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

Abstract

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.

Surface-plasmon-enhanced ethanol electrocatalysis and enhancement mechanism of nanoporous AuPd with wide-spectrum response characteristics under visible light irradiation

“…2g), and similar phenomena have been reported in the literature. 69 In addition, NP AuPd under 400–800 nm light irradiation achieved an EOR activity comparable to that at 40–46 °C solution temperatures (Fig. 2f).…”

Bimetallic Pd–Co Aerogel Three-Dimensional Architecture: Developing Self-Assembled Materials for Advanced Ethanol Oxidation

“…As illustrated, electrocatalysis of EtOH generates two strong peaks in the forward and reverse sweeps. The first peaks were generated because of the decomposition of EtOH molecules at the surface of four samples. ,− These interactions not only delivered the high current density but also produced the carbonaceous intermediates . Hence, other peaks appeared in backward scans because of the elimination of produced carbonaceous intermediates.…”

“…Hence, other peaks appeared in backward scans because of the elimination of produced carbonaceous intermediates. Subsequently, it can be logically concluded that the current density ratio generated in the forward ( J f ) to reverse ( J b ) scans can be used as a reliable parameter to evaluate the power of an electrocatalyst. ,− By comparing the achieved plots, the Pd 92 Co 8 aerogel ( J f / J b = 1.17), Pd 95 Co 5 aerogel ( J f / J b = 1.13), and Pd 89 Co 11 aerogel ( J f / J b = 0.96) reveal a stronger tolerance to poisoning relative to Pd/C ( J f / J b = 0.6). Additionally, the decomposition reaction of EtOH for Pd 92 Co 8 aerogel (−0.548 V), Pd 95 Co 5 aerogel (−0.538 V), and Pd 89 Co 11 aerogel (−0.532 V) started at a more negative potential in comparison to Pd/C (−0.460 V), corroborating the improved kinetics for these resultant 3D superstructures. , Moreover, the Pd 92 Co 8 aerogel, Pd 95 Co 5 aerogel, Pd 89 Co 11 aerogel, and Pd/C generated the mass activity of 4302.1, 3380.9, 2135.1, and 1007.9 mA/mg Pd .…”

Exposing an Environmentally Friendly Gelation Strategy to Fabricate Modern Three-Dimensional M–Ag (M = Pt and Pd) Aerogels with Excellent Green Energy Generation

“…These high activities are due to the interaction of all electrocatalysts with the clean available active sites. However, the cleavage of CH 3 CH 2 OH molecules leads not only to the generation and adsorption of intermediate species on the aerogel surface but also to a sharp decrease in the specific activity owing to the poisoning and blocking of the active sites. − The steeper slope of the CA profile for Pt–Ag aerogel suggests a greater poisoning and less stability against Pd–Ag aerogel. Additionally, the gradual decrease in CA plots for both engineered aerogels relative to the Pd/C catalyst highlights their incredible electrocatalytic durability.…”