Quantifying hot carrier and thermal contributions in plasmonic photocatalysis

• Published in: Science (American Association for the Advancement of Science) Vol. 362; no. 6410; pp. 69 - 72
• Main Authors: Zhou, Linan, Swearer, Dayne F, Zhang, Chao, Robatjazi, Hossein, Zhao, Hangqi, Henderson, Luke, Dong, Liangliang, Christopher, Phillip, Carter, Emily A, Nordlander, Peter, Halas, Naomi J
• Format: Journal Article
• Language: English
• Published: United States The American Association for the Advancement of Science 05.10.2018
• Subjects: Activation; Ammonia; Catalysis; Catalysts; Copper base alloys; Current carriers; Decomposition; Decomposition reactions; Energy efficiency; Light; Light effects; Luminous intensity; Nanoparticles; Nitrogen atoms; Optical activity; Organic chemistry; Photocatalysis; Photocatalysts; Photochemistry; Reduction; Ruthenium; Surface temperature; Wavelengths
• ISSN: 0036-8075; 1095-9203
• DOI: 10.1126/science.aat6967

Photocatalysis based on optically active, "plasmonic" metal nanoparticles has emerged as a promising approach to facilitate light-driven chemical conversions under far milder conditions than thermal catalysis. However, an understanding of the relation between thermal and electronic excitations has been lacking. We report the substantial light-induced reduction of the thermal activation barrier for ammonia decomposition on a plasmonic photocatalyst. We introduce the concept of a light-dependent activation barrier to account for the effect of light illumination on electronic and thermal excitations in a single unified picture. This framework provides insight into the specific role of hot carriers in plasmon-mediated photochemistry, which is critically important for designing energy-efficient plasmonic photocatalysts.