Research Article Online first
Rationally construction of atomic-precise interfacial charge transfer channel and strong build-in electric field in nanocluster-based Z-scheme heterojunctions with enhanced photocatalytic hydrogen production
Nano Research
Published: 29 February 2024

The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters (NC)-based heterostructures, resulting in poor photocatalytic performance. Herein, a Z-scheme NC-based heterojunction (Pt1Ag28-BTT/CoP, BTT = 1,3,5-benzenetrithiol) with strong internal electric field is constructed via interfacial Co–S bond, which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h−1·g−1 H2 production rate, 25.77% apparent quantum yield at 420 nm, and ~ 100% activity retention in stability, compared with Pt1Ag28-BDT/CoP (BDT = 1,3-benzenedithiol), Ag29-BDT/CoP, and CoP. The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC, wherein, the center Pt single atom doping regulates the band structure of NC to match well with CoP, builds internal electric field, and then drives photogenerated electrons steering; the accurate surface S modification promotes the formation of Co–S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration. This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.

Open Access Research Article Issue
Ligand-correlated crystalline assembly of nanoclusters with atomic precision
Polyoxometalates 2023, 2 (4): 9140035
Published: 22 September 2023

Understanding the assembly pattern of metal nanoclusters in crystalline units at the atomic level is crucial for an in-depth understanding of their supramolecular interactions and structure–property correlations. In this study, two Au9Ag6 nanoclusters bearing a similar framework were controllably synthesized and structurally determined. By tailoring the peripheral thiol ligands from SPhpOMe to SPhoMe (HSPhpOMe = 4-methoxythiophenol, HSPhoMe = 2-methylbenzenethiol), the hierarchical assembly of cluster molecules in their superlattice varied from “ABAB” to “ABCDABCD”. Based on the atomically precise structures of the two nanoclusters, we proposed that such differences in crystalline packing modes resulted from a combination of their structural differences, including intramolecular coordination preferences (Au–P vs. Ag–Cl), steric hindrance effects of thiol ligands (SPhpOMe vs. SPhoMe), and intra-/inter-cluster interactions (C–H···π, π···π, and H···H). We also investigated the structure/assembly-dependent optical properties of the two clusters at different states and rationalized the obtained structure–property correlations at the atomic level. Moreover, this study presented an interesting case for analyzing the hierarchical assembly of metal nanoclusters, allowing an in-depth understanding of the ligand effect on the crystalline assemblies of metal nanoclusters with atomic precision.

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