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

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

Boje, Astrid, 1991 (författare): Chalmers tekniska högskola,Chalmers University of Technology

Taifan, William E. (författare): Lehigh University

Ström, Henrik, 1981 (författare): Chalmers tekniska högskola,Chalmers University of Technology

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Bucko, Tomas (författare): Slovak Academy of Sciences,Univerzita Komenskeho v Bratislave,Comenius University in Bratislava

Baltrusaitis, Jonas (författare): Lehigh University

Hellman, Anders, 1974 (författare): Chalmers tekniska högskola,Chalmers University of Technology

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(creator_code:org_t)

2021
2021
Engelska.
Ingår i: Catalysis Science and Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 11:20, s. 6682-6694

Relaterad länk:: https://research.cha... (primary) (free); visa fler...; https://pubs.rsc.org...; https://research.cha...; https://doi.org/10.1...; visa färre...

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Abstract Ämnesord

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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.

Ämnesord

TEKNIK OCH TEKNOLOGIER -- Annan teknik -- Övrig annan teknik (hsv//swe)
ENGINEERING AND TECHNOLOGY -- Other Engineering and Technologies -- Other Engineering and Technologies not elsewhere specified (hsv//eng)
TEKNIK OCH TEKNOLOGIER -- Kemiteknik -- Annan kemiteknik (hsv//swe)
ENGINEERING AND TECHNOLOGY -- Chemical Engineering -- Other Chemical Engineering (hsv//eng)
NATURVETENSKAP -- Fysik -- Annan fysik (hsv//swe)
NATURAL SCIENCES -- Physical Sciences -- Other Physics Topics (hsv//eng)

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Av författaren/redakt...: Boje, Astrid, 19 ...; Taifan, William ...; Ström, Henrik, 1 ...; Bucko, Tomas; Baltrusaitis, Jo ...; Hellman, Anders, ...

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TEKNIK OCH TEKNOLOGIER: TEKNIK OCH TEKNO ...; och Annan teknik; och Övrig annan tekn ...

TEKNIK OCH TEKNOLOGIER: TEKNIK OCH TEKNO ...; och Kemiteknik; och Annan kemiteknik

NATURVETENSKAP: NATURVETENSKAP; och Fysik; och Annan fysik

Artiklar i publikationen: Catalysis Scienc ...

Av lärosätet: Chalmers tekniska högskola

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