Particle size effect on the Langmuir-Hinshelwood barrier for CO oxidation on regular arrays of Pd clusters supported on ultrathin alumina films

TL;DR

This study investigates how particle size influences the activation barrier and pre-exponential factor for CO oxidation on Pd clusters supported on ultrathin alumina, revealing size-dependent variations in catalytic behavior.

Contribution

It provides the first detailed measurement of the Langmuir-Hinshelwood barrier for different Pd cluster sizes supported on alumina, highlighting size-dependent electronic and atomic structure effects.

Findings

Larger Pd clusters (~3.5 nm) have similar barriers to bulk Pd.

Smaller clusters (~2.1-2.7 nm) exhibit significantly different activation barriers.

Size influences electronic structure and catalytic activity of Pd clusters.

Abstract

The Langmuir-Hinshelwood barrier (ELH) and the pre-exponential factor ($\nu$LH) for CO oxidation have been measured at high temperature on hexagonal arrays of Pd clusters supported on an ultrathin alumina film on Ni3Al(111). The Pd clusters have a sharp size distribution and the mean sizes are: 174$\pm$13, 360$\pm$19 and 768$\pm$28 atoms. ELH and $\nu$LH are determined from the initial reaction rate of a CO molecular beam with a saturation layer of adsorbed oxygen on the Pd clusters, measured at different temperatures (493$\le$T (K) $\le$613). The largest particles (3.5 nm) give values of ELH and $\nu$LH similar to those measured on Pd (111) [2]. However, smaller particles (2.7 and 2.1 nm) show very different behavior. The origin of this size effect is discussed in terms of variation of the electronic structure and of the atomic structure of the Pd clusters.