Identifying key mononuclear Fe species for low-temperature methane oxidation

Tao Yu; Zhi Li; Wilm Jones; Yuanshuai Liu; Qian He; Weiyu Song; Pengfei Du; Bing Yang; Hongyu An; Daniela M. Farmer; Chengwu Qiu; Aiqin Wang; Bert M. Weckhuysen; Andrew M. Beale; Wenhao Luo

doi:10.1039/D0SC06067D

Identifying key mononuclear Fe species for low-temperature methane oxidation†

Tao Yu,

^ab Zhi Li,^c Wilm Jones,

^de Yuanshuai Liu,^f Qian He,

^g Weiyu Song,

^c Pengfei Du,^bh Bing Yang,

^h Hongyu An,

^f Daniela M. Farmer,^de Chengwu Qiu,^de Aiqin Wang,

^ai Bert M. Weckhuysen,

*^f Andrew M. Beale

*^de and Wenhao Luo

*^a

Author affiliations

* Corresponding authors

^a CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, China
E-mail: w.luo@dicp.ac.cn

^b University of Chinese Academy of Sciences, Beijing 100049, China

^c State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China

^d Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
E-mail: andrew.beale@ucl.ac.uk

^e Research Complex at Harwell (RCaH), Rutherford Appleton Laboratory, Harwell, Didcot, Oxon OX11 0FA, UK

^f Inorganic Chemistry and Catalysis Group, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, Utrecht, The Netherlands
E-mail: B.M.Weckuysen@uu.nl

^g Department of Materials Science and Engineering, National University of Singapore, Engineering Drive 1, Singapore, Singapore

^h Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, China

ⁱ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Abstract

The direct functionalization of methane into platform chemicals is arguably one of the holy grails in chemistry. The actual active sites for methane activation are intensively debated. By correlating a wide variety of characterization results with catalytic performance data we have been able to identify mononuclear Fe species as the active site in the Fe/ZSM-5 zeolites for the mild oxidation of methane with H₂O₂ at 50 °C. The 0.1% Fe/ZSM-5 catalyst with dominant mononuclear Fe species possess an excellent turnover rate (TOR) of 66 mol_MeOH mol_Fe⁻¹ h⁻¹, approximately 4 times higher compared to the state-of-the-art dimer-containing Fe/ZSM-5 catalysts. Based on a series of advanced in situ spectroscopic studies and ¹H- and ¹³C- nuclear magnetic resonance (NMR), we found that methane activation initially proceeds on the Fe site of mononuclear Fe species. With the aid of adjacent Brønsted acid sites (BAS), methane can be first oxidized to CH₃OOH and CH₃OH, and then subsequently converted into HOCH₂OOH and consecutively into HCOOH. These findings will facilitate the search towards new metal-zeolite combinations for the activation of C–H bonds in various hydrocarbons, for light alkanes and beyond.

This article is part of the themed collection: 2021 Chemical Science HOT Article Collection

Chemical Science

Identifying key mononuclear Fe species for low-temperature methane oxidation†

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Identifying key mononuclear Fe species for low-temperature methane oxidation

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