Elucidating the Mechanistic Origins of Photocatalytic Hydrogen Evolution Mediated by MoS₂/CdS Quantum-Dot...

Solar fuel generation mediated by semiconductor heterostructures represents a promising strategy for sustainable energy conversion and storage. The design of semiconductor heterostructures for photocatalytic energy conversion requires the separation of photogenerated charge carriers in real space and their delivery to active catalytic sites at the appropriate overpotentials to initiate redox reactions. Operation of the desired sequence of light harvesting, charge separation, and charge transport events within heterostructures is governed by the thermodynamic energy offsets of the two components and their photoexcited charge-transfer reactivity, which determine the extent to which desirable processes can outcompete unproductive recombination channels. Here, we map energetic offsets and track the dynamics of electron transfer in MoS₂/CdS architectures, prepared by interfacing two-dimensional MoS₂ nanosheets with CdS quantum dots (QDs), and correlate the observed charge separation to photocatalytic activity in the hydrogen evolution reaction. The energetic offsets between MoS₂ and CdS have been determined using hard and soft X-ray photoemission spectroscopy (XPS) in conjunction with density functional theory. A staggered type-II interface is observed, which facilitates electron and hole separation across the interface. Transient absorption spectroscopy measurements demonstrate ultrafast electron injection occurring within sub-5 ps from CdS QDs to MoS₂, allowing for creation of a long-lived charge-separated state. The increase of electron concentration in MoS₂ is evidenced with the aid of spectroelectrochemical measurements and by identifying the distinctive signatures of electron-phonon scattering in picosecond-resolution transient absorption spectra. Ultrafast charge separation across the type-II interface of MoS₂/CdS heterostructures enables a high Faradaic efficiency of ∼99.4 ± 1.2% to be achieved in the hydrogen evolution reaction (HER) and provides a 40-fold increase in the photocatalytic activity of dispersed photocatalysts for H₂ generation. The accurate mapping of thermodynamic driving forces and dynamics of charge transfer in these heterostructures suggests a means of engineering ultrafast electron transfer and effective charge separation to design viable photocatalytic architectures.