Charge redistribution on Pd mediated by electronically asymmetric carbon for boosting ethanol oxidation

Pd-based materials as the promising catalysts for ethanol oxidation reaction (EOR) are still intrinsically limited by the surface electronic-structure trade-off between ethanol adsorption and CH 3 CO intermediate desorption. Herein, the Pd supported on N/S co-doped carbon (Pd@SNC) catalyst is synthesized, in which the doped S and N atoms could transfer moderate amounts electron to Pd, leading to opportune electron structure of Pd. Moreover, the moderate negative shift of d -band center demonstrate that the opportune Pd electron structure can strengthen adsorption of ethanol/OH − and promote the desorption of intermediate (CH 3 CO*), which may facilitate the kinetics. As a result, Pd@SNC exhibiting the highest catalytic activity for EOR (945.49 mA mg Pd −1 ), surpassing to that of Pd@NC and Pd@C. Due to the fact that the electronic structure of Pd is properly regulated by co-doped N and S atoms, as shown by the theoretical calculation results, Pd@SNC exhibits the lowest reaction energy barrier of the dehydrogenation during the process of EOR.