight of 86 g/mol or greater.
24. The adsorption material of claim 1 , wherein
each respective ligand in the plurality of ligands comprises:
R 6 has a molecular weight of between 72 g/mol and 500 g/mol.
25. The adsorption material of claim 1 , wherein
each respective ligand in the plurality of ligands comprises:
R 6 has a molecular weight of between 58 g/mol and 400 g/mol.
26. The adsorption material of claim 1 , wherein
each respective ligand in the plurality of ligands comprises:
R 6 has a molecular weight of between 44 g/mol and 300 g/mol.