Experimental energies of formation reactions for adsorbates on late transition metal surfaces: A database update

Abstract

The energies of adsorbates containing H, C, O, N and I, that are of interest as intermediates and/or solvents in heterogeneous catalytic reactions have been measured accurately on clean and well-defined single crystal surfaces by a variety of methods, including temperature programmed desorption (TPD), pulsed molecular beam (PMB) surface residence time measurements, and singe crystal adsorption calorimetry (SCAC). In 2016, Silbaugh and Campbell¹ published a large collection of those experimental adsorption energies which were consider to be particularly reliable based on reproducibility by other groups, comparisons to results for closely related systems, and/or reliability of other results reported by the same group. That database included the enthalpies and energies of 81 molecular and dissociative adsorption reactions that were measured on many different metal single crystal surfaces, as well as the standard enthalpies of formation of the adsorbates thus produced. In this paper, we tabulate the enthalpies and energies of an additional set of 26 molecular and dissociative adsorption reactions that were measured on 7 different metal single crystal faces of 5 different late transition metals (Pt, Pd, Ni, Cu and Au), based on more recent measurements from our own groups. We also tabulate the standard heats of formation of the 26 adsorbates thus produced. Taken together, these databases provide 107 benchmark energies for validating the energy accuracies of computational methods used for estimating surface reaction energies and building microkinetic models of catalytic reactions.