The journal Nanoscale Horizons features on its inside front cover the recently published research article “Supramolecular nanocapsules as two-fold stabilizers of outer-cavity sub-nanometric Ru NPs and inner-cavity ultra-small Ru clusters”, a collaboration between Université de Toulouse and the group of Xavi Ribas.
The synthesis of metallic nanoparticles (MNP) with high surface area and controlled shape is of paramount importance to increase their catalytic performance. The detailed growing process of NP is mostly unknown and understanding the specific steps would pave the way for a rational synthesis of the desired MNP. Here we take advantage of the stabilization properties exerted by the tetragonal prismatic supramolecular nanocapsule 8(BArF)8 to develop a synthetic methodology for sub-nanometric RuNP (0.6–0.7 nm). The catalytic properties of these sub-nanometric nanoparticles were tested on the hydrogenation of styrene, obtaining excellent selectivity for the hydrogenation of the alkene moiety. In addition, the encapsulation of [Ru5] clusters inside the nanocapsule is strikingly observed in most of the experimental conditions, as ascertained by HR-MS. Moreover, a thorough DFT study enlightens the nature of the [Ru5] clusters as tb-Ru5H2(g6-PhH)2(g6-pyz)3 (2) trapped by two arene moieties of the clip, or as tb-Ru5H2(g1-pyz)6(g6-pyz)3 (3) trapped between the two Zn–porphyrin units of the nanocapsule. Both options fulfill the Wade-Mingos counting rules, i.e. 72 CVEs for the closo tb. The trapped [Ru5] metallic clusters are proposed to be the first-grown seeds of subsequent formation of the subnanometric RuNP. Moreover, the double role of the nanocapsule in stabilising B0.7 nm NPs and also in hosting ultra-small Ru clusters, is unprecedented and may pave the way towards the synthesis of ultrasmall metallic clusters for catalytic purposes.
The corresponding paper was published recently in Nanoscale Horizons:
E. Ubasart, I. Mustieles Marin, J.M. Asensio, G. Mencia, Á.M. López-Vinasco, C. García-Simón, I. del Rosal, R. Poteau, B. Chaudret and X. Ribas
“Supramolecular nanocapsules as two-fold stabilizers of outer-cavity sub-nanometric Ru NPs and inner-cavity ultra-small Ru clusters”
Nanoscale Horiz. 2022, 7, 607-615
DOI: 10.1039/D1NH00677K
Girona, June 8, 2022
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