High Chemical Potential Driven Amorphization of Pd-based Nanoalloys.

Amorphous metals and alloys are promising candidates for superior catalysts in many catalytic and electrocatalytic reactions. It is of great urgency to develop a general method to construct amorphous alloys and further clarify the growth mechanism in a wet-chemical system. Herein, inspired by the conservation of energy during the crystallization process, amorphous PdCu nanoalloys have been successfully synthesized by promoting the chemical potential of the building blocks in solution. Benefiting from the abundant active sites and enhanced corrosion resistance, the synthesized amorphous PdCu nanostructures exhibit superior catalytic activity and durability over the face-centered cubic one in formic acid decomposition reaction. More importantly, the successful fabrications of amorphous PdFe, PdCo, and PdNi further demonstrate the universality of the above strategy. This proposed strategy is promising to diversify the amorphous family.

Optimization of gold-palladium core-shell nanowires towards H2O2 reduction by adjusting shell thickness.

Designable bimetallic core-shell nanoparticles exhibit superb performance in many fields including industrial catalysis, energy conversion and chemical sensing, due to their outstanding properties associated with their tunable electronic structure. Herein, Au-Pd core-shell (AurichPd@AuPdrich) nanowires (NWs) were synthesized through a one-pot facile chemical reduction method in the presence of cetyltrimethyl ammonium bromide (CTAB) surfactant. The thickness of the Pd shell could be adjusted by directly controlling the Au/Pd feeding ratio while maintaining the nanowire morphology. The as-obtained Au75Pd25 core-shell NWs with a thin Pdrich shell showed significantly enhanced activities towards the reduction of hydrogen peroxide with the sensitivity reaching 338 µA cm-2 mM-1 and a linear range up to 10 mM. In sum, Pd shell thickness could be used to adjust the electronic structure, thereby optimizing the catalytic activity.

Surfactant dependent evolution of Au-Pd alloy nanocrystals from trisoctahedron to excavated rhombic dodecahedron and multipod: a matter of crystal growth kinetics.

In wet chemical syntheses of noble metal nanocrystals, surfactants play crucial roles in regulating their morphology. To date, more attention has been paid to the effect of the surfactant on the surface energy of crystal facets, while less attention has been paid to its effect on the growth kinetics. In this paper, using the growth of Au-Pd alloy nanocrystals as an example, we demonstrate that different concentration of surfactant hexadecyltrimethyl ammonium chloride (CTAC) may cause the different packing density of CTA+ bilayers on different sites (face, edge or vertex) of crystallite surface, which would change the crystal growth kinetics and result in preferential crystal growth along the edge or vertex of crystallites. The unique shape evolution from trisoctahedron to excavated rhombic dodecahedron and multipod structure for Au-Pd alloy nanocrystals was successfully achieved by simply adjusting the concentration of CTAC. These results help to understand the effect of surfactants on the shape evolution of nanocrystals and open up avenues to the rational synthesis of nanocrystals with the thermodynamically unfavorable morphologies.