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First-principles-informed energy span and microkinetic analysis of ethanol catalytic conversion to 1,3-butadiene on MgO

revised on 11.03.2021, 11:15 and posted on 12.03.2021, 05:31 by Astrid Boje, William E. Taifan, Henrik Ström, Tomas Bucko, Jonas Baltrusaitis, Anders Hellman
Kinetic modeling of single-step catalytic conversion of ethanol to 1,3-butadiene is necessary to inform accurate process design. This paper uses first-principles-informed energy span and microkinetic analysis to explore the reaction free energy landscapes and kinetic limitations of competing reaction pathways on a MgO (100) step-edge. Previous studies suggested mechanisms proceeding via both dehydrogenation and dehydration of ethanol, and highlighted sensitivity to conditions and catalyst composition. Here, we use the energy span concept to characterize the theoretical maximum turnover and degree of turnover frequency control for states in each reaction pathway, finding the dehydration route to be less active for 1,3-butadiene, and suggesting rate-determining states in the dehydrogenation, dehydration, and condensation steps. The influence of temperature on the relative rate contribution of each state is quantified and explained through the varying temperature sensitivity of the free energy landscape. A microkinetic model is developed to explore competition between pathways, interaction with gas-phase species, and surface coverage limitations. This suggests that the turnover may be significantly lower than predicted solely based on energetics. Turnover frequency determining states found to have high surface coverage include adsorbed ethanol and two longer, oxygenated hydrocarbons. The combined energy span and microkinetic analysis permits investigation of a complex system from two perspectives and helps elucidate conflicting observations of rate determining steps and product distribution by considering both energetic and kinetic limitations. The impact of uncertainty in the energy landscape is quantified using a correlated error model. While the range of predictions is large, the average performance and trends are similar.


Knut and Alice Wallenberg Foundation (Project 2015.0057)

Swedish Research Council (Project 2015-03773)

National Science Foundation (Grant CHE 1710120)

National Science Foundation (ACI-1053575)


Email Address of Submitting Author


Chalmers University of Technology



ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest

Version Notes

Revisions include adding structures and selectivity maps to the SI and moving some UQ analysis to the main text.