Electrocatalysis on Shape‐Controlled Titanium Nitride Nanocrystals for the Oxygen Reduction Reaction

The high price of platinum (Pt)-based cathode catalysts for the oxygen reduction reaction (ORR) have slowed down the practical application of fuel cells. Thanks to their low cost, and outstanding, stable catalytic properties, titanium nitrides (TiN) are among the most promising non-precious metal electrocatalysts for replacing Pt. However, the shape-activity relationships of TiN electrocatalysts have not been well-studied or understood up to now. In this work, by simply adjusting the shape of TiO2 precursor, we are able to tailor the morphology of the TiN catalysts from nanoparticles to nanotubes. We have synthetized uniform carbon-coated titanium nitride nanotubes (carbon-coated TiN NTs) through a nitridation reaction in NH3 flow using a TiO2 nanotubes/melamine mixture as precursor. The carbon-coated TiN NTs hybrids exhibit excellent electrocatalytic activity for the ORR, coupled with superior methanol tolerance and long-term stability in comparison to commercial Pt/C, through an efficient four-electron-dominant ORR process. Compared with nanoparticles, the one-dimensional and hollow structure of the nanotubes result in greater diffusion of electrolyte and superior electrical conductivity, and contribute to the greatly improved electrocatalytic performance of the carbon-coated TiN NTs nanocomposites.