Iron metal organic framework materials
The invention relates to an improved process for preparing metal-organic framework materials, metal-organic frameworks obtainable by such processes, methods using the same, and the use thereof. The process of the invention provides an improved process for preparing metal-organic frameworks in particular monocrystalline metal-organic frameworks having large crystal sizes. The invention also relates to metal organic frameworks comprising iron or titanium, and their uses.
1. A single crystal iron metal-organic framework, the metal organic framework comprising at least one metal-ligand cluster comprising a metal cluster and one or more ligands having two or more carboxylate groups;
wherein the metal cluster has the formula Fe 2 XO, where X is a metal ion selected from the group consisting of Fe, Co, Mn, Zn, Ni, Mg, Cu, and Ca;
wherein the single crystal has a size greater than or equal to 10 μm; the metal organic framework comprises cavities having a free diameter of about 4 to about 40 Å; and the metal organic framework comprises pores having a pore volume of from about 0.1 cm 3 /g to about 4 cm 3 /g.
2. The single crystal iron metal-organic framework of claim 1 , wherein the crystal is monocrystalline or polycrystalline.
3. The single crystal metal-organic framework according to claim 1 , having a Brunauer-Emmett-Teller (BET) specific surface area of at least 200 m 2 /g.
4. The single crystal metal-organic framework according to claim 1 , having a surface area of less than or equal to 8000 m 2 /g.
5. The single crystal metal-organic framework according to claim 1 , the metal-organic framework comprising cavities having a free diameter of from about 5 Å to about 25 Å.
6. The single crystal metal-organic framework according to claim 1 , the metal-organic framework comprising pores having a pore volume from about 0.2 cm 3 /g to about 3 cm 3 /g.
7. The single crystal metal-organic framework according to claim 1 , having a size greater than or equal to 20 μm.
8. The single crystal metal-organic framework according to claim 1 , having a crystal size from 10 μm to about 2000 μm.
9. The single crystal metal-organic framework according to claim 1 , wherein the one or more ligands are derived from a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, a hexacarboxylic acid, or a octacarboxylic acid.
10. The single crystal metal-organic framework according to claim 1 , wherein each metal cluster is coordinated with 4, 5, or 6 ligands.
11. The single crystal of a metal-organic framework according to claim 1 , wherein the at least one metal ion is Fe(II) or Fe(III).
12. The single crystal of a metal-organic framework according to claim 1 , wherein the metal cluster has a formula Fe 3 O.
13. A process for preparing the single crystal iron metal-organic framework of claim 1 , the process comprising:
reacting a starting compound of formula M 3 O(CH 3 COO) 6 with a ligand precursor having at least two carboxylic acid groups in the presence of acetic acid to provide a metal-organic framework comprising a M 3 O cluster where at least one (CH 3 COO) ligand is replaced by at least one ligand having at least two carboxylate groups; wherein M 3 has the formula Fe 2 X, where X is a metal ion selected from the group consisting of Fe, Co, Mn, Zn, Ni, Mg, Cu, and Ca.
14. The process according to claim 13 , wherein the starting compound has a formula Fe 2 MO(CH 3 COO) 6 or Fe 3 O(CH 3 COO) 6 , where M is Co, Mn, Zn, or Ni.