Selective Enhancement of Surface and Bulk E‑Field within Porous AuRh and AuRu Nanorods

A variety of multisegmented nanorods (NRs) composed of dense Au and porous Rh and Ru segments with lengths controlled down to ca. 10 nm are synthesized within porous anodic aluminum oxide membranes. Despite the high Rh and Ru porosity (i.e., ∼40%), the porous metal segments are able to efficiently couple with the longitudinal localized surface plasmon resonance (LSPR) of Au NRs. Finite-difference time-domain simulations show that the LSPR wavelength can be precisely tuned by adjusting the Rh and Ru porosity. Additionally, light absorption inside Rh and Ru segments and the surface electric field (E-field) at Rh and Ru can be independently and selectively enhanced by varying the position of the Rh and Ru segment within the Au NR. The ability to selectively control and decouple the generation of high-energy, surface hot electrons and low-energy, bulk hot electrons within photocatalytic metals such as Rh and Ru makes these bimetallic structures great platforms for fundamental studies in plasmonics and hot-electron science.