Boosting the Plasmon-Mediated Electrochemical Oxidation of p-Aminothiophenol with p-Hydroxythiophenol as Molecular Cocatalyst.

Plasmon-mediated electrochemistry is an emerging area of interest in which the electrochemical reactions are enhanced by employing metal nanostructures possessing localized surface plasmon resonance (LSPR). However, the reaction efficacy is still far below its theoretical limit due to the ultrafast relaxation of LSPR-generated hot carriers. Herein, we introduce p-hydroxythiophenol (PHTP) as a molecular cocatalyst to significantly improve the reaction efficacy in plasmon-mediated electrochemical oxidation of p-aminothiophenol (PATP) on gold nanoparticles. Using electrochemical techniques, in situ Raman spectroscopy, and theoretical calculations, we elucidate that the presence of PHTP improves the hot hole-mediated electrochemical oxidation of PATP by 2-fold through the trapping of plasmon-mediated hot electrons. In addition, the selectivity of PATP oxidation could also be modulated by the introduction of PHTP cocatalyst. This tactic of employing molecular cocatalyst can be drawn out to endorse various plasmonic electrochemical reactions because of its simple protocol, high efficiency, and high selectivity.

Direct pyrolysis and ultrasound assisted preparation of N, S co-doped graphene/Fe3C nanocomposite as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions.

Bifunctional electrocatalysts to enable efficient oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential for fabricating high performance metal-air batteries and fuel cells. Here, a defect rich nitrogen and sulfur co-doped graphene/iron carbide (NS-GR/Fe3C) nanocomposite as an electrocatalyst for ORR and OER is demonstrated. An ink of NS-GR/Fe3C is developed by homogeneously dispersing the catalyst in a Nafion containing solvent mixture using an ultrasonication bath (Model-DC150H; power - 150 W; frequency - 40 kHz). The ultrasonically prepared ink is used for preparing the electrode for electrochemical studies. In the case of ORR, the positive half-wave potential displayed by NS-GR/Fe3C is 0.859 V (vs. RHE) and for the OER, onset potential is 1.489 V (vs. RHE) with enhanced current density. The optimized NS-GR/Fe3C electrode exhibited excellent ORR/OER bifunctional activities, high methanol tolerance and excellent long-term cycling stability in an alkaline medium. The observed onset potential for NS-GR/Fe3C electrocatalyst is comparable with the commercial noble metal catalyst, thereby revealing one of the best low-cost alternative air-cathode catalysts for the energy conversion and storage application.