Mechanistic study of an immobilized molecular electrocatalyst by in situ gap-plasmon-assisted spectro-electrochemistry

Abstract

Immobilised first-row transition metal complexes are potential low-cost electrocatalysts for selective CO2 conversion to produce renewable fuels. Mechanistic understanding of their function is vital for the development of next-generation catalysts, though poor surface sensitivity of many techniques makes this challenging. Here, a nickel bis(terpyridine) complex is introduced as a CO2 reduction electrocatalyst in a unique electrode geometry, sandwiched by thiol anchoring moieties between two gold surfaces. Gap-plasmon-assisted surface-enhanced Raman scattering spectroscopy coupled with density functional theory calculations reveals the nature of the anchoring group plays a pivotal role in the catalytic mechanism by eliminating ligand loss. Our in-situ spectro-electrochemical measurement enables the detection of as few as 8 molecules undergoing redox transformations in the individual gold-sandwiched nanocavities, together with the calibration of electrical fields via vibrational Stark effects. This advance allows rapid exploration of non-resonant redox reactions at the few-molecule level and provides scope for future mechanistic studies of single-molecules.