Plasmonic Metal Mediated Charge Transfer in Stacked Core-Shell Semiconductor Heterojunction for Significantly...

Construction of core-shell semiconductor heterojunctions and plasmonic metal/semiconductor heterostructures represents two promising routes to improved light harvesting and promoted charge separation, but their photocatalytic activities are respectively limited by sluggish consumption of charge carriers confined in the cores, and contradictory migration directions of plasmon-induced hot electrons and semiconductor-generated electrons. Herein, a semiconductor/metal/semiconductor stacked core-shell design is demonstrated to overcome these limitations and significantly boost the photoactivity in CO₂  reduction. In this smart design, sandwiched Au serves as a "stone", which "kills two birds" by inducing localized surface plasmon resonance for hot electron generation and mediating unidirectional transmission of conduction band electrons and hot electrons from TiO₂  core to MoS₂  shell. Meanwhile, upward band bending of TiO₂  drives core-to-shell migration of holes through TiO₂ -MoS₂  interface. The co-existence of TiO₂  → Au → MoS₂  electron flow and TiO₂  → MoS₂  hole flow contributes to spatial charge separation on different locations of MoS₂  outer layer for overall redox reactions. Additionally, reduction potential of photoelectrons participating in the CO₂  reduction is elaborately adjusted by tuning the thickness of MoS₂  shell, and thus the product selectivity is delicately regulated. This work provides fresh hints for rationally controlling the charge transfer pathways toward high-efficiency CO₂  photoreduction.