Plasmonic Enhanced Catalytic Durability of CO ₂ Hydrogenation

ABSTRACT Solar‐driven carbon dioxide (CO ₂ ) hydrogenation represents a promising route for producing value‐added chemicals/fuels with a negative carbon footprint. Plasmonic catalysis attracts significant attention as it synergistically employs thermochemistry and photochemistry, facilitated by multiple thermal and/or nonthermal effects, including efficient solar energy harvesting, localized heating, localized electric field, and hot carrier excitations. Herein, a metallic cobalt nanowire array is employed as the plasmonic catalyst to demonstrate that the reaction kinetics of CO ₂ hydrogenation are effectively improved by light‐excited plasmonic localized electric field through regulating the binding strength of reactive intermediates. Theoretical simulations and operando spectroscopic data further reveal that the catalytic durability is significantly enhanced compared to traditional thermocatalysis because of the localized electric field‐assisted suppression of coking deactivation. This work presents the first demonstration of plasmonic‐enhanced catalytic durability, delivering key mechanistic insights for the future design of efficient and stable plasmonic catalysts.