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1. (WO2017155475) SILVER-DECORATED METAL-ORGANIC FRAMEWORK FOR OLEFIN/ALKANE SEPARATION
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Claims

1. A porous metal-organic framework comprising

- a Hafnium or Zirconium metal;

- an aromatic compound substituted with at least one carboxylate and optionally with at least one functional group selected from F, CF3, NH2, NO2, O", S", COO", SO2" and PO3"; and

- a silver cation complexed to the aromatic compound.

2. The porous metal-organic framework of claim 1, wherein the substituted aromatic compound is selected from benzene, 1, 3, 5-triphenyl-benzene, benzo-tris-thiophene, triazine, 2, 4, 6-tribenzene, 1, 3, 5, -trinaphthyl benzene.

3. The porous metal-organic framework of claim 1 or 2, wherein the substituted aromatic compound is selected from a compound re resented as Formula (I):


Figure (I)

wherein m is an integer selected from 1 to 3;

n is an integer selected from 0 to 4;

wherein m + n <6; and

FG is a functional group as defined above.

4. The porous metal-organic framework of any one of claims 1 to 3, wherein the functional group is anionic, optionally selected from the group consisting of O", S", COO", SO2" and PO3-.

5. The porous metal-organic framework of any one of claims 1 to 4, wherein the substituted aromatic compound is selected from a compound represented as Formula (la):


Formula (la)

wherein n and FG is as defined above.

The porous metal-organic framework of any one of claims 1 to 4, wherein the substituted aromatic compound is selected from a compound represented as Formula (lb):

"OOC. ^ oo-

Formula (lb)

wherein n is an integer from 0 to 3 and FG is as defined above.

7. The porous metal-organic framework of any one of claims 1 to 5, wherein the substituted aromatic compound is selected from 2-sulfo terephthalic acid.

8. The porous metal-organic framework of any one of claims 1 to 7, wherein the silver cation has an oxidation state of Ag(I), optionally

wherein the silver cation is present in about 5-30 atomic %, preferably in about 8-20 atomic%, more preferably in about 10-15 atomic % of the aromatic compound.

9. The porous metal-organic framework of any one of claims 1 to 8, wherein the porous metal-organic framework has a surface area of not exceeding 1,500 cm2 g"1, optionally wherein the porous metal-organic framework has a surface area of about 500 - 1,500 cm2 g"1, preferably of about 800 - 1,400 cm2 g"1, more preferably of about 1,000 - 1,200 cm2 g"

1

10. The porous metal-organic framework of any one of claims 1 to 9, wherein the porous metal-organic framework is crystalline.

11. A method for preparing a porous metal-organic framework of any one of claims 1-10, comprising

i) dissolving an aromatic compound, substituted with at least one carboxylic acid and optionally at least one functional group selected from F, CF3, NH2, NO2, O", S", COO", SO2" and PO3", and a zirconium or hafnium salt in a solvent mixture of water and an organic acid, heating the solution to a temperature of 50-200°C for 12-60 h to obtain a solid,

ii) suspending the obtained solid and a silver salt in a solvent mixture of water and an organic solvent.

12. The method of claim 11, wherein the aromatic compound is selected from a compound represented as Formula (II):


Figure (II)

wherein m is an integer selected from 1 to 3;

n is an integer selected from 0 to 4;

wherein m + n <6; and

FG is a functional group as defined in any one of claims 2 to 7.

13. The method of claim 11, wherein the halogen of the zirconium or hafnium salt is a halogen salt, preferably a chloride salt, optionally

wherein the zirconium or hafnium of the zirconium or hafnium salt has an oxidation state of +4.

14. The method of any one of claims 11 to 13, wherein the organic acid is acetic acid.

15. The method of any one of claims 11 to 14, wherein after step i) the obtained solid is washed with an organic solvent, preferably an alcohol, more preferably methanol.

16. The method of any one of claims 11 to 15, wherein in step ii) the organic solvent is water-soluble, preferably acetonitrile.

17. A process for separating an olefin from an alkane comprising placing a porous metal- organic framework of any one of claims 1-10 into a container and purging the container with a mixture of an olefin and an alkane, wherein the olefin is preferentially retained within the porous metal-organic framework, optionally

wherein the process is a pressure swing adsorption process.

18. The process of claim 17, wherein the porous metal-organic framework is recyclable.

19. The process of claim 17 or 18, wherein the olefin and the alkane are selected from aliphatic carbon compounds, preferably wherein the aliphatic carbon compounds are

selected from Ci-salkanes and C2-salkenes., optionally wherein the unsaturated organic compound is selected from C2-salkenes, more preferably from ethane and propene, and the saturated organic compound is selected from Ci-salkanes, more preferably from ethane and propane.

20. The process of any one of claims 17 to 19, wherein the retaining of the olefin is based on the interaction of the π orbitals of the olefin with the s orbitals of the silver cation and the d orbitals of the silver cation to the vacant π* orbitals of olefins.