Linker-Assisted Assembly of Ligand-Bridged CdS/MoS2 Heterostructures: Tunable Light-Harvesting Properties and Ligand-Dependent Control of Charge-Transfer Dynamics and Photocatalytic Hydrogen EvolutionClick to copy article linkArticle link copied!
- Arianna R.M. RothfussArianna R.M. RothfussDepartment of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, United StatesMore by Arianna R.M. Rothfuss
- Jaime R. AyalaJaime R. AyalaDepartment of Chemistry, Texas A&M University, College Station, Texas 77843-3012, United StatesDepartment of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843-3012, United StatesMore by Jaime R. Ayala
- Joseph V. HandyJoseph V. HandyDepartment of Chemistry, Texas A&M University, College Station, Texas 77843-3012, United StatesDepartment of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843-3012, United StatesMore by Joseph V. Handy
- Caitlin R. McGranahanCaitlin R. McGranahanDepartment of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, United StatesMore by Caitlin R. McGranahan
- Karoline E. García-PedrazaKaroline E. García-PedrazaDepartment of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, United StatesMore by Karoline E. García-Pedraza
- Sarbajit Banerjee*Sarbajit Banerjee*Email: [email protected]Department of Chemistry, Texas A&M University, College Station, Texas 77843-3012, United StatesDepartment of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843-3012, United StatesMore by Sarbajit Banerjee
- David F. Watson*David F. Watson*Email: [email protected]Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, United StatesMore by David F. Watson
Abstract
We used linker-assisted assembly (LAA) to tether CdS quantum dots (QDs) to MoS2 nanosheets via L-cysteine (cys) or mercaptoalkanoic acids (MAAs) of varying lengths, yielding ligand-bridged CdS/MoS2 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 MoS2 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) × 106 s–1 for the extraction of electrons from trap states within heterostructures incorporating the longest MAAs to >5 × 109 s–1 for the extraction of electrons from band-edge or trap states in heterostructures with cys or 3-mercaptopropionic acid (3MPA) linkers. Ultrafast transient absorption measurements revealed that electrons were transferred within 0.5–2 ps or less for CdS-cys-MoS2 and CdS-3MPA-MoS2 heterostructures, corresponding to rate constants ≥5 × 109 s–1. Photoinduced CdS-to-MoS2 electron transfer could be exploited in photocatalytic hydrogen evolution reaction (HER) via the reduction of H+ to H2 in concert with the oxidation of lactic acid. CdS-L-MoS2-functionalized FTO electrodes promoted HER under oxidative conditions wherein H2 was evolved at a Pt counter electrode with Faradaic efficiencies of 90% or higher and under reductive conditions wherein H2 was evolved at the CdS-L-MoS2-heterostructure-functionalized working electrode with Faradaic efficiencies of 25–40%. Dispersed CdS-L-MoS2 heterostructures promoted photocatalytic HER (15.1 μmol h–1) under white-light illumination, whereas free cys-capped CdS QDs produced threefold less H2 and unfunctionalized MoS2 nanosheets produced no measurable H2. Charge separation across the CdS/MoS2 interface is thus pivotal for redox photocatalysis. Our results reveal that LAA affords tunability of the properties of constituent CdS QDs and MoS2 nanosheets and precise, programmable, ligand-dependent control over the assembly, interfacial structure, charge-transfer dynamics, and photocatalytic reactivity of CdS-L-MoS2 heterostructures.
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