Issue 20, 2021

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

Abstract

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
09 Mar 2021
Accepted
27 Jul 2021
First published
09 Aug 2021
This article is Open Access
Creative Commons BY-NC license

Catal. Sci. Technol., 2021,11, 6682-6694

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

A. Boje, W. E. Taifan, H. Ström, T. Bučko, J. Baltrusaitis and A. Hellman, Catal. Sci. Technol., 2021, 11, 6682 DOI: 10.1039/D1CY00419K

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