Title :

Carbon-Fixation by Plasmonic Catalysts

Abstract :

Mimicking plant photosynthesis requires a synthetic photocatalyst that absorbs sunlight and uses that energy efficiently to convert CO2 into energy-dense hydrocarbons. My talk will make the case that noble metal nanostructures, which exhibit collective free electron resonances called plasmons, may be well-suited to this task. Not only do plasmonic nanoparticles of Au, Ag, and Cu offer a means to absorb visible light efficiently, their strong-light-matter interaction can be paired with their ability to activate small molecules, such as CO2. We have had preliminary success with plasmonic catalysts, which under visible-light-excitation, can drive kinetically challenging multi-electron multi-proton processes such as methane generation. Moreover, the product selectivity is controllable by the nature of the exciting light, which suggests that a novel phenomenon is at work. In order to understand the light-driven pathway for CO2 reduction, we have probed with single-site spatial resolution the dynamics of a plasmonic photocatalyst under operando conditions. From captured intermediates and density functional theory simulations, we are beginning to understand the mechanism which plasmonic excitation activates physisorbed CO2. It is clear that a close interplay between photoexcited states and surfaces is involved in this scheme of artificial photosynthesis.