Journal
ACS CATALYSIS
Volume 9, Issue 5, Pages 4477-4487Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.9b00664
Keywords
catalysis; kinetics; alcohols; esters; physical chemistry; chemical engineering
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Funding
- Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0012573]
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The utility of the surface reactivity observed for model systems under ultrahigh vacuum for predicting the performance of catalytic materials under ambient flow conditions is a highly debated topic in heterogeneous catalysis. Herein we show that vast differences in selectivity observed for methanol self-coupling across wide ranges of temperature and reactant pressure can be accurately predicted utilizing the kinetics and mechanism obtained from model studies on gold single crystals in ultrahigh vacuum regressed to fit transient pulse responses over nanoporous gold (Ag0.03Au0.97) at low pressures. Specifically, microkinetic modeling of the complex sequence of elementary steps governing this reaction predicts the dramatic effect of reactant partial pressure on the product distribution and leads to conclusion that the gas phase partial pressures of both reactants and the reaction temperature determine the changes in selectivity to methyl formate formation. Moreover, thorough analysis of the reaction network indicates that the product distribution becomes increasingly insensitive to kinetic effects at pressures approaching 1 bar, leading toward 100% selectivity methyl formate. A rigorous kinetic sensitivity analysis also demonstrates the complex interplay of the kinetics of the elementary steps and the overall catalytic behavior.
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