Amorphous MoOx with High Oxophilicity Interfaced with PtMo Alloy Nanoparticles Boosts Anti-CO Hydrogen Electrocatalysis.

Abstract

Advancing electrocatalysts for alkaline hydrogen oxidation/evolution reaction (HOR/HER) is essential for anion exchange membrane-based devices. The state-of-the-art Pt-based electrocatalysts for alkaline HOR suffer from low intrinsic activities and severe CO poisoning due to the challenge of simultaneously optimizing surface adsorption toward different adsorbates. Herein, this challenge is overcome by tuning an atomic MoOx layer with high oxophilicity onto PtMo nanoparticles (NPs) with optimized Had , OHad , and COad adsorption for boosting anti-CO-poisoning hydrogen-cycle electrocatalysis in alkaline media. For alkaline HOR, this catalyst exhibits high kinetics and an exchange current density of 3.19mAµgPt -1 at 50mV versus reversible hydrogen electrode and 0.83mAcmPt -2 , 10.3- and 3.8-fold higher than those of commercial Pt/C, respectively. For alkaline HER, it achieves an unprecedented overpotential of 37mV at 10mAcm-2 . Experimental and theoretical studies show that the orchestrated electronic and oxophilic regulation of the PtMo/MoOx interface NPs simultaneously optimizes Had and OHad adsorption for boosting alkaline hydrogen electrocatalysis, whereas reactive oxygen from the amorphous MoOx atomic layer lowers the CO oxidation reaction barrier, leading to superior anti-poisoning ability even at 100ppm CO.