Influence of local defects on the dynamics of O-H bond breaking and formation on a magnetite surface

A. Bourgund, B. A. J. Lechner, M. Meier, C. Franchini, G. S. Parkinson, U. Heiz, F. Esch

Chair of Physical Chemistry, Department of Chemistry & Catalysis Research Center, Technical University of Munich, 85748 Garching, Germany
Institut für Angewandte Physik, TU Wien, 1040 Wien, Austria
Center for Computational Materials Science, Faculty of Physics, University of Vienna, 1090 Vienna, Austria

J. Phys. Chem. C 123 (2019) 19742-19747

The transport of H adatoms across oxide supports plays an important role in many catalytic reactions. We investigate the dynamics of H/Fe3O4(001) between 295 and 382 K. By scanning tunneling microscopy at frame rates of up to 19.6 fps, we observe the thermally activated switching of H between two O atoms on neighboring Fe rows. This switching rate changes in proximity to a defect, explained by density functional theory as a distortion in the Fe-O lattice shortening the diffusion path. Quantitative analysis yields an apparent activation barrier of 0.94 ± 0.07 eV on a pristine surface. The present work highlights the importance of local techniques in the study of atomic-scale dynamics at defective surfaces such as oxide supports.

Corresponding author: Barbara A. J. Lechner. Reprints also available from Gareth S. Parkinson (parkinson at iap_tuwien_ac_at).

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