Au nanocrystals (NCs) with an unprecedented hexoctahedral structure enclosed exclusively by high-index {321} facets have been prepared for the first time. Manipulating the NC growth kinetics by controlling the amount of reductant and the reaction temperature in the presence of a suitable surfactant was the key synthetic lever for controlling the morphology of the Au NCs. The hexoctahedral Au NCs exhibited efficient optical and surface-enhanced Raman scattering activities due to their unique morphological characteristics.
Precise control over the topology of plasmonic metal-semiconductor heteronanostructures is essential for fully harnessing their plasmonic function and hence for designing innovative solar energy conversion platforms. Here, we present a rational synthesis strategy for the realization of plasmonic metal-semiconductor heteronanocrystals with intended configurations through the site-selective overgrowth of semiconductor CuO on desired sites of anisotropic Au nanocrystals. Both the exploitation of structural characteristics of Au nanocrystals and the selective stabilization of their surfaces are keys to the construction of heteronanocrystals with a specific configuration. Our approach can provide an opportunity to precisely explore the link between the solar energy conversion efficiency and the structure of heteronanocrystals as well as to obtain important insights into the underpinning mechanism. Heteronanocrystals produced by CuO overgrowth preferentially on the multiple high-curvature sites of Au nanocrystals exhibited prominent photocatalytic hydrogen production activity due to efficient charge separation by strong plasmon excitation at the Au-CuO interface and subsequent sustainable hot electron transfer from Au to CuO.
A synthesis strategy for the preparation of ultrathin free-standing ternary-alloy nanosheets is reported. Ultrathin Pd-Pt-Ag nanosheets with a thickness of approximately 3 nm were successfully prepared by co-reduction of the metal precursors in an appropriate molar ratio in the presence of CO. Both the presence of CO and the interplay between the constituent metals provide fine control over the anisotropic two-dimensional growth of the ternary-alloy nanostructure. The prepared Pd-Pt-Ag nanosheets were superior catalysts of ethanol electrooxidation owing to their specific structural and compositional characteristics. This approach will pave the way for the design of multicomponent 2D nanomaterials with unprecedented functions.
The synthesis of shape-, facet-, and composition-controlled Pd-based nanocrystals and the study of their catalytic reaction mechanisms are significant to and challenging for the development of advanced catalysts applicable to direct liquid-fuel cells (DLFCs). In the present study, we prepared (100)-faceted β-PdH cubes and ( 111)faceted β-PdH octahedra, which offered the opportunity to investigate the link between catalytic performance and the shape/facet/composition of nanocrystals. The β-PdH cubes and octahedra remarkably boosted catalytic activity and stability to the formic acid/methanol oxidation reaction (FAOR/MOR), due to the ligand effect originating from the interstitial alloying of β-PdH. Notably in this regard, β-PdH cubes exhibited the highest FAOR/MOR activity among Pdbased catalysts, owing to the relatively high CO tolerance on the Pd(100) facets. Our results confirm that simultaneous control of ligand and facet effects is an effective approach to the design of catalysts suitable for liquid fuel oxidation electrocatalysis.
Modification of the electronic structure and lattice contraction of Pt alloy nanocatalysts through control over their morphology and composition has been a crucial issue for improving their electrocatalytic oxygen reduction reaction (ORR) activity. In the present work, we synthesized PtCo alloy nanocubes with controlled compositions (Pt(x)Co NCs, x = 2, 3, 5, 7, and 9) by regulating the ratio of surfactants and the amount of Co precursor to elucidate the effect of the composition of nanocatalysts on their ORR activity. Pt(x)Co NCs had a Pt-skin structure after electrochemical treatment. The electrocatalysis experiments revealed a strong correlation between ORR activity and Co composition. Pt₃Co NCs exhibited the best ORR performance among the various Pt(x)Co NCs. From density functional theory calculations, a typical volcano-type relationship was established between ORR activity and oxygen binding energy (E(OB)) on NC surfaces, which showed that Pt₃Co NCs had the optimal E(OB) to achieve the maximum ORR activity. X-ray photoelectron spectroscopy and X-ray diffraction measurements demonstrated that the electronic structure and lattice contraction of the Pt(x)Co NCs could be tuned by controlling the composition of NCs, which are highly correlated with the trends of E(OB) change.
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