Predicting a Sharp Decline in Selectivity for Catalytic Esterification of Alcohols from van der Waals Interactions

Abstract

This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Moving from Fundamental Knowledge of Kinetics and Mechanisms on Surfaces to Prediction of Catalyst Performance in Reactors

“…Thus, the extrapolation of the catalytic performance to higher alcohols predicts that nanoporous gold is not an effective catalyst for gas-phase catalyzed self-coupling of higher alcohols. 116 The general extension of this type of analysis to other catalytic reaction systems is evident.…”

“…Excellent agreement was obtained between the selectivities predicted for C 2 –C 4 alcohols (Figure ); in all cases, unlike methanol, aldehyde production dominated the reaction. Thus, the extrapolation of the catalytic performance to higher alcohols predicts that nanoporous gold is not an effective catalyst for gas-phase catalyzed self-coupling of higher alcohols . The general extension of this type of analysis to other catalytic reaction systems is evident.…”

“…We employed a combination of experiment and theory to create a robust method of scaling. 116 Since DFT generally indicates correct trends for binding energies for homologous species, it can be used to estimate each ΔE reaction by calculating the energies of the reactants and products, including van der Waals stabilization. The activation energies known for each step in methanol self-coupling (Table 3) then provide a basis for the determination of b; if a can be obtained, b can be determined for each reaction step from the known value of ΔE reaction .…”

“…For the oxygen-assisted self-coupling of higher-molecular-weight aliphatic alcohols over nanoporous gold catalysts, the reaction network is known to be the same as that for methanol (Figure ), the difference being that the methyl group is replaced by a longer alkyl group. , In order to predict the behavior of nanoporous gold for the self-coupling of these alcohols, the rate constants for the individual elementary steps must be determined. We employed a combination of experiment and theory to create a robust method of scaling . Since DFT generally indicates correct trends for binding energies for homologous species, it can be used to estimate each Δ E reaction by calculating the energies of the reactants and products, including van der Waals stabilization.…”

“…Reaction conditions: 2% alcohol and 4% oxygen balanced with He at 423 K at a flow rate of 50 mL/min. Adapted with permission from ref . Copyright 2020 Wiley-VCH.…”