Highly corrosion resistant platinum–niobium oxide–carbon nanotube electrodes for the oxygen reduction in PEM fuel cells

Nanocomposite materials consisting of platinum deposited on carbon nanotubes are emerging electrocatalysts for the oxygen reduction reaction in PEM fuel cells. However, these materials albeit showing promising electrocatalytic activities suffer from unacceptable rates of corrosion during service. This study demonstrates an effective strategy for creating highly corrosion-resistant electrocatalysts utilizing metal oxide coated carbon nanotubes as a support for Pt. The electrode geometry consisted of a three-dimensional array of multi-walled carbon nanotubes grown directly on Inconel and conformally covered by a bilayer of Pt/niobium oxide. The activities of these hybrid carbon-metal oxide materials are on par with commercially available carbon-supported Pt catalysts. We show that a sub-nanometre interlayer of NbO2 provides effective protection from electrode corrosion. After 10,000 cyclic voltammetry cycles from 0.5 V to 1.4 V, the loss of electrochemical surface area, reduction of the half-wave potential, and the loss of specific activity of the NbO2 supported Pt were 10.8%, 8 mV and 10.3%, respectively. Under the same conditions, the catalytic layers with Pt directly deposited onto carbon nanotubes had a loss of electrochemical area, reduction of half-wave potential and loss of specific activity of 47.3%, 65 mV and 65.8%, respectively. The improved corrosion resistance is supported by microstructural observations of both electrodes in their post-cycled state. First principles calculations at the density functional theory level were performed to gain further insight into changes in wetting properties, stability and electronic structure introduced by the insertion of the thin NbO2 film.