Michelle A. Nguyen, Elsayed M. Zahran, Azaan S. Wilbon, Alexander V. Besmer, Vincent J. Cendan, William A. Ranson, Randy L. Lawrence, Joshua L. Cohn, Leonidas G. Bachas, Marc R. Knecht

We report a synthetic approach to form cubic Cu2O/Pd composite structures and demonstrate their use as photocatalytic materials for tandem catalysis. Pd nanoparticles were deposited onto Cu2O cubes, and their tandem catalytic reactivity was studied via the reductive dehalogenation of polychlorinated biphenyls. The Pd content of the materials was gradually increased to examine its influence on particle morphology and catalytic performance. Materials were prepared at different Pd amounts and demonstrated a range of tandem catalytic reactivity. H2 was generated via photocatalytic proton reduction initiated by Cu2O, followed by Pd-catalyzed dehalogenation using in situ generated H2. The results indicate that material morphology and composition and substrate steric effects play important roles in controlling the overall reaction rate. Additionally, analysis of the postreacted materials revealed that a small number of the cubes had become hollow during the photodechlorination reaction. Such findings offer important insights regarding photocatalytic active sites and mechanisms, providing a pathway toward converting light-based energy to chemical energy for sustainable catalytic reactions not typically driven via light.