title: Heterometallic antenna-reactor complexes for photocatalysis.
abstract: 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.
authors.affiliation: Department of Chemistry, Rice University, Houston, TX 77005;
authors.forename: Dayne F
authors.initials: DF
authors.lastname: Swearer
authors.affiliation: Department of Electrical and Computer Engineering, Rice University, Houston, TX 77005;
authors.forename: Hangqi
authors.initials: H
authors.lastname: Zhao
authors.affiliation: Department of Chemistry, Rice University, Houston, TX 77005;
authors.forename: Linan
authors.initials: L
authors.lastname: Zhou
authors.affiliation: Department of Electrical and Computer Engineering, Rice University, Houston, TX 77005;
authors.forename: Chao
authors.initials: C
authors.lastname: Zhang
authors.affiliation: Department of Electrical and Computer Engineering, Rice University, Houston, TX 77005;
authors.forename: Hossein
authors.initials: H
authors.lastname: Robatjazi
authors.affiliation: Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544;
authors.forename: John Mark P
authors.initials: JM
authors.lastname: Martirez
authors.affiliation: Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544;
authors.forename: Caroline M
authors.initials: CM
authors.lastname: Krauter
authors.affiliation: Department of Material Science and Nanoengineering, Rice University, Houston, TX 77005;
authors.forename: Sadegh
authors.initials: S
authors.lastname: Yazdi
authors.affiliation: Department of Chemistry, Rice University, Houston, TX 77005;
authors.forename: Michael J
authors.initials: MJ
authors.lastname: McClain
authors.affiliation: Department of Chemistry, Rice University, Houston, TX 77005; Department of Material Science and Nanoengineering, Rice University, Houston, TX 77005;
authors.forename: Emilie
authors.initials: E
authors.lastname: Ringe
authors.affiliation: Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544; Program in Applied and Computational Mathematics, Princeton University, Princeton, NJ 08544; Andlinger Center for Energy and the Environment, Princeton University, Princeton, NJ 08544;
authors.forename: Emily A
authors.initials: EA
authors.lastname: Carter
authors.affiliation: Department of Electrical and Computer Engineering, Rice University, Houston, TX 77005; Department of Material Science and Nanoengineering, Rice University, Houston, TX 77005; Department of Physics and Astronomy, Rice University, Houston, TX 77005 halas@rice.edu nordland@rice.edu.
authors.forename: Peter
authors.initials: P
authors.lastname: Nordlander
authors.affiliation: Department of Chemistry, Rice University, Houston, TX 77005; Department of Electrical and Computer Engineering, Rice University, Houston, TX 77005; Department of Material Science and Nanoengineering, Rice University, Houston, TX 77005; Department of Physics and Astronomy, Rice University, Houston, TX 77005 halas@rice.edu nordland@rice.edu.
authors.forename: Naomi J
authors.initials: NJ
authors.lastname: Halas
keywords: aluminum; catalysis; nanoparticle; photocatalysis; plasmon