Search for: All records

Abstract Ceria (CeO 2 ) possesses a distinctive redox property due to a reversible conversion to its nonstoichiometric oxide and has been considered as a promising catalyst in the oxidative coupling of methane. Since a heterogeneously catalytic process usually takes place only on the surface of catalysts, it is reasonably expected that the performance of a catalyst, such as CeO 2 , highly relies on its size- and shape-dependent surface structure. We report our recent progress in achieving exclusive crystal facet-terminated CeO 2 nanocrystals using a shape-controlled synthesis protocol in a one-pot colloidal system. We modified a two-phase solvothermal approach to fabricate cubic and truncated octahedral CeO 2 nanocrystals with a size-control. During the two-phase solvothermal process, we propose that the Ce-precursors transfer from the aqueous layer to the interface of the organic phase, promoted by the capping ligands (as known as phase-transfer catalysts), for the oxidation and nucleation, and subsequently form CeO 2 nanocrystals in the organic layer. As different capping ligands favor binding on diverse crystal facets, tuning the composition of the capping ligand with a precise control could generate nanocrystals that are dominated by a single type of facets with a relatively narrow size distribution. 

ABSTRACT We report a facile method to fabricate CuNi nano-octahedra and nanocubes using a colloidal synthesis approach. The CuNi nanocrystals terminated with exclusive crystallographic facets were controlled and achieved by a group of synergetic capping ligands in a hot solution system. Specifically, the growth of {111}-bounded CuNi nano-octahedra is derived by a thermodynamic control, whereas the generation of {100}-terminated CuNi nanocubes is steered by a kinetic capping of chloride. Using a reduction of 4-nitrophenol with sodium borohydride as a model reaction, CuNi nano-octahedra and nanocubes demonstrated a strong facet-dependence due to their different surface energies although both exhibited remarkable catalytic activity with the high rate constant over mass (k/m). A kinetic study indicated that this is a pseudo first-order reaction with an excess of sodium borohydride. CuNi nanocubes as the catalysts showed better catalytic performance (k/m = 385 s -1 •g -1 ) than the CuNi nano-octahedra (k/m = 120 s -1 •g -1 ), indicating that 4-nitrophenol and hydrogen were adsorbed on the {100} facets with their molecules parallel to the surface much easier than those on {111} facets. 

ABSTRACT In this work, we demonstrate a size-controlled synthesis of CuNi octahedral nanocrystals (NCs) using a hot colloidal solution approach. Two different sizes of CuNi nano-octahedra are chosen and investigated. It is determined that the reagent concentration remarkably plays a key role in the formation of the size-defined CuNi octahedral NCs. In terms of the reduction of 4-nitrophenol (4-NP), it uncovers that the obtained CuNi octahedral NCs (in both sizes) exhibit higher catalytic activity than those of CuNi spherical NCs reported previously. It further indicates that the catalytic performance is strongly size-dependent due to their devise specific surface areas of the exposed crystallographic planes. 

ABSTRACT In the synthesis of metallic nanocrystals (NCs) using a high-temperature colloidal approach, the competition between deposition and diffusion of “free atom (or clusters)” plays an important role as it can direct the morphology of NCs during their evolution. This competition is closely associated with some dynamic conditions such as heat and mass transfer. Stirring speed and ramp rate of heating are two factors that greatly impact the heat and mass transfer processes and consequently determine the morphology of the products but rarely discussed in most synthetic protocols. Herein, we study the syntheses of Pt-M (M = Ni, Fe) NCs as model reactions, showing that a low stirring speed and high ramp rate of heating result in ununiform pod-like NCs, whereas the inverse conditions promote NCs in a uniform shape. This observation can be plausibly explained using a competition mechanism between the deposition and diffusion of the newly reduced atoms during a stage of the NC’s growth.