期刊
ACS CATALYSIS
卷 9, 期 9, 页码 8731-8737出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.9b02213
关键词
heterogeneous catalysis; zeolite; computational chemistry; methane dehydroaromatization; cooperation
资金
- NWO veni grant [016.Veni.172.034]
- Ministry of education and Science of the Russian Federation [11.1706.2017/4.6]
Mo/ZSM-5 is one of the most studied and efficient catalysts for the dehydroaromatization of methane (MDA), but. the mechanism of its operation remains controversial. Here, we combine an ab initio thermodynamic analysis with a comprehensive mechanistic density functional theory study to address Mo-speciation in the zeolite and identify the active sites under the reaction conditions. We show that the exposure of Mo/ZSM-5 to the MDA conditions yields a range of reduced sites including mono- and binuclear Mo-oxo and Mo-carbide complexes. These sites can catalyze the MDA reaction via two alternative reaction channels, namely, the C-C coupling (ethylene) and the hydrocarbon-pool propagation mechanisms. Our calculations point toward the binuclear Mo-carbide species operating through the hydrocarbon-pool mechanism to be the most catalytically potent species. Although all other Mo sites in the activated catalyst can promote C-H activation in methane, they fail to provide a successful path to the desirable low-molecular-weight products.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据