Charge Transport Surmounting Hierarchical Ligand Confinement toward Multifarious Photoredox Catalysis

Metal nanoparticles (NPs) have been deemed an imperative sector of nanomaterial for triggering the Schottky-junction-driven electron flow in photoredox catalysis, but they suffer from sluggish charge-transfer kinetics, rendering efficient charge flow difficult. Here, we report the construction of unidirectional charge-transfer channel in a metal/semiconductor heterostructure via a ligand-triggered self-assembly method, by which hierarchically branched ligands (DMAP)-capped Pd NPs were controllably attached on the WO₃ nanorods (NRs) scaffold, resulting in the well-defined Pd@DMAP/WO₃ NRs heterostructures. The pinpointed deposition of Pd@DMAP on the WO₃ NRs endows the Pd@DMAP/WO₃ NRs heterostructure with conspicuously improved photoactivities for organic pollutant mineralization, as well as the capacities for photocatalytic selective oxidation of aromatic alcohols to aldehydes and photoreduction of chromium ions under the irradiation of simulated sunlight and visible light, far surpassing the applicability of blank WO₃ NRs. This is due to the imperative contribution of Pd@DMAP as efficient electron reservoir in accelerating the unidirectional flow of electrons from Pd@DMAP to WO₃ NRs, overcoming the confinement of spatially hierarchically branched ligand and interface configuration. Moreover, interfacial charge transport efficiency is finely tuned by the interface configuration engineering. The active species in the multifarious photoreactions were unveiled, and a linker-triggered photoredox catalysis mechanism was put forward. It is hoped that our current work would afford new strategies for strategically constructing metal/semiconductor heterostructures for versatile photocatalytic applications.