Institute of Theoretical and Computational Chemistry, Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
Phys Chem Chem Phys. 2011 May 28;13(20):9622-31. doi: 10.1039/c1cp20067d. Epub 2011 Apr 13.
Plane-wave density functional theory calculations have been carried out to explore possible pathways in methanol steam reforming (MSR) on Cu(111). We focus on reactions involving the adsorbed formaldehyde intermediate (CH(2)O) produced by methanol decomposition and the surface hydroxyl (OH) species generated by dissociative adsorption of H(2)O. Several possible pathways leading to the H(2) + CO(2) products have been identified. The two most likely pathways involve the formate (CHOO), rather than the carboxyl (COOH), intermediate, and they possess barriers lower than that of the rate-limiting step of MSR, namely the dehydrogenation of adsorbed methoxyl (CH(3)O) species.
采用平面波密度泛函理论计算研究了甲醇蒸汽重整（MSR）在 Cu(111)表面上可能的反应途径。我们主要关注甲醇分解生成的吸附态甲醛（CH(2)O）中间体和 H(2)O 离解吸附生成的表面羟基（OH）物种所参与的反应。我们已经确定了几种生成 H(2) + CO(2)产物的可能途径。其中两条最有可能的途径涉及甲酸盐（CHOO）而不是羧基（COOH）中间体，它们的势垒低于 MSR 的速控步骤，即吸附甲氧基（CH(3)O）物种的脱氢反应。
