(627a) Computational Discovery of Design Principles for Cu Alloy Plasmonic Photocatalysts

Plasmonic “antenna reactor” alloys consist of a plasmonic material doped with a catalytically active metal, and have shown strong photocatalytic performance for multiple important reactions. However, simple design principles for these materials remain elusive, which slows down development of improved systems. Here, we use dynamic, real-time time-dependent density functional theory (RT-TDDFT) simulations to calculate trends in small molecule activation on Cu-based antenna reactors. We then develop simple principles for rationalizing and predicting these trends.

Specifically, we studied the activation of four catalytically important small molecules (CH₄, CO₂, H₂O and N₂) on a series of Cu nanoparticles doped with active metals. For each system, we performed RT-TDDFT simulations to study bond activation when the system is exposed to light (i.e., an oscillating electric field). The trends in bond activation vary for different molecules, indicating that it is not purely the nanoparticle properties that affect photoactivation, but instead the molecule-nanoparticle interaction. We found that the magnitude of charge oscillations between the molecule and nanoparticle is well correlated with bond activation, providing a simple rationalization of trends. We also found that the orbital overlap between the molecule and dopant correlates with the bond activation, which provides an intuitive and computationally simple method for initial screening of antenna reactors.