The Role of Surface Hydroxyls in Dehydration and Dehydrogenation of Formic Acid on Fe3O4(001)

Sharp, Marcus A.; Nguyen, Hoan K. K.; Lee, Christopher J.; Sauter, Eric; Wang, Yuemin; Wöll, Christof; Jackson, Benjamin A.; Lee, Mal-Soon; Kay, Bruce D.; Raugei, Simone; Árnadóttir, Líney; Dohnálek, Zdenek

doi:10.1021/acs.jpcc.4c07537

Title: The Role of Surface Hydroxyls in Dehydration and Dehydrogenation of Formic Acid on Fe₃O₄(001)

Journal Article · Mon Feb 03 00:00:00 UTC 2025 · The Journal of Physical Chemistry C

DOI: https://doi.org/10.1021/acs.jpcc.4c07537 · OSTI ID:2586454

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Washington State University, Pullman, WA (United States)
Oregon State University, Corvallis, OR (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen (Germany)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Oregon State University, Corvallis, OR (United States)

Understanding the role of surface structure and hydroxylation in catalytic reactions on metal oxide surfaces is important for developing a mechanistic insight into the complex interface processes. Here, we investigate the reactivity of formic acid on reconstructed Fe₃O₄(001) using a combination of X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, temperature-programmed reaction spectroscopy, low energy electron diffraction, and electronic structure calculations. We find that formic acid initially dissociates at low temperatures (< 80 K) into bidentate formate and a hydroxyl up to an initial dosed coverage of two HCOOH per Fe₃O₄(001) unit cell. At higher temperatures (> 450 K), formate largely decomposes along the dehydration pathway, producing CO and H₂O, with dehydrogenation to CO₂ being a minority side reaction. As a first step, water formation leads to surface oxygen extraction via the Mars-van Krevelen mechanism. Computational studies reveal formate embedded in oxygen vacancies as a key intermediate in the CO formation mechanism. CO formation proceeds via two reaction pathways with desorption that peaks at 530 K on the hydroxyl-rich surface and 560 K on the hydroxyl-deficient surface. Atomic hydrogen coadsorption experiments and ab initio calculations reveal that the presence of surface hydroxyls reduces the CO formation barrier. Furthermore, these results highlight the complex interactions between substrate and intermediate species occurring during reactions on metal oxide surfaces.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2586454

Report Number(s):: PNNL-SA--207890

Journal Information:: The Journal of Physical Chemistry C, Journal Name: The Journal of Physical Chemistry C Journal Issue: 6 Vol. 129; ISSN 1932-7455; ISSN 1932-7447

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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