We interfaced β-Pbx/β'-CuyV2O5 compounds, with varying stoichiometries of precisely positioned Pb-ions (x) and Cu-ions (y) in interstitial sites along a tunnel-structured ζ-V2O5 framework, with cysteine-capped CdS (cysCdS) quantum dots (QDs) to yield heterostructured photocatalysts. β-Pbx/β'-CuyV2O5 compounds exhibit midgap electronic states with orbital contributions from both Cu 3d and stereochemically active Pb 6s states that show distinctive light-initiated reactivity with photoexcited QDs. β-Pbx/β'-CuyV2O5/CdS heterostructures were prepared by linker-assisted assembly (LAA). Scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy revealed that cysCdS QDs were deposited onto surfaces of β-Pbx/β'-CuyV2O5 via LAA. HAXPES revealed that the site-selective positioning of Pb-ions and Cu-ions promoted close energetic alignment of the midgap states of β-Pbx/β'-CuyV2O5 compounds with the valence-band maximum of cysCdS QDs. Transient absorption spectroscopy revealed that photogenerated holes were transferred from CdS QDs to midgap states of β-Pbx/β'-CuyV2O5 compounds on time scales <50 ps. Finally, photoelectrochemical and photochemical experiments revealed that β-Pbx/β'-CuyV2O5/CdS heterostructures promoted the photocatalytic reduction of H+ to H2. In photoelectrochemical experiments, under oxidative conditions, for all β-Pbx/β'-CuyV2O5/CdS heterostructures, H2 was evolved at a Pt counter electrode while a sacrificial donor was oxidized at the heterostructure-functionalized working electrode. In contrast, under reductive conditions, for β-Pb0.152V2O5/CdS and β-Pbx/β'-CuyV2O5/CdS heterostructures, H2 was evolved at the working electrode. In photochemical experiments, dispersed β-Pbx/β'-CuyV2O5/CdS heterostructures promoted the reduction of H+ to H2 under white-light illumination; β'-Cu0.55V2O5/CdS and β-Pbx/β'-CuyV2O5/CdS heterostructures, for which midgap states have Cu 3d orbital character, generated 2-fold more H2 than β-Pb0.152V2O5/CdS heterostructures. Cu-ion insertion thus appends additional acceptor surface states that improve ligand-mediated hole transfer from photoexcited QDs, but such states are intrinsically limited in mediating hole transport to the substrate as a result of the low mobility of holes in narrow Cu 3d-states. Our results reveal that the density and orbital character of midgap states of β-Pbx/β'-CuyV2O5 compounds, tunable through recently developed site-selective ion insertion strategies, determine efficiencies of charge-transfer and charge-transport mechanisms that underpin photocatalysis.
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