Carbon-supported hafnium oxynitride as cathode catalyst for polymer electrolyte membrane fuel cells

Highly stable carbon-supported hafnium oxynitride (HfO_xN_y-C) was synthesized by heating carbon-supported hafnium oxide, prepared using an impregnation method, under NH₃ gas in various conditions. X-ray diffraction patterns, X-ray photoelectron spectra, and field-emission transmission electron microscope images confirmed that HfO_xN_y nanoparticles were dispersed onto commercial carbon black, Vulcan XC-72. The stability of HfO_xN_y-C in 0.1 mol dm⁻³ H₂SO₄ at 303 K was evaluated by measuring the mass ratio of dissolved hafnium to immersed HfO_xN_y-C using inductively coupled plasma atomic emission spectroscopy. It saturated at a low level of 0.8–4.0 mg g⁻¹ with increasing immersion time up to ∼24 h. The oxygen reduction reaction (ORR) activity and rate were evaluated by obtaining cyclic voltammograms and rotating disk electrode voltammograms, respectively. The HfO_xN_y-C exhibited higher ORR activity and a lower Tafel slope than NH₃-treated C under identical conditions, demonstrating that HfO_xN_y is active toward ORR. The ORR activity most depended on the heating temperature. The ORR rate increased with increasing the heating time at 1223 K which could be due to the increased y in HfO_xN_y-C. The maximum onset potential for ORR was 0.78 V vs. standard hydrogen electrode, which is 0.18 V lower than that of carbon-supported platinum.