Energies of Formation Reactions Measured for Adsorbates on Late Transition Metal Surfaces

Abstract

The energies of adsorbates containing H, N, C, O, and halogens that are of interest as intermediates, poisons, and promoters in catalytic reactions have been measured on well-defined single-crystal surfaces by equilibrium adsorption isotherms, temperature-programmed desorption (TPD), and single-crystal adsorption calorimetry (SCAC). Here we tabulate a large collection of those experimental adsorption energies which we 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. Specifically, we list the enthalpies and energies of 81 molecular and dissociative adsorption reactions that were measured on 26 different metal single-crystal faces of 12 different late transition metals, and we extract from these the standard enthalpies of formation of the adsorbates thus produced. These can serve as benchmarks for validating computational methods for estimating surface reaction energies.

Bond Energies of Adsorbed Intermediates to Metal Surfaces: Correlation with Hydrogen–Ligand and Hydrogen–Surface Bond Energies and Electronegativities

“…Karp and co‐workers found a similar correlation with slope of unity between the bond enthalpies of oxygen‐bound molecular fragments [−OH, −OCH 3 , and −O(O)CH] to the Pt(111) surface and their corresponding RO−H bond enthalpies in the gas phase . These bond enthalpies (shown in Figure ) have been corrected slightly (by RT) from their original value due to a systematic error that has been discussed previously . These relationships provide methods to predict the bond enthalpies of other species to Pt(111) from their corresponding gas‐phase hydrogen‐to‐ligand bond strengths, which are well‐known …”

“…Note that this manipulation removes completely the troublesome D (M−M) term but introduces a new term, D (H−M). This is a value which can be used that is specific to metal atoms on a specific surface of a metal, since the heat of adsorption of H atoms on many metal surfaces is known . Table lists the values used here for D (H−Pt(111)) and D (H−Ni(111)), and other values are given below.…”

“…[b] The H−M(111) bond enthalpies listed here were calculated from the experimental enthalpies of formation of H gas and H adatoms reported in Ref. , except for Cu, where we assumed the same value for the (111) face as reported for the Cu(110) face in Ref. .…”

General concepts, assumptions, drawbacks, and misuses in kinetic Monte Carlo and microkinetic modeling simulations applied to computational heterogeneous catalysis

“…Fortunately, most of the often‐used codes include the contribution of dispersion terms even the choice of the appropriate methods is still a matter of debate . Here, is important that recent experiments for energies of formation reactions measured from accurate microcalorimetry techniques constitute an invaluable dataset to benchmark the different available methods …”

Rational design of selective metal catalysts for alcohol amination with ammonia

“…53 The calculated adsorption energy for methanol on Pt(111) at 1/9 ML coverage (0.51 eV) agrees well with single-crystal adsorption calorimetry. 54 Microkinetic modelling method: For mapping the catalytic activity, we used the descriptor-based microkinetic software 13 package CatMAP developed by Medford et al, 46 which is based on scaling and BEP relations. However, some essential modifications were introduced into the original software to obtain correct steady-state coverages, since the default approach to solve the microkinetic model in CatMAP was found to yield incorrect zero activity for some descriptor combinations (more details could be found in Supplementary Methods).…”