Multiple redox mechanisms for water-gas shift reaction on Fe3O4 (1 1 1) surface: A density functional theory and mean-field microkinetic modeling study

Yoo, Pilsun; Liao, Peilin

doi:10.1016/j.apsusc.2023.157501

Title: Multiple redox mechanisms for water-gas shift reaction on Fe₃O₄ (1 1 1) surface: A density functional theory and mean-field microkinetic modeling study

Journal Article · Sat May 13 00:00:00 EDT 2023 · Applied Surface Science

DOI:https://doi.org/10.1016/j.apsusc.2023.157501· OSTI ID:1975342

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Purdue Univ., West Lafayette, IN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Purdue Univ., West Lafayette, IN (United States)

In this work, we investigated redox mechanisms for the high temperature (HT) water–gas shift reaction (WGSR) on the Fe₃O₄ (1 1 1) surface using density functional theory (DFT) calculations and mean-field microkinetic modeling (MKM). The redox pathways branched into three Langmuir-Hinshelwood processes (LH1, LH2 and LH3) and one Mars-van-Krevelen (MVK) process (in the presence of oxygen vacancy) from multidentate binding of CO and CO₂ over four available reactive sites (Fe_oct2, Fe_tet1, Fe bridge, and O1). We found that the LH1 and LH2 processes have CO adsorption at a single iron site (Fe_oct2 or Fe_tet1), while the LH3 and MVK processes have stronger chemisorption of CO or CO₂ by both the Fe_oct2 site and the O₁ site. From the mechanistic study of these reaction path, we recognized that availability of O₁ sites was key to proceed to either CO oxidation by the single site (LH1, LH2) or by the dual site (LH3, MVK). We observed that the reaction energetics were significantly different in the CO oxidation steps, where the single or dual site results in markedly different apparent activation energy (73–281 kJ/mol) and reaction rates (10^-3–10^-10 mol∙m^-2∙s^-1) among the four reaction mechanisms. The utilization of mean field MKM with DFT reaction energetics helps explain the experimental debates for the catalytic reaction details as well as providing a possible direction to engineer the catalyst with higher activity.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1975342

Journal Information:: Applied Surface Science, Vol. 630, Issue 1; ISSN 0169-4332

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Water–gas shift catalyst
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Fe3O4 (1 1 1) surface
Density functional theory calculations
Mean field microkinetic modeling
Redox mechanism

Title: Multiple redox mechanisms for water-gas shift reaction on Fe3O4 (1 1 1) surface: A density functional theory and mean-field microkinetic modeling study

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Title: Multiple redox mechanisms for water-gas shift reaction on Fe₃O₄ (1 1 1) surface: A density functional theory and mean-field microkinetic modeling study