Heterometallic antenna-reactor complexes for photocatalysis.
Swearer, Dayne F
Krauter, Caroline M
McClain, Michael J
Carter, Emily A
Proceedings of the National Academy of Sciences of the United States of America
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Swearer, D. F., Zhao, H., Zhou, L., Zhang, C., Robatjazi, H., Martirez, J. M. P., Krauter, C. M., et al. (2016). Heterometallic antenna-reactor complexes for photocatalysis.. Proceedings of the National Academy of Sciences of the United States of America, 113 (32), 8916-8920. https://doi.org/10.1073/pnas.1609769113
Metallic nanoparticles with strong optically resonant properties behave as nanoscale optical antennas, and have recently shown extraordinary promise as light-driven catalysts. Traditionally, however, heterogeneous catalysis has relied upon weakly light-absorbing metals such as Pd, Pt, Ru, or Rh to lower the activation energy for chemical reactions. Here we show that coupling a plasmonic nanoantenna directly to catalytic nanoparticles enables the light-induced generation of hot carriers within the catalyst nanoparticles, transforming the entire complex into an efficient light-controlled reactive catalyst. In Pd-decorated Al nanocrystals, photocatalytic hydrogen desorption closely follows the antenna-induced local absorption cross-section of the Pd islands, and a supralinear power dependence strongly suggests that hot-carrier-induced desorption occurs at the Pd island surface. When acetylene is present along with hydrogen, the selectivity for photocatalytic ethylene production relative to ethane is strongly enhanced, approaching 40:1. These observations indicate that antenna−reactor complexes may greatly expand possibilities for developing designer photocatalytic substrates.
External DOI: https://doi.org/10.1073/pnas.1609769113
This record's URL: https://www.repository.cam.ac.uk/handle/1810/283282