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

作者: Edina Rosta , Edina Rosta , Erwin Reisner , Qianqi Lin , Andreas Wagner

DOI: 10.1038/S41929-020-00566-X

关键词:

摘要: Immobilized first-row transition metal complexes are potential low-cost electrocatalysts for selective CO2 conversion in the production of renewable fuels. Mechanistic understanding their function is vital development next-generation catalysts, although poor surface sensitivity many techniques makes this challenging. Here, a nickel bis(terpyridine) complex introduced as reduction electrocatalyst 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 that nature anchoring group plays pivotal role catalytic mechanism. Our situ spectro-electrochemical measurement enables detection few eight molecules undergoing redox transformations individual plasmonic hotspots, together calibration electrical fields via vibrational Stark effects. This advance allows rapid exploration non-resonant reactions at few-molecule level and provides scope future mechanistic studies single molecules. Tracking immobilized molecular under conditions Now, has been elucidated gap-plasmon-assisted SERS DFT calculations.

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