Adsorption of formic acid on the Fe3O4(001) surface

O. Gamba, H. Noei, J. Pavelec, R. Bliem, M. Schmid, U. Diebold, A. Stierle, G. S. Parkinson

Institut für Angewandte Physik, TU Wien, 1040 Wien, Austria
Deutsches Elektronen-Synchrotron (DESY), 22607 Hamburg, Germany
Fachbereich Physik, Universität Hamburg, 20355 Hamburg, Germany

J. Phys. Chem. C 119 (2015) 20459-20465

The adsorption of formic acid (HCOOH) on the Fe3O4(001) surface was studied using X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy (IRRAS), low-energy electron diffraction, and scanning tunneling microscopy (STM). At room temperature, HCOOH dissociates to form formate (HCOO-) and hydroxyl groups, facilitated by the close proximity of undercoordinated Fe3+/O2- cation/anion pairs at the Fe3O4(001) surface. Bidentate formate species are observed in IRRAS, and their position on Fe-Fe bridge sites can be inferred from STM data. At 70 K, HCOOH is adsorbed both dissociatively and molecularly, suggesting two active sites for dissociation. Our study also demonstrates that IRRAS is possible on Fe3O4 single crystals with good sensitivity but that unusual peak shapes occur because the substrate is midway between a perfect conductor and a perfect dielectric.

Corresponding author: Gareth Parkinson (parkinson at iap_tuwien_ac_at).

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