Plasmon-Enhanced C-C Bond Cleavage toward Efficient Ethanol Electrooxidation.

Ethanol, as a sustainable biomass fuel, is endowed with the merits of theoretically high energy density and environmental friendliness yet suffers from sluggish kinetics and low selectivity toward the desired complete electrooxidation (C1 pathway). Here, the localized surface plasmon resonance (LSPR) effect is explored as a manipulating knob to boost electrocatalytic ethanol oxidation reaction in alkaline media under ambient conditions by appropriate visible light. Under illumination, Au@Pt nanoparticles with plasmonic core and active shell exhibit concurrently higher activity (from 2.30 to 4.05 A mg Pt -1 at 0.8 V vs RHE) and C1 selectivity (from 9 to 38% at 0.8 V). In situ attenuated total reflection-surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) provides a molecular level insight into the LSPR promoted C-C bond cleavage and the subsequent CO oxidation. This work not only extends the methodology hyphenating plasmonic electrocatalysis and in situ surface IR spectroscopy but also presents a promising approach for tuning complex reaction pathways.