Photoactivation of catalytic materials through plasmon-coupled energy transfer has created new possibilities for expanding the scope of light-driven heterogeneous catalysis. Here we present a nanoengineered plasmonic photocatalyst consisting of catalytic Pd islands preferentially grown on vertices of Al nanocubes. The regioselective Pd deposition on Al nanocubes does not rely on complex surface ligands, in contrast to site-specific transition-metal deposition on gold nanoparticles. We show that the strong local field enhancement on the sharp nanocube vertices provides a mechanism for efficient coupling of the plasmonic Al antenna to adjacent Pd nanoparticles. A substantial increase in photocatalytic H2 dissociation on Pd-bound Al nanocubes relative to pristine Al nanocubes can be observed, incentivizing further engineering of heterometallic antenna-reactor photocatalysts. Controlled growth of catalytic materials on plasmonic hot spots can result in more efficient use of the localized surface plasmon energy for photocatalysis, while minimizing the amount and cost of precious transition-metal catalysts.
Keywords: aluminum nanocubes; antenna−reactor; plasmonic photocatalysis; regioselective growth.