Graphene membrane filter for gas separation
The invention relates to carbon supported crack- and tear-free graphene membranes of large area useful for selective gas separation, method of preparation and uses thereof. In particular, the invention relates to carbon supported crack- and tear-free graphene membranes having good gas separation performance, in particular high H 2 permeance and H 2 /CH 4 selectivities.
1. A gas selective separation filter comprising a nanoporous graphene membrane having a thickness of about 0.34 to 2 nm and a porosity greater than 0.001%, a porous carbon substrate on which the graphene membrane is mounted, the porous carbon substrate having a porosity in a range of 5% to 90%, and a porous support structure on which the graphene membrane and porous carbon substrate are mechanically supported.
2. The gas selective separation filter according to claim 1 , wherein pores of the nanoporous graphene membrane have a mean size between about 0.2 nm and about 0.5 nm.
3. The gas selective separation filter according to claim 1 , wherein the porous carbon substrate has a porosity in a range of 10% to 80% and comprises pores having a mean size in a range of about 10 to 1000 nm.
4. The gas selective separation filter according to claim 1 , wherein the porous support structure has a porosity in a range of 2% to 60% formed by pores having a mean size in a range of 0.01 μm to 100 μm and a thickness in a range of 10 μm to 10000 μm.
5. A method for the preparation of a gas selective separation filter comprising the steps of:
a) providing a graphene membrane on a sacrificial support layer;
b) coating said graphene membrane with an organic precursor of a porous carbon substrate;
c) subjecting the organic precursor to a pyrolysis transforming the organic precursor into said porous carbon substrate on the graphene membrane, wherein the porous carbon substrate has a porosity between 5% and 90%;
d) mounting the combined porous carbon substrate and graphene membrane on a macroporous support structure; and
e) removing, before or after step d), at least portions of the sacrificial support layer.
6. The method according to claim 5 , wherein in step e), removing at least portions of the sacrificial support layer comprises etching said portions of the sacrificial support layer.
7. The method according to claim 6 , wherein the etching is performed prior to step d) to obtain a free-standing combined porous carbon substrate and graphene membrane suspended in the etchant solution.
8. The method according to claim 5 , wherein in step e) the combined porous carbon substrate and graphene membrane is mounted on said macroporous support structure by a wet transfer process in a liquid bath.
9. The method according to claim 5 , wherein in step b) said organic precursor is in a solution and the solution is dried until a film of the organic precursor is formed at the surface of the graphene membrane.
10. The method according to claim 9 , wherein the solution is a solution of turanose and block-copolymer polystyrene-co-poly(4-vinylpyridine) (PS-P4VP) dissolved in N,N-dimethylformamide.
11. The method according to claim 5 , wherein the organic precursor is an amphipathic block copolymer of polyvinylpyridine and polystyrene monomers.
12. The method according to claim 11 , wherein the block-copolymer is polystyrene-co-poly(4-vinylpyridine) (PS-P4VP).
13. The method according to claim 5 , wherein the organic precursor of a porous structure is an amphipathic block copolymer.
14. The method according to claim 5 , wherein in step c) pyrolysis is conducted during about 0.25 to about 1.5 hours, at a temperature in a range of 400° C. to 1000° C.
15. The method according to claim 5 , wherein in step c) pyrolysis is conducted under a H 2 /Ar flow.
16. The method according to claim 5 , further comprising a treatment of the graphene membrane with ozone under inert atmosphere for about 1 ms to about 1 month or for about 30 s to about 60 minutes.
17. The method according to claim 5 , further comprising a treatment of the graphene membrane with ozone at a temperature between about 25° C. and 300° C.
18. The method according to claim 17 , wherein the temperature is between 25° C. and about 100° C.
19. A method of separating components of a gas comprising applying a gas to the gas selective separation filter according to claim 1 and separating the components of the gas.
20. The method according to claim 19 , wherein the method separates H 2 or CH 4 from CO 2 .