Stable catalyst layers for hydrogen permeable composite membranes
The present invention provides a hydrogen separation membrane based on nanoporous, composite metal carbide or metal sulfide coated membranes capable of high flux and permselectivity for hydrogen without platinum group metals. The present invention is capable of being operated over a broad temperature range, including at elevated temperatures, while maintaining hydrogen selectivity.
1. A method for making a hydrogen separation membrane, comprising:
providing a inorganic substrate;
applying at least one transition metal catalyst layer to said inorganic substrate, wherein the hydrogen separation membrane does not include a platinum metal group material; and
determining if a repair of said inorganic substrate is necessary by performing a permeation test with an inert gas.
2. The method of claim 1 , wherein said inorganic substrate is selected from the group consisting of an inorganic porous substrate and a body center cubic dense metal substrate.
3. The method of claim 2 , wherein said inorganic substrate is said body centered cubic dense metal substrate and wherein said body centered cubic dense metal substrate is selected from the group consisting of vanadium, tantalum, niobium, combinations thereof and alloys thereof.
4. The method of claim 1 , wherein said transition metal catalyst layer is selected from the group consisting of a transition metal carbide, a transition metal nitride, a transition metal sulfide and combinations thereof.
5. The method of claim 1 , wherein said transition metal catalyst layer comprises a transition metal selected from the group consisting of a molybdenum, tungsten and combinations thereof.
6. The method of claim 1 , wherein said transition metal catalyst layer is applied at a temperature between about room temperature and about 600° C.
7. The method of claim 1 , further comprising coating said substrate with a polymer material to repair oversized pores on a top surface of said inorganic substrate.
8. The method of claim 1 , further comprising a porous layer, wherein said porous layer is a material selected from the group consisting of an alumina, a silica, a zirconia, a ceria, a titania and combinations thereof.
9. The method of claim 1 , wherein the at least one transition metal catalyst layer is applied by a vapor deposition method.
10. The method of claim 9 , wherein the vapor deposition method is selected from the group consisting of sputtering, chemical deposition and plasma enhanced chemical vapor deposition.
11. The method of claim 2 , wherein said inorganic substrate is said body centered cubic dense metal substrate and wherein a thin film of said body centered cubic dense metal substrate is deposited on a porous support layer.
12. The method of claim 1 , wherein the at least one transition metal catalyst layer is applied by solution deposition.
13. A method for applying a transition metal catalyst layer to an inorganic substrate to form a hydrogen permeable membrane, comprising:
providing an inorganic substrate;
applying a transition metal precursor to said inorganic substrate, wherein the transition metal precursor is a Group VI transition metal selected from the group consisting of molybdenum, tungsten and alloys thereof; and
converting said transition metal precursor to a transition metal catalyst layer, wherein the hydrogen permeable membrane does not contain a platinum metal group material, and wherein a thickness of the transition metal catalyst layer is between about 2 nanometers to about 50 nanometers.
14. The method of claim 13 , further comprising determining if a repair of said substrate is necessary by performing a permeation test with an inert gas.
15. The method of claim 13 , further comprising coating said substrate with a polymer material to repair oversized pores on a top surface of said substrate.
16. The method of claim 15 , wherein said polymer material is removed by oxidizing said substrate in air having a temperature of at least about 400° C.
17. The method of claim 13 , further comprising coating said substrate with an inorganic material to repair oversized pores on a top surface of said substrate.
18. The method of claim 13 , wherein a top surface of said substrate is a porous oxide coating.
19. The method of claim 18 , wherein said porous oxide coating is selected from the group consisting of an alumina, a silica, a zirconia, a ceria, and a titania.
20. The method of claim 13 , wherein said metal precursor is selected from the group consisting of a WF 6 , a MoF 6 , a W(CO) 6 , a Mo(CO) 6 and a MoCl 5 .
21. A hydrogen separation membrane comprising,
an inorganic substrate, wherein said inorganic substrate is selected from the group consisting of a porous inorganic substrate and a body centered cubic metal substrate; and
a transition metal catalyst layer deposited on two sides at a thickness of between about 2 nanometers to about 50 nanometers of said inorganic substrate, where the transition metal is a Group VI transition metal selected from the group consisting of molybdenum, tungsten and alloys thereof.
22. The hydrogen separation membrane of claim 21 , wherein said inorganic substrate is said porous inorganic substrate, wherein said porous inorganic substrate is a stainless steel material.
23. The hydrogen separation membrane of claim 22 , wherein said stainless steel material is coated with a porous oxide coating is selected from the group consisting of an alumina, a silica, a zirconia, a ceria, and a titania.
24. The hydrogen separation membrane of claim 21 , wherein said Group VI transition metal is selected from the group consisting of a molybdenum and a tungsten.
25. The hydrogen separation membrane of claim 21 , wherein said body centered cubic dense metal substrate is a foil.
26. The hydrogen separation membrane of claim 21 , wherein said transition metal catalyst is a transition metal sulfide.
27. The hydrogen separation membrane of claim 21 , wherein said transition metal catalyst is a transition metal nitride.
28. The hydrogen separation membrane of claim 21 , wherein said transition metal catalyst is a transition metal carbide.