In-situ oxidation of Palladium-Iridium nanoalloy anchored on Nitrogen-doped graphene as an efficient catalyst for methanol electrooxidation.

Palladium (Pd)-based materials have been widely used as catalysts for the methanol oxidation reaction (MOR). Unfortunately, the catalytic activity was limited by structure, carbon monoxide intermediates (CO) tolerance and stability. It was currently difficult to be used in large-scale commercial production. Herein, to further improve their electrocatalytic activity, a facile oxidation method to achieve in-situ oxidation of palladium-iridium (PdIr) alloy on nitrogen-doped graphene (NGS) is used, which is named as Pd-Ir-O/NGS. The new catalyst exhibits remarkable MOR activity (1374.8 mA mg), CO tolerance (the onset oxidation potential reach 0.725 V) and stability (the current density retention rate after 500 cycles of cyclic voltammetry is 44.9%). As a catalyst for MOR, the Pd-Ir-O/NGS has more outstanding electrocatalytic performance compared with commercial Pd/C and other counterparts. The mechanism study shows that the excellent catalytic performance is attributed to (1) the synergistic electronic effect of Pd-Ir-O due to the introduction of Ir and O, (2) the insertion of O into PdIr alloy that kinetically accelerated the oxidation of poisoning methoxy intermediates and (3) the vital roles of unique three-dimensional (3D) structure of NGS with abundant nitrogen atoms. Our findings herald a new paradigm for the modification of palladium-based materials for MOR and provide an alternative design principle for novel 3D carbon-based material for various application.