Size and structure effects on platinum nanocatalysts: theoretical insights from methanol dehydrogenation.

Methanol dehydrogenation on Pt nanoparticles was studied as a model reaction with the focus on size and structure effects employing the density functional theory approach. The effect of cluster morphology is manifested by the higher adsorption energy of COHx intermediates on vertexes and edges of model nanoparticles compared to closely packed terraces. Moreover, due to the size effect, the adsorption sites of Pt79 nanoparticles (1.2 nm in diameter) exhibit considerably higher adsorption activity than the same sites of Pt201 (1.7 nm). Thus, particles with a size of about 1 nm are shown to be more active due to the superposition of two effects: (i) a higher surface fraction of low-coordinated adsorption sites and (ii) higher activity of these sites compared to particles with a size of about 2 nm.

Pd Single-Atom Sites on the Surface of PdAu Nanoparticles: A DFT-Based Topological Search for Suitable Compositions.

Structure of model bimetallic PdAu nanoparticles is analyzed aiming to find Pd:Au ratios optimal for existence of Pd1 single-atom surface sites inside outer Au atomic shell. The analysis is performed using density-functional theory (DFT) calculations and topological approach based on DFT-parameterized topological energy expression. The number of the surface Pd1 sites in the absence of adsorbates is calculated as a function of Pd concentration inside the particles. At low Pd contents none of the Pd atoms emerge on the surface in the lowest-energy chemical orderings. However, surface Pd1 sites become stable, when Pd content inside a Pd-Au particle reaches ca. 60%. Further Pd content increase up to almost pure Pd core is accompanied by increased concentration of surface Pd atoms, mostly as Pd1 sites, although larger Pd ensembles as dimers and linear trimers are formed as well. Analysis of the chemical orderings inside PdAu nanoparticles at different Pd contents revealed that enrichment of the subsurface shell by Pd with predominant occupation of its edge positions precedes emergence of Pd surface species.

Suppression of hysteresis in absorption of hydrogen by a Pd-Au alloy.

Hydrogen absorption by Pd exhibits hysteresis loops (provided the temperature is not too high) and represents one of the classical examples of first-order phase transitions in metals. Experiments indicate that addition of even a small amount of Au is able to suppress hysteresis. From this perspective, we analyze the energetics of hydrogen in a Pd-Au alloy by using extensive density-functional-theory (DFT) calculations. The dependence of the hydrogen binding energy on the number (n) of Au atoms forming an adsorption site is found to be appreciably nonlinear. With the DFT input for statistical calculations, we reproduce special features of the hydrogen absorption isotherms and explain the rapid decrease of the corresponding critical temperature with increasing Au fraction. The key factor here is that the phase transition is related primarily to absorption in sites formed only by Pd. With increasing Au amount, the fraction of such sites rapidly decreases, the distance between H atoms located there becomes on average larger, the interaction between them becomes weaker, and accordingly the driving force for the phase transition decreases. It is of interest that all these effects can be illustrated by taking only the configurations with n≤2 into account. This means that in the context under consideration the fine details of the dependence of the hydrogen binding energy on n are in fact not too important.