Oxygen reduction reaction on electrochemically deposited sub-monolayers and ultra-thin layers of Pt on (Nb-Ti)2AlC substrate

Abstract

Catalytic activity towards the oxygen reduction reaction (ORR) in 0.5 M H2SO4 was investigated at sub-monolayers and ultra-thin layers (corresponding to 10, 30 and 100 monolayers, (MLs)) of Pt electrochemically deposited on (Nb-Ti)2AlC substrate. Electrochemical deposition of Pt layers on (Nb-Ti)2AlC substrate was achieved from the solution containing 3 mM K2PtCl4 + 0.5 M NaCl (pH 4) under the conditions of convective diffusion (RPM = 400) using linear sweep voltammetry (LSV) at a sweep rate of 2 mV s-1 , by determining limiting potential for deposition of each Pt sample from the QPt vs. E curves. The Pt samples were characterized X-ray photoelectron spectroscopy (XPS). XPS analysis showed that practically the whole surface of (Nb-Ti)2AlC substrate is covered with homogeneous layer of Pt, while Pt ion reduction was complete to metallic form - Pt(0) valence state. Then oxygen reduction was studied at rotating disc electrode by cyclic voltammetry and linear sweep voltammetry. Two different Tafel slopes were observed, one close to 60 mV dec-1 in low current densities region and second one ~ 120 mV dec-1 in high current densities region. This novel catalyst exhibited higher activity in comparison to carbon supported one, in terms of mass activity - kinetic current density normalized to Pt loading.