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Predicting a Sharp Decline in Selectivity for Catalytic Esterification of Alcohols from van der Waals Interactions
Author(s) -
Reece Christian,
Luneau Mathilde,
Friend Cynthia M.,
Madix Robert J.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202001576
Subject(s) - van der waals force , catalysis , chemistry , selectivity , nanoporous , computational chemistry , aldehyde , alkyl , methanol , kinetics , catalytic cycle , molecule , thermodynamics , chemical physics , organic chemistry , physics , quantum mechanics
Abstract Controlling the selectivity of catalytic reactions is a critical aspect of improving energy efficiency in the chemical industry; thus, predictive models are of key importance. Herein the performance of a heterogeneous, nanoporous Au catalyst is predicted for the complex catalytic self‐coupling of the series of C 2 –C 4 alkyl alcohols, based solely on the known kinetics of the elementary steps of the catalytic cycle for methanol coupling, using scaling methods augmented by density functional theory. Notably, a sharp decrease in selectivity for ester formation with increasing molecular weight to favor the aldehyde due to van der Waals interactions of reaction intermediates with the surface was predicted and subsequently verified quantitatively by experiment. Further, the agreement between theory and experiment clearly demonstrates the efficacy of this approach for building a predictive model of catalytic behavior for a homologous set of reactants using a small set of experimental information.