Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode
文献情報
Gustav S. Karlberg, Jan Rossmeisl, Jeff Greeley, Hannes Jónsson, Jens K. Nørskov
We present results of density functional theory calculations on a Pt(111) slab with a bilayer of water, solvated protons in the water layer, and excess electrons in the metal surface. In this way we model the electrochemical double layer at a platinum electrode. By varying the number of protons/electrons in the double layer we investigate the system as a function of the electrode potential. We study the elementary processes involved in the hydrogen evolution reaction, 2(H+ + e−) → H2, and determine the activation energy and predominant reaction mechanism as a function of electrode potential. We confirm by explicit calculations the notion that the variation of the activation barrier with potential can be viewed as a manifestation of the Brønsted–Evans–Polanyi-type relationship between activation energy and reaction energy found throughout surface chemistry.
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