Engineering Support and Distribution of Palladium and Tin on MXene with Modulation of the d-Band Center for CO-resilient Methanol Oxidation.

The efficiency of direct methanol fuel cell (DMFC) is largely determined by the activity and durability of methanol oxidation reaction (MOR) catalysts. Herein, we present a CO-resilient MOR catalyst of palladium-tin nano-alloy anchored on Se-doped MXene (PdSn 0.5 /Se-Ti 3 C 2 ) via a progressive one-step electrochemical deposition strategy. MOR mass activity resulting from Pd/Se-Ti 3 C 2 catalyst (1046.2 mA mg -1 ) is over 2-fold larger than that of Pd/Ti 3 C 2 , suggesting that the introduction of Se atoms on MXene might accelerate the reaction kinetics. PdSn 0.5 /Se-Ti 3 C 2 with Se-doping progress of MXene and the cooperated Pd-Sn sites has a superior MOR mass activity (4762.8 mA mg -1 ), outperforming many other reported Pd-based catalysts. Both experimental results and theoretical calculation reveal that boosted electron interaction of metal crystals with Se-doped MXene and optimized distribution of Pd-Sn sites can modulate the d band center, reduce adsorption energies of CO* at Pd site and enhance OH* generation at Sn site, resulting in highly efficient removal of CO intermediates by reaction with neighboring OH species on adjacent Sn sites.