Interfacial Electron Engineering of PdSn‐NbN/C for Highly Efficient Cleavage of the C–C Bonds in Alkaline Ethanol Electrooxidation

Abstract The splitting of the C–C bonds of ethanol remains a key issue to be addressed, despite tremendous efforts made over the past several decades. This study highlights the enhancement mechanism of inexpensive NbN‐modified Pd 1 Sn 3 ‐NbN/C towards the C–C bonds cleavage for alkaline ethanol oxidation reaction (EOR). The optimal Pd 1 Sn 3 ‐NbN/C delivers a catalytic activity up to 43.5 times higher than that of commercial Pd/C and high carbonate selectivity (20.5%) toward alkaline EOR. Most impressively, the Pd 1 Sn 3 ‐NbN/C presents good durability even after 25 200 s of chronoamperometric testing. The enhanced catalytic performance is mainly due to the interfacial interaction between PdSn and NbN, demonstrated by multiple structural characterization results. In addition, in situ ATR‐SEIRAS (Attenuated total reflection‐surface enhanced infrared absorption spectroscopy) results suggest that NbN facilitates the C–C bonds cleavage towards the alkaline EOR, followed by the enhanced OH adsorption to promote the subsequent oxidation of C1 intermediates after doping Sn. DFT (density functional theory) calculations indicate that the activation barriers of the C–H bond cleavage in CH 3 CH 2 OH, CH 3 CHOH, CH 3 CHO, CH 3 CO, CH 2 CO, and the C–C bond cleavage in CH 3 CO, CH 2 CO, CHCO are evidently reduced and the removal of adsorbed CH 3 CO and CO becomes easier on the PdSn‐NbN/C catalyst surface.