4.8 Article

Plasmonic Photocatalysis with Chemically and Spatially Specific Antenna-Dual Reactor Complexes

Journal

ACS NANO
Volume 16, Issue 10, Pages 17365-17375

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsnano.2c08191

Keywords

plasmonic; photocatalysis; antenna-reactor; ammonia; synergistic effect

Funding

  1. Robert A. Welch Foundation [C-1220, C-1222]
  2. Defense Threat Reduction Agency-Joint Science and Technology Office for Chemical and Biological Defense Basic Research [HDTRA 1-16-1-0042]
  3. Air Force Office of Science and Research [FA9550-15-1-0022]

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Investigated planar plasmonic antenna-reactor photocatalysts with two chemically distinct and spatially separated active sites, demonstrating different effects of reaction positioning. This study is important for precise control of complex chemical reactions.
Plasmonic antenna-reactor photocatalysts have been shown to convert light efficiently to chemical energy. Virtually all chemical reactions mediated by such complexes to date, however, have involved relatively simple reactions that require only a single type of reaction site. Here, we investigate a planar Al nanodisk antenna with two chemically distinct and spatially separated active sites in the form of Pd and Fe nanodisks, fabricated in 90 degrees and 180 degrees trimer configurations. The photocatalytic reactions H-2 + D-2 -> 2HD and NH3 + D-2 -> NH2D + HD were both investigated on these nanostructured complexes. While the H-2-D-2 exchange reaction showed an additive behavior for the linear (180 degrees) nanodisk complex, the NH3 + D-2 reaction shows a clear synergistic effect of the position of the reactor nanodisks relative to the central Al nanodisk antenna. This study shows that light-driven chemical reactions can be performed with both chemical and spatial control of the specific reaction steps, demonstrating precisely designed antennas with multiple reactors for tailored control of chemical reactions of increasing complexity.

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