Department of Chemistry and Institute of Applied Chemistry, Chinese Culture University, Taipei 111, Taiwan.
Langmuir. 2010 Jan 19;26(2):775-81. doi: 10.1021/la9021646.
Spin-polarized density functional theory calculation was carried out to characterize the adsorption and dissociation of CO(2) molecule on the Fe(111) surface. It was shown that the barriers for the stepwise CO(2) dissociation reaction, CO(2(g)) --> C(a) + 2O(a), are 21.73 kcal/mol (for OC-O bond activation) and 23.87 kcal/mol (for C-O bond activation), and the entire process is 35.73 kcal/mol exothermic. The rate constants for the dissociative adsorption of CO(2) have been predicted with variational RRKM theory, and the predicted rate constants, k(CO(2)) (in units of cm(3) molecule(-1) s(-1)), can be represented by the equations 2.12 x 10(-8)T(-0.842) exp(-0.258 kcal mol(-1)/RT) at T = 100-1000 K. To gain insights into high catalytic activity of the Fe(111) surface, the interaction nature between adsorbate and substrate is also analyzed by the detailed electronic analysis.
采用自旋极化密度泛函理论计算研究了 CO(2)分子在 Fe(111)表面上的吸附和解离。结果表明，CO(2)分步解离反应 CO(2(g)) --> C(a) + 2O(a) 的势垒分别为 21.73 kcal/mol（OC-O 键活化）和 23.87 kcal/mol（C-O 键活化），整个过程是 35.73 kcal/mol 的放热反应。用变分 RRKM 理论预测了 CO(2)的离解吸附速率常数，预测的 CO(2)速率常数 k(CO(2))（单位为 cm(3)分子(-1) s(-1))可以用以下方程表示：在 T = 100-1000 K 时，2.12 x 10(-8)T(-0.842) exp(-0.258 kcal mol(-1)/RT)。为了深入了解 Fe(111)表面的高催化活性，还通过详细的电子分析研究了吸附物和底物之间的相互作用性质。
