Department of Chemistry, Nankai University, Tianjin 300071, People's Republic of China.
J Comput Chem. 2010 Jul 30;31(10):2023-37. doi: 10.1002/jcc.21487.
The decomposition mechanisms of methanol on five different Pt surfaces, the flat surface of Pt(111), Pt-defect, Pt-step, Pt(110)(1 x 1), and Pt(110)(2 x 1), have been studied with the DFT-GGA method using the repeated slab model. The adsorption energies under the most stable configuration of the possible species and the activation energy barriers of the possible elementary reactions involved are obtained in this work. Through systematic calculations for the reaction mechanism of methanol decomposition on these surfaces, we found that such a reaction shows the same reaction mechanism on these Pt-based model catalysts, that is, the final products are all H (H(ads)) and CO (CO(ads)) via O-H bond breaking in methanol and C-H bond scission in methoxy. These results are in general agreement with the previous experimental observations.
采用 DFT-GGA 方法和重复层模型研究了甲醇在五种不同 Pt 表面（Pt(111)平面、Pt 缺陷、Pt 台阶、Pt(110)(1 x 1)和 Pt(110)(2 x 1)）上的分解机制。在可能物种的最稳定构型下获得了吸附能和可能基本反应的活化能垒。通过对这些表面上甲醇分解反应机理的系统计算，我们发现该反应在这些基于 Pt 的模型催化剂上表现出相同的反应机理，即最终产物均为 H（H(ads)）和 CO（CO(ads)），甲醇中通过 O-H 键断裂，甲氧基中通过 C-H 键断裂。这些结果与之前的实验观察结果基本一致。
