Linker-Assisted Assembly of Ligand-Bridged CdS/MoS Heterostructures: Tunable Light-Harvesting Properties and Ligand-Dependent Control of Charge-Transfer Dynamics and Photocatalytic Hydrogen Evolution.

We used linker-assisted assembly (LAA) to tether CdS quantum dots (QDs) to MoS nanosheets via -cysteine () or mercaptoalkanoic acids (MAAs) of varying lengths, yielding ligand-bridged CdS/MoS heterostructures for redox photocatalysis. LAA afforded precise control over the light-harvesting properties of QDs within heterostructures. Photoexcited CdS QDs transferred electrons to molecularly linked MoS nanosheets from both band-edge and trap states; the electron-transfer dynamics was tunable with the properties of bridging ligands. Rate constants of electron transfer, estimated from time-correlated single photon counting (TCSPC) measurements, ranged from (9.8 ± 3.8) × 10 s for the extraction of electrons from trap states within heterostructures incorporating the longest MAAs to >5 × 10 s for the extraction of electrons from band-edge or trap states in heterostructures with or 3-mercaptopropionic acid (3MPA) linkers. Ultrafast transient absorption measurements revealed that electrons were transferred within 0.5-2 ps or less for CdS--MoS and CdS-3MPA-MoS heterostructures, corresponding to rate constants ≥5 × 10 s. Photoinduced CdS-to-MoS electron transfer could be exploited in photocatalytic hydrogen evolution reaction (HER) via the reduction of H to H in concert with the oxidation of lactic acid. CdS--MoS-functionalized FTO electrodes promoted HER under oxidative conditions wherein H was evolved at a Pt counter electrode with Faradaic efficiencies of 90% or higher and under reductive conditions wherein H was evolved at the CdS--MoS-heterostructure-functionalized working electrode with Faradaic efficiencies of 25-40%. Dispersed CdS--MoS heterostructures promoted photocatalytic HER (15.1 μmol h) under white-light illumination, whereas free -capped CdS QDs produced threefold less H and unfunctionalized MoS nanosheets produced no measurable H. Charge separation across the CdS/MoS interface is thus pivotal for redox photocatalysis. Our results reveal that LAA affords tunability of the properties of constituent CdS QDs and MoS nanosheets and precise, programmable, ligand-dependent control over the assembly, interfacial structure, charge-transfer dynamics, and photocatalytic reactivity of CdS--MoS heterostructures.