Calculated phase diagrams for the electrochemical oxidation and reduction of water over Pt(111)

被引:367
作者
Rossmeisl, Jan [1 ]
Norskov, Jens K.
Taylor, Christopher D.
Janik, Michael J.
Neurock, Matthew
机构
[1] Tech Univ Denmark, Ctr Atomscale Mat Phys, NanoDTU, Dept Phys, DK-2800 Lyngby, Denmark
[2] Univ Virginia, Dept Chem Engn, Charlottesville, VA 22904 USA
[3] Univ Virginia, Dept Chem, Charlottesville, VA 22904 USA
关键词
D O I
10.1021/jp0631735
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Ab initio density functional theory is used to calculate the electrochemical phase diagram for the oxidation and reduction of water over the Pt(111) surface. Three different schemes proposed in the literature are used to calculate the potential-dependent free energy of hydrogen, water, hydroxyl, and oxygen species adsorbed to the surface. Despite the different foundations for the models and their different complexity, they can be directly related to one another through a systematic Taylor series expansion of the Nernst equation. The simplest model, which includes the potential only as a shift in the chemical potential of the electrons, accounts very well for the thermochemical features determining the phase-diagram.
引用
收藏
页码:21833 / 21839
页数:7
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