Exploiting hot electrons from a plasmon nanohybrid system for the photoelectroreduction of CO₂

Plasmonic materials convert light into hot carriers and heat to mediate catalytic transformation. The participation of hot carriers (photocatalysis) remains a subject of vigorous debate, often argued on the basis that carriers have ultrashort lifetime incompatible with drive photochemical processes. This study utilises plasmon hot electrons directly in the photoelectrocatalytic reduction of CO₂ to CO via a Ppasmonic nanohybrid. Through the deliberate construction of a plasmonic nanohybrid system comprising NiO/Au/Re^I(phen-NH₂)(CO)₃Cl (phen-NH₂ = 1,10-Phenanthrolin-5-amine) that is unstable above 580 K; it was possible to demonstrate hot electrons are the main culprit in CO₂ reduction. The engagement of hot electrons in the catalytic process is derived from many approaches that cover the processes in real-time, from ultrafast charge generation and separation to catalysis occurring on the minute scale. Unbiased in situ FTIR spectroscopy confirmed the stepwise reduction of the catalytic system. This, coupled with the low thermal stability of the Re^I(phen-NH₂)(CO)₃Cl complex, explicitly establishes plasmonic hot carriers as the primary contributors to the process. Therefore, mediating catalytic reactions by plasmon hot carriers is feasible and holds promise for further exploration. Plasmonic nanohybrid systems can leverage plasmon's unique photophysics and capabilities because they expedite the carrier's lifetime.