MOF Encapsulated Sub-nm Pd skin/Au Nanoparticles as Antenna-Reactor Plasmonic Catalyst for Light Driven CO2 Hydrogenation

Abstract Activation of CO2 with plasmon induced hot electrons has attracted great attention due to its moderate reaction conditions, but high-efficiency plasmonic catalysts still remains challenging. Herein, we designedly prepared an antenna-reactor plasmonic catalyst with core-shell structure, i.e. sub-nm Pd skin/Au NPs encapsulated within UiO-66-NH2 (Au@Pd@UiO-66-NH2-0.5) for CO2 hydrogenation under light-heat dual activation. Under the photo-thermal synergism, CO2 can be efficiently converted into CO and the optimal production rate reaches 3737 µmol/gmetal/h at 150 °C. Thereinto, ultrafast transient absorption spectroscopy reveals that the sub-nm Pd skin provides a longer time window for hot electron transfer and efficient retardation of energy dissipation. Theoretical calculations further confirm the significant reductions in HOMO-LUMO gap of CO2 and reaction energy barrier from CO2⁎ to COOH⁎ through adsorption of CO2 on sub-nm Pd skin, promoting its efficiency and selectivity. Our findings provide new insights into design of bimetallic plasmonic catalysts for low-temperature catalysis.