The reversible hydrogen electrode: Potential-dependent activation energies over platinum from quantum theory

被引:69
作者
Cai, Y [1 ]
Anderson, AB [1 ]
机构
[1] Case Western Reserve Univ, Dept Chem, Cleveland, OH 44106 USA
关键词
D O I
10.1021/jp037126d
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
Potential-dependent activation energies are calculated quantum mechanically, using a local reaction center model, for the hydrogen reduction-oxidation reaction over platinum by the Volmer-Heyrovsky mechanism, Pt-H + H+ + e(-)(U) <----> Pt + H-2 (i), modeled by Pt-(HH)-H-...+(OH2)(OH2)(2) + e(-)(U) <----> Pt...H-H...OH2(OH2)(2) (ii). A contribution from the electrolyte to the potential of the reaction centers in ii is included in the ab initio Hamiltonian. The reversible potential predicted for i based on model ii is 0.04 V, close to the standard hydrogen electrode value of 0 V, and the predicted activation energy at the predicted reversible potential is 0.076 eV, close to the literature value of 0.12 eV for the apparent activation energy. The theoretical results validate the possibility of the Volmer-Heyrovsky mechanism being followed on platinum.
引用
收藏
页码:9829 / 9833
页数:5
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