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Title: Adsorption and reaction of methanol on Fe3O4 (001)

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5139418 · OSTI ID:1602775
 [1];  [2];  [1]; ORCiD logo [3]; ORCiD logo [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [4];  [1]; ORCiD logo [3]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate and Inst. for Integrated Catalysis
  2. Aarhus Univ. (Denmark)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate and Inst. for Integrated Catalysis; Washington State Univ., Pullman, WA (United States)
  4. Vienna Univ. of Technology (Austria). Inst. of Applied Physics
+ Show Author Affiliations

The interaction of methanol with iron oxide surfaces is of interest due to its potential in hydrogen storage, and from a fundamental perspective as a chemical probe of the reactivity. We present here a study examining the adsorption and reaction of methanol on magnetite Fe3O4(001) at cryogenic temperatures using a combination of temperature programmed desorption, x-ray photoelectron spectroscopy, and scanning tunneling microscopy. We report the methanol desorption profile from Fe3O4(001) is complex, exhibiting peaks at 145, 175, 238, and 273 K, corresponding to the desorption of intact methanol, as well as peaks at 350 and 500 K due to the reaction of methoxy intermediates. The saturation of a monolayer of methanol corresponds to ~5 molecules/unit cell (u.c.), which is slightly higher than the number of surface octahedral iron atoms of 4/u.c. We probe the kinetics and thermodynamics of the desorption of molecular methanol using inversion analysis. The deconvolution of the complex desorption profile into individual peaks allows for calculations of both the desorption energy and the prefactor of each feature. The initial 0.7 methanol/u.c. reacts to form a methoxy and hydroxy intermediates by 180 K, which remains on the surface above room temperature after intact methanol has desorbed. The methoxy species react via one of two channels, a recombination reaction with surface hydroxyls to form additional methanol at ~350 K, and a disproportionation reaction to form methanol and formaldehyde at ~500 K. Only 20% of the methoxy species undergo the disproportionation reaction, with most of them reacting via the 350 K pathway.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
Austrian Science Fund (FWF) START; Innovation Fund Denmark; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1602775
Report Number(s):
PNNL-SA--149459
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 152; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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