Abstract
Ultrafine metal nanoparticles (MNPs) with size <2 nm are of great interest due to their superior catalytic capabilities. Herein, we report the size-controlled synthesis of gold nanoparticles (Au NPs) by using a thiacalixarene-based coordination cage CIAC-108 as a confined host or stabilizer. The Au NPs encapsulated within the cavity of CIAC-108 (Au@CIAC-108) show smaller size (∼1.3 nm) than the ones (∼4.7 nm) anchored on the surface of CIAC-108 (Au/CIAC-108). The cage-embedded Au NPs can be used as a homogeneous catalyst in a mixture of methanol and dichloromethane while as a heterogeneous catalyst in methanol. The homogeneous catalyst Au@CIAC-108-homo exhibits significantly enhanced catalytic activities toward nitroarene reduction and organic dye decomposition, as compared with its larger counterpart Au/CIAC-108-homo and its heterogeneous counterpart Au@CIAC-108-hetero. More importantly, the as-prepared Au@CIAC-108-homo possesses remarkable stability and durability.
Highlights
CIAC-108 is synthesized according to a modi ed literature method.[60]
Fourier transform infrared (FT-IR) spectra of the product are all consistent with those previously reported (Fig. S1†), con rming the successful formation of CIAC-108
Power X-ray diffraction (PXRD) measurements demonstrate that desolvated CIAC-108 shows weak diffraction peaks in the range 5–50 in which the crystal X-ray diffraction data are collected owing to the loss of crystallinity upon solvent removal (Fig. S2†)
Summary
The homogeneous catalyst Au@CIAC-108-homo exhibits remarkable catalytic activity for various chemical transformations, along with excellent stability and durability that there is no signi cant decline in catalytic performance over 6 cycles. The Au/CIAC-108-homo counterpart with larger particle sizes exhibits lower catalytic activity with 62.5% conversion in 90 min (n(Au)/n(4-NPh) 1⁄4 1/156) (Fig. 3b).
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