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

Abstract

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° and 180° trimer configurations. The photocatalytic reactions H2 + D2 → 2HD and NH3 + D2 → NH2D + HD were both investigated on these nanostructured complexes. While the H2–D2 exchange reaction showed an additive behavior for the linear (180°) nanodisk complex, the NH3 + D2 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.

First-Principles Insights into the Thermocatalytic Cracking of Ammonia-Hydrogen Blends on Fe(110): 1. Thermodynamics

“…Fe, orange; N, blue; H, gray. Inset structures were adapted with permission from ref . Copyright 2022 American Chemical Society.…”

“…Orange sphere, Fe; dark blue, N; white, H. (b) Cumulative free energy for the formation of ( m – n )*NH + n *N + false( 2 m + n false) 2 H 2 ( g ) from m NH 3 (eq ) for m = 3 and n = 0 (pure NH) to 3 (pure N) at the temperatures of near degeneracy for these two species (Figure ) and at the same equilibrium partial pressures as in Figure ( P total of 2 bar (initial NH 3 :H 2 = 9:1)). Structures were adapted with permission from ref . Copyright 2022 American Chemical Society.…”

“…N and NH adsorb at long-bridge and hollow sites, whereas H adsorbs exclusively at hollow sites. Orange sphere, Fe; dark blue, N; white, H. Adapted with permission from ref . Copyright 2022 American Chemical Society.…”

Active Site Engineering on Plasmonic Nanostructures for Efficient Photocatalysis

“…142 Following a similar process, an Al−Pd−Fe heterotrimer was obtained by integrating plasmonic Al with two active sites (Pd and Fe). 143 By simply varying the evaporation angle, the relative distance and orientation between different metal active sites and Al can be precisely controlled. With these clear catalyst structures, the authors were able to study the influence of the polarization angle of the incident light on plasmonic photocatalysis using some model reactions (e.g., H 2 −D 2 exchange reaction).…”

“…For example, Halas and co-workers prepared Al–Pd nanodisk heterodimers by sequentially evaporating Al (plasmonic metal) and Pd (active site) onto the substrate with the assistance of an Au hole mask fabricated by lithography (Figure b) . Following a similar process, an Al–Pd–Fe heterotrimer was obtained by integrating plasmonic Al with two active sites (Pd and Fe) . By simply varying the evaporation angle, the relative distance and orientation between different metal active sites and Al can be precisely controlled.…”