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Advances in Physical Chemistry
Volume 2011 (2011), Article ID 305634, 8 pages
Research Article

Hydrogen Adsorption on Palladium and Platinum Overlayers: DFT Study

1Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11158 Belgrade, Serbia
2Serbian Academy of Sciences and Arts, Knez Mihajlova 35, 11185 Belgrade, Serbia

Received 15 February 2011; Accepted 13 May 2011

Academic Editor: Milan M. Jaksic

Copyright © 2011 Igor A. Pašti et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


Hydrogen adsorption on twenty different palladium and platinum overlayer surfaces with (111) crystallographic orientation was studied by means of periodic DFT calculations on the GGA-PBE level. Palladium and platinum overlayers here denote either the Pd and Pt mono- and bilayers deposited over (111) crystallographic plane of Pd, Pt, Cu, and Au monocrystals or the (111) crystallographic plane of Pd and Pt monocrystals with inserted one-atom-thick surface underlayer of Pd, Pt, Cu, and Au. The attention was focused on the bond lengths, hydrogen adsorption energetics, mobility of adsorbed hydrogen, and surface reactivity toward hydrogen electrode reactions. Both the ligand and strain effects were considered, found to lead to a significant modification of the electronic structure of Pd and Pt overlayers, described through the position of the d-band center, and tuning of the hydrogen adsorption energy in the range that covers approximately 120 kJmol−1. Mobility of hydrogen adsorbed on studied overlayers was found to be determined by hydrogen-metal binding energy. Obtained results regarding Pd layers on Pt(111) and Au(111) surfaces, in conjunction with some of the recent experimental data, were used to explain its electrocatalytic activity towards hydrogen evolution reaction.