Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode
Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode
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DOI：
10.1039/b700099e
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发表时间：
2007-01-01
影响因子：
3.3
通讯作者：
Norskov, Jens K.
中科院分区：
文献类型：
--
作者：
Skulason, Egill;Karlberg, Gustav S.;Norskov, Jens K.
我们提出了密度泛函理论计算的结果，在Pt（111）板上有双层水，水层中溶剂化的质子，金属表面有多余的电子。用这种方法模拟了铂电极上的电化学双层。通过改变双层中质子/电子的数量，我们研究了该系统作为电极电位的函数。我们研究了析氢反应2(H+ + e(-)) -> H-2的基本过程，并确定了作为电极电位函数的活化能和主要反应机理。我们通过显式计算证实了活化势垒随电位的变化可以看作是整个表面化学中发现的活化能和反应能之间的Bronsted - Evans - polanyi型关系的表现。
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(-)) -> H-2, 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 Bronsted - Evans - Polanyi-type relationship between activation energy and reaction energy found throughout surface chemistry.