Bridging the gap between nanoparticles and extended surfaces in electrochemistry

PHYS 203

Timo Jacob, jacob@fhi-berlin.mpg.de, Theory, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, Berlin, 14195, Germany, Matthias Scheffler, Theory Department, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, 14195, Germany, and Theodore E. Madey, madey@physics.rutgers.edu, Department of Physics and Astronomy, Rutgers University, 136 Frelinghuysen Road, Piscataway, NJ 08854.
While experiments in surface science or basic electrochemistry are predominantly performed on single crystals, realistic fuel cells employ highly-dispersed nanoparticles to catalyze the occurring reactions. However, those combine a variety of different functional groups on their surfaces (planes, step-edges, or kinks), making it difficult to transfer effects observed in single crystal electrochemistry to realistic systems directly. Here faceting of single crystal surfaces, leading to homogeneous and well-defined nanostructures, might be a possibility to bridge the gap between nanoparticles and extended surfaces. Motivated by the UHV-experiments in the group of Madey, we used density functional theory calculations in combination with our newly formulated extension of the ab initio atomistic thermodynamics approach to generate (p/T/Φ)-phase diagrams for the facet formation on Ir(210)- and Re(11-21)-surfaces. The calculated phase diagrams exactly reveal the experimentally found structures and predict that applying an electrode potential might induce facet formation on these rough surfaces. By this potential-induced formation of self-assembled nanostructures, one might be able to obtain deeper insights into the catalytic behavior of nanoparticles in electrocatalysis.