Methyl radical chemistry in non-oxidative methane activation over metal single sites

Xin Huang, Daniel Eggart, Gangqiang Qin, Bidyut Bikash Sarma, Abhijeet Gaur, Jiuzhong Yang, Yang Pan, Mingrun Li, Jianqi Hao, Hongfei Yu, Anna Zimina, Xiaoguang Guo, Jianping Xiao, Jan-Dierk Grunwaldt (), Xiulian Pan () and Xinhe Bao ()
Additional contact information
Xin Huang: Chinese Academy of Sciences
Daniel Eggart: Karlsruhe Institute of Technology
Gangqiang Qin: Chinese Academy of Sciences
Bidyut Bikash Sarma: Karlsruhe Institute of Technology
Abhijeet Gaur: Karlsruhe Institute of Technology
Jiuzhong Yang: University of Science and Technology
Yang Pan: University of Science and Technology
Mingrun Li: Chinese Academy of Sciences
Jianqi Hao: Chinese Academy of Sciences
Hongfei Yu: Chinese Academy of Sciences
Anna Zimina: Karlsruhe Institute of Technology
Xiaoguang Guo: Chinese Academy of Sciences
Jianping Xiao: Chinese Academy of Sciences
Jan-Dierk Grunwaldt: Karlsruhe Institute of Technology
Xiulian Pan: Chinese Academy of Sciences
Xinhe Bao: Chinese Academy of Sciences

Nature Communications, 2023, vol. 14, issue 1, 1-9

Abstract: Abstract Molybdenum supported on zeolites has been extensively studied as a catalyst for methane dehydroaromatization. Despite significant progress, the actual intermediates and particularly the first C-C bond formation have not yet been elucidated. Herein we report evolution of methyl radicals during non-oxidative methane activation over molybdenum single sites, which leads selectively to value-added chemicals. Operando X-ray absorption spectroscopy and online synchrotron vacuum ultraviolet photoionization mass spectroscopy in combination with electron microscopy and density functional theory calculations reveal the essential role of molybdenum single sites in the generation of methyl radicals and that the formation rate of methyl radicals is linearly correlated with the number of molybdenum single sites. Methyl radicals transform to ethane in the gas phase, which readily dehydrogenates to ethylene in the absence of zeolites. This is essentially similar to the reaction pathway over the previously reported SiO2 lattice-confined single site iron catalyst. However, the availability of a zeolite, either in a physical mixture or as a support, directs the subsequent reaction pathway towards aromatization within the zeolite confined pores, resulting in benzene as the dominant hydrocarbon product. The findings reveal that methyl radical chemistry could be a general feature for metal single site catalysis regardless of the support (either zeolites MCM-22 and ZSM-5 or SiO2) whereas the reaction over aggregated molybdenum carbide nanoparticles likely facilitates carbon deposition through surface C-C coupling. These findings allow furthering the fundamental insights into non-oxidative methane conversion to value-added chemicals.

Date: 2023
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DOI: 10.1038/s41467-023-41192-y

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