Method of fabricating electrode catalyst layers with directionally oriented carbon support for proton exchange membrane fuel cell

1. A membrane electrode assembly (MEA) comprising an anode and a cathode and a proton conductive membrane therebetween, the anode and the cathode each comprising a patterned sheet of longitudinally aligned transition metal-containing graphitic carbon nanotubes, wherein the carbon nanotubes are in contact with and are aligned generally perpendicular to the membrane, wherein a catalytically active transition metal is incorporated longitudinally and is atomically distributed throughout the graphitic carbon walls of said nanotubes, and transition metal or precious metal crystallites are present on the surface of the nanotubes.

2. The MEA of claim 1 wherein the catalytically active transition metal comprises Fe, Ni, Co, Cr, Mn, or a combination thereof.

3. The MEA of claim 1 wherein the catalytically active transition metal comprises Fe, Ni, Co, or a combination thereof.

4. The MEA of claim 1 wherein the nanotubes form a three dimensional pattern of gas-flow channels on the membrane.

5. The MEA of claim 1 produced by:

(a) introducing a combination of a transition metal-containing carbon nanotube precursor and a gaseous mixture comprising an inert gas and a reducing gas into a first reactor zone maintained at a first temperature and for a period of time sufficient to vaporize the transition metal-containing carbon nanotube precursor, introducing the vaporized material to a second reactor zone maintained at a second temperature that is higher than the first temperature and for a period of time sufficient to pyrolyze the transition metal-containing carbon nanotube precursor, and grow longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes onto a substrate present in the second reactor zone, wherein the substrate is patterned with a template for forming longitudinally-aligned carbon nanotubes perpendicular to the substrate surface, and the carbon nanotube precursor is selected from the group consisting of a transition metal phthalocyanine, a transition metal porphyrin compound, a transition metal organometallic compound, or a combination thereof, optionally as a solution in an aromatic hydrocarbon solvent;

(b) introducing transition metal or precious metal crystallites onto the surface of the nanotubes;

(c) depositing a layer of an ionomeric polymer over the carbon nanotubes and drying the polymer to form a nanotube-containing polymeric decal having an outer polymeric side and an inner nanotube side in contact with the substrate;

(d) fusing the polymeric side of two such decals to both sides of a proton-conductive membrane at an elevated temperature and pressure; and

(e) removing the substrates to thereby form the MEA.

6. The MEA of claim 5 wherein the gaseous mixture comprises argon and hydrogen and optionally includes ammonia, and the transition metal-containing carbon nanotube precursor comprises Fe, Ni, Co, Cr, Mn, or mixtures thereof.

7. The MEA of claim 5 wherein the temperature in the first reactor zone is maintained in the range of from about 150° C. to about 700° C. and the temperature in the second reactor zone is maintained in the range of from about 700° C. to about 1000° C.

8. The MEA of claim 5 wherein the material is maintained in the reactor zones for a period of time in the range of from about 5 to about 45 minutes.

9. The MEA of claim 5 wherein the nanotubes form a three dimensional (3D) pattern of gas-flow channels on the membrane.

10. The MEA of claim 5 wherein the carbon nanotube precursor contains a transition metal selected from the group consisting of Fe, Ni, Co, and a mixture thereof.

11. The MEA of claim 5 wherein the nanotubes are generally straight or include spiral or bamboo shaped or bellows shaped nanotubes.

12. The MEA of claim 5 wherein one transition metal-containing nanotube decal of the MEA includes an oxidation catalyst and the other decal includes a reduction catalyst.

13. The MEA of claim 5 wherein a plurality of the MEAs are assembled into a proton exchange membrane fuel cell (PEMFC) by alternately stacking bipolar plates between the MEAs.

14. A membrane electrode assembly (MEA) comprising an anode and a cathode and a proton conductive membrane therebetween, one or more of the anode and the cathode comprising a patterned sheet of longitudinally aligned transition metal-containing graphitic carbon nanotubes, wherein the carbon nanotubes are in contact with and are aligned generally perpendicular to the membrane, wherein a catalytically active transition metal is incorporated longitudinally and is atomically distributed throughout the graphitic carbon walls of said nanotubes, and transition metal or precious metal crystallites are present on the surface of the nanotubes, and wherein the MEA is produced by:

forming a sheet of longitudinally aligned graphitic nanotubes on a substrate including a three dimensional pattern for aligning the nanotubes in a gas-flow pattern by chemical vapor deposition (CVD), and transferring the so-formed sheet of nanotubes to a surface of a proton conductive membrane, wherein the chemical vapor deposition comprises pyrolysis of a transition metal-containing organometallic material to form nanotubes that include the transition metal within the nanotube structure.

15. The MEA of claim 14 wherein the catalytically active transition metal comprises Fe, Ni, Co, Cr, Mn, or a combination thereof.

16. A membrane for a proton exchange membrane fuel cell (PEMFC) comprising a proton conductive membrane that includes longitudinally aligned graphitic carbon nanotubes generally perpendicular to the proton exchange membrane and in contact with a surface thereof, a catalytically active transition metal being incorporated longitudinally to the nanotubes and being atomically distributed throughout the graphitic carbon walls of said nanotubes, and transition metal or precious metal crystallites on the surface of the nanotubes.

17. The membrane of claim 16 produced by forming longitudinally aligned graphitic nanotubes with a catalytically active transition metal in the nanotubes on a substrate by chemical vapor deposition (CVD), transferring the longitudinally aligned graphitic nanotubes from or with the substrate to the proton conductive membrane with the longitudinally aligned graphitic nanotubes being generally perpendicular to the proton exchange membrane and in contact therewith.

18. The membrane of claim 16 wherein the catalytically active transition metal comprises Fe, Ni, Co, Cr, Mn, or a combination thereof.

19. The membrane of claim 16 wherein the nanotubes form a three dimensional pattern of gas channels on the surface of the membrane.