Inverted temperature gradients in gold-palladium antenna-reactor nanoparticles

In addition to enhanced fields and possible charge transfer, the concentration of photothermal energy at the nanoscale is a central feature of plasmon-driven photochemistry. It is well known that light energy can be efficiently concentrated in metal nanoparticles to length scales far below the wavelength of light. Here we demonstrate that the energy absorbed by a gold nanoparticle can be further localized within a bimetallic gold-paladium nanoparticle system by the dissipation of energy into the attached palladium satellite nanoparticles. After pulsed excitation of the gold core, the satellites collect nearly all photothermal energy and heat up by 180 K while the light-absorbing gold core remains much colder. By comparing transient absorption dynamics of a series of bimetallic nanoparticles with a three-temperature model, we can precisely assess the temperatures of the electronic and vibrational subsystems. We find a strong inverted temperature gradient that opposes the direction of energy input and concentrates the light energy at the active catalytic nanosite.