Heterometallic antenna–reactor complexes for photocatalysis

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 l...

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Published inProceedings of the National Academy of Sciences - PNAS Vol. 113; no. 32; pp. 8916 - 8920
Main Authors Swearer, Dayne F., Zhao, Hangqi, Zhou, Linan, Zhang, Chao, Robatjazi, Hossein, Martirez, John Mark P., Krauter, Caroline M., Yazdi, Sadegh, McClain, Michael J., Ringe, Emilie, Carter, Emily A., Nordlander, Peter, Halas, Naomi J.
Format Journal Article
LanguageEnglish
Published United States National Academy of Sciences 09.08.2016
Subjects
Catalysis
Chemical reactions
Desorption
Ethylene
Nanocrystals
Nanoparticles
Physical Sciences
catalysis
nanoparticle
aluminum
photocatalysis
plasmon
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Summary: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.
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Reviewers: M.M., University of California, Santa Barbara; and W.D.W., University of Florida.
Contributed by Naomi J. Halas, June 20, 2016 (sent for review May 31, 2016; reviewed by Martin Moskovits and Wei David Wei)
Author contributions: P.N. and N.J.H. designed research; D.F.S., H.Z., L.Z., C.Z., H.R., J.M.P.M., C.M.K., S.Y., and M.J.M. performed research; D.F.S., H.Z., J.M.P.M., C.M.K., E.R., E.A.C., P.N., and N.J.H. analyzed data; D.F.S., H.Z., J.M.P.M., C.M.K., E.R., E.A.C., P.N., and N.J.H. wrote the paper; D.F.S., S.Y., and E.R. performed STEM-EELS experiments; and P.N. and N.J.H. conceived the antenna−reactor concept.
ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.1609769113