Plasmon-Driven Highly Selective CO2 Photoreduction to C2H4 on Ionic Liquid-Mediated Copper Nanowires.

ABSTRACT

Selective CO2 photoreduction to value-added multi-carbon (C2+) feedstocks, such as C2H4, holds great promise in direct solar-to-chemical conversion for a carbon-neutral future. Nevertheless, the performance is largely inhibited by the high energy barrier of C-C coupling process, thereby leading to C2+ products with low selectivity. Here we report that through facile surface immobilization of a 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) ionic liquid, plasmonic Cu nanowires could enable highly selective CO2 photoreduction to C2H4 product. At an optimal condition, the resultant plasmonic photocatalyst exhibits C2H4 production with selectivity up to 96.7% under 450 nm monochromatic light irradiation, greatly surpassing its pristine Cu counterpart. Combined in situ spectroscopies and computational calculations unravel that the addition of EMIM-BF4 ionic liquid modulates the local electronic structure of Cu, resulting in its enhanced adsorption strength of *CO intermediate and significantly reduced energy barrier of C-C coupling process. This work paves new path for Cu surface plasmons in selective artificial photosynthesis to targeted products.