In this paper, we reported a solvothermal method for the synthesis of octahedral Pt-Cu bimetallic alloy nanocrystals （NCs） with tunable composition. Inspired by the result from our previous exploration on octahedral Pt-Cu alloy NCs that Cu contents can be tuned from 10 % to 50 %, we further tuned the Cu portion from 50 % to 75 % by simply introducing n-butylamine in the reaction system. It is believed that n-butylamine plays a key role in breaking through a thermodynamic constraint in the formation of Pt-Cu alloy nanocrystals （NCs）. The synergistic effect of underpotential deposition-like Cu reduction and the different complexion abilities of amine group of n-butylamine with two metal species effectively tuned the reduction kinetics, by which each reduced Pt atom is able to catalyze reduction of more Cu atoms and be fully covered with 12 Cu atoms in the Pt-Cu alloy crystal, while Cu precursor is not able to be reduced solely and bind solely with Cu atoms, resulting in the successful tuning of Cu composition from 50 % to 75 %. In addition, we investigated the electro-catalytic activity of Pt-Cu bimetallic alloy NCs with different composition in electro-oxidation of methanol. The as-prepared PtCu3 NCs exhibit excellent electro-catalytic performance and stability in comparison with commercial Pt black and other compositional Pt-Cu alloy NCs.
Surface structure control of functional nano-/micro-crystallites has attracted great attention because many important physicochemical properties depend on their surface. Guided by the supersaturation-dependent surface structure evolution strategy we proposed recently, NaTaO3 submicrometer crystals with morphologies of cubes, corner truncated cubes, edge and corner truncated cubes, and quasi-spheres can be synthesized by changing the volume ratio of ethylene glycol to water and the amount of NaOH in the composite solvent. Under low supersaturation condition, NaTaO3 cubic crystals with low energy {100} facets were obtained. As the supersaturation increases, the corners and edges of NaTaO3 cubic crystals, which possess higher surface energy, were gradually truncated. Surprisingly, quasi-sphere crystallites formed under extremely high supersaturation condition, which is difficult to be explained by the classical crystal growth theories. By analyzing the formation work of two-dimension crystal nuclei, we concluded that the crystal growth tend to be isotropic at extremely high supersaturation, which well explained the formation of the quasi-sphere crystallites.
Atomically dispersed catalysts have shown promising prospects in catalysis studies.Among all of the developed methods for synthesizing atomically dispersed catalysts,the photochemical approach has recently aroused much attention owing to its simple procedure and mild preparation conditions involved.In the present study,we demonstrate the application of the photochemical method to synthesize atomically dispersed Pd catalysts on(001)‐exposed anatase nanocrystals and commercial TiO2(P25).The as‐prepared catalysts exhibit both high activity and stability in the hydrogenation of styrene and catalytic oxidation of CO.
Spin-polarized density functional theory （DPT） calculations are carried out to determine the site preference of H adsorption on Pd（100） surface and subsurface, We carefully scrutinize the energy difference between different patterns at θ=0.50 ML and confirm the LEED observation that surface adsorption can form c（2×2） ordering structure. On the contrary, we disclose that p（2×1） structure become more favorable than c（2×2） for subsurface adsorption. These site preferences are rationalized via an analysis of the layer and orbital resolved density of states. Furthermore, we propose that the interstitial charge as a key factor determining the preferred H adsorbed site.
This paper describes a robust method for the synthesis of high-quality ZIF-8 nanocrystals using reverse micelles as discrete nanoscale reactors.The precise size control of ZIF-8 nanocrystals is conveniently achieved by tuning the concentration of precursors,reaction temperatures,the amount of water,and the structure of surfactants.The as-synthesized ZIF-8 nanocrystals are of narrow distribution and tunable size.A size-dependent catalytic activity for Knoevenagel condensation reaction is further demonstrated by using ZIF-8 nanocrystals with different sizes as the catalysts.This facile method opens up a new opportunity in the synthesis of various ZIFs nanocrystals.
