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Two Hybrid Nanoclusters of Noble-metal and Titanium Oxide Display Structure Dependent Optical Limiting Effects

Jun 12, 2018

TiO2 has been widely used as supports of noble-metal (e.g. Au, Ag, Pt) nanoparticles with photo or catalytic applications. Thus, the introduction of noble-metal to titanium-oxo clusters with direct Mx-TimOn interactions can act as real molecular models to understand strong metal-support interactions. However, the molecular combination of noble-metal and semiconductive nanoclusters remains a challenge.

Recently, Prof. ZHANG Jian’s group at Fujian Institute of Research on the Structure of Matter of Chinese Academy of Sciences successfully obtained the first two hybrid nanoclusters of noble-metal and titanium oxide which display structure dependent optical limiting effects. The study was published in Angew. Chem. Int. Ed. 

In these two clusters, the octahedral Ag6 core with strong Ag-Ag interactions was encapsulated by Ti16-oxo shell through direct Ag-O-Ti coordination interactions. The hybrid cluster core was further stabilized by benzoate ligands, forming a triple core–shell construction of Ag6@Ti16@(benzoate)26.

The relative configuration of the Ag6 core inside the Ti-O cavity presented about 45o rotation in the two clusters, which further influences their optical limiting effects.

Moreover, the transmittance reduction effect exhibited nearly linear dependence on concentration, and the transmittance at 532 nm laser can be reduced to a minimum of 57%, making these hybrid clusters potential candidates for the fabrication of future optical limiting devices.

The study presented a breakthrough in the construction of hybrid noble-metal/Ti-O nanoclusters.

Noble-metal and semiconductive nanoclusters with atomically precise structures have great potential for their structural and reactive models.

 

Illustration of the Ag6@Ti16-Oxo core-shell nanostructure (Image by Prof. ZHANG’s group) 

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