A composite electrode structure and methods of making and using thereof are disclosed. The structure has a metal substrate with a metal oxide layer. The average thickness of the metal oxide layer is less than 150 nm, and comprises at least a first metal and a second metal, wherein the first metal and the second metal are different elements. A plurality of carbon nanotubes is disposed on a first surface of the metal oxide layer. At least a portion of the carbon nanotubes are disposed such that one end of the carbon nanotube is positioned at least 5 nm below the surface of the metal oxide layer.