Pt₁₄₇ Nanoclusters Soft-Landed on WS₂ Nanosheets for Catalysis and Energy Harvesting

Abstract

Understanding the interaction between metal nanoclusters and two-dimensional (2D) layered materials presents a route toward the creation and tuning of hybrid materials. Here, we synthesize hybrid materials composed of mass-selected platinum nanoclusters produced using a magnetron sputtering gas aggregation cluster beam source with a lateral time-of-flight mass filter (mass resolution M/ΔΜ = 20) and large-area tungsten disulfide (WS2) 2D atomic layers. We employ aberration-corrected scanning transmission electron microscopy (STEM) in high-angle annular dark-field (HAADF) mode and micro-Raman spectroscopy to study the interaction between Pt147 and suspended WS2 atomic layers. HAADF-STEM analysis reveals that soft-landed Pt147 nanoclusters are situated on top of few-layered WS2 stacks, rather than being embedded or pinned. We observed a red shift in both E2g and A1g modes and striking enhancement of A1g mode in the micro-Raman signatures of WS2, which provide evidence that Pt147 clusters are soft-landed on the WS2 basal plane without disrupting the crystalline structure of the WS2 and of charge transfer from Pt147 to WS2, respectively. In contrast, the measured change in line width of the E2g mode of WS2 reveals a strong interaction between Pt147 and WS2 layers. Direct evidence for the relative stability of Pt147 clusters on WS2 is assessed by position-dependent Raman profiling and real-time HAADF-STEM imaging. Our approach offers a novel route to the controlled incorporation of size-selected nanoclusters on the 2D WS2 basal plane for catalysis and energy harvesting device applications.

Electron beam-induced demetallation of Fe, Co, Ni, Cu, Zn, Pd, and Pt metalloporphyrins: insights in e-beam chemistry and metal cluster formations

“…The grids were then dried in vacuum (10 À3 mbar) before being subjected to TEM analysis. Compared to previously published metal atom deposition techniques, such as thermal evaporation, 33 e-beam deposition, 34 soft-landing deposition, 35 atomic layer deposition, 36 chemical vapor deposition, 37 or magnetron sputtering, 38 our solution-based deposition is a highly versatile and easily accessible method that does not require any additional equipment. We initiated our investigation with PtTPP, which features the Pt in the +II oxidation state.…”

Enhanced magnetic anisotropy of iridium dimers on antisite defects of two-dimensional transition-metal dichalcogenides

“…24 Experimentally, the feasible methods of formatting ultrasmall clusters on 2D materials have been reported. These include deposition of atoms on graphene substrates with further growth to clusters; 25 direct deposition of clusters on WS 2 substrates through a cluster-beam process; 26 direct etching of 2D metal selenide to create Mo on MoSe 2 atom-by-atom; 27 dropping ligand-protected clusters on 2D material substrates. 28 Consequently, it is expected that a combination of a TM dimer and TMD nanosheets will also enhance the MAE of the composite system.…”

Atomically Precise Platinum Carbonyl Nanoclusters: Synthesis, Total Structure, and Electrochemical Investigation of [Pt27(CO)31]4– Displaying a Defective Structure

“…Atomically precise metal nanoclusters have attracted impressive interest since the discovery of the thiolate-protected Au 102 . − Most of the literature has been dedicated to molecular Au nanoclusters and then to Cu and Ag nanoclusters as well as related molecular alloy nanoclusters. − The researches on atomically precise Pt nanoclusters have also grown, in view of the widespread use of Pt complexes, nanoparticles, and crystallites in catalysis and electrocatalysis. − Gaining atomic precision on Pt nanoclusters dispersed on supports and electrode materials would offer the possibility of increasing our knowledge on the fundamental steps involved in catalytic and electrocatalytic processes. − Moreover, the properties of such materials could be improved and finely tuned depending on the dimension and structure of the Pt nanoclusters.…”