Electrochemical chlorine evolution at rutile oxide (110) surfaces

被引:334
作者
Hansen, Heine A. [1 ]
Man, Isabela C. [2 ]
Studt, Felix [1 ,2 ]
Abild-Pedersen, Frank [1 ,2 ]
Bligaard, Thomas [1 ,3 ]
Rossmeisl, Jan [1 ]
机构
[1] Tech Univ Denmark, Ctr Atom Scale Mat Design, Dept Phys, DK-2800 Lyngby, Denmark
[2] Computat Mat Design ApS, DK-2800 Lyngby, Denmark
[3] Lawrence Berkeley Natl Lab, Div Mat Sci, Berkeley, CA 94720 USA
关键词
IMPLANTED TITANIUM ELECTRODES; DENSITY-FUNCTIONAL THEORY; TRANSITION-METAL OXIDE; OXYGEN REDUCTION; HETEROGENEOUS CATALYSIS; ION-IMPLANTATION; ANODIC EVOLUTION; DEACON PROCESS; HCL OXIDATION; RUO2;
D O I
10.1039/b917459a
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
Based on density functional theory (DFT) calculations we study the electrochemical chlorine evolution reaction on rutile (110) oxide surfaces. First we construct the Pourbaix surface diagram for IrO2 and RuO2, and from this we find the chlorine evolution reaction intermediates and identify the lowest overpotential at which all elementary reaction steps in the chlorine evolution reaction are downhill in free energy. This condition is then used as a measure for catalytic activity. Linear scaling relations between the binding energies of the intermediates and the oxygen binding energies at cus-sites are established for MO2 (M being Ir, Ru, Pt, Ti). The linear relations form the basis for constructing a generalized surface phase diagram where two parameters, the potential and the binding energy of oxygen, are needed to determine the surface composition. We calculate the catalytic activity as function of the oxygen binding energy, giving rise to a Sabatier volcano. By combining the surface phase diagram and the volcano describing the catalytic activity, we find that the reaction mechanism differs depending on catalyst material. The flexibility in reaction path means that the chlorine evolution activity is high for a wide range of oxygen binding energies. We find that the required overpotential for chlorine evolution is lower than the overpotential necessary for oxygen evolution.
引用
收藏
页码:283 / 290
页数:8
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