The mechanism of borohydride oxidation and the competing hydrolysis reaction are examined over Pt(1 1 1) using density functional theory (DFT) methods. Adsorption of BH4- over Au(1 1 1) and Pt(1 1 1) is examined. Adsorption over Pt(1 1 1) is dissociative and extremely exothermic at potentials of interest, leading to a high surface coverage of H-center dot for which gaseous hydrogen evolution is competitive with oxidation. Elementary surface reactions oxidizing B-containing intermediates are favorable over Pt(1 1 1) at -0.85 V (SHE), consistent with experimental voltammetry results in the literature. The energetics of the initial adsorption step dictate the activity limitation of gold anodes and the selectivity limitation of platinum electrodes. This adsorption energy can be rapidly calculated with DFT methods, enabling screening of pure metals, alloys, poisons, and promoters to optimize borohydride oxidation catalyst design. (c) 2009 Elsevier Ltd. All rights reserved.