Spectroscopic Identification of the α-Fe/α-O Active Site in Fe-CHA Zeolite for the Low-Temperature Activation of the Methane C-H Bond

Journal of the American Chemical Society
Max L BolsBert F Sels

Abstract

The formation of single-site α-Fe in the CHA zeolite topology is demonstrated. The site is shown to be active in oxygen atom abstraction from N2O to form a highly reactive α-O, capable of methane activation at room temperature to form methanol. The methanol product can subsequently be desorbed by online steaming at 200 °C. For the intermediate steps of the reaction cycle, the evolution of the Fe active site is monitored by UV-vis-NIR and Mössbauer spectroscopy. A B3LYP-DFT model of the α-Fe site in CHA is constructed, and the ligand field transitions are calculated by CASPT2. The model is experimentally substantiated by the preferential formation of α-Fe over other Fe species, the requirement of paired framework aluminum and a MeOH/Fe ratio indicating a mononuclear active site. The simple CHA topology is shown to mitigate the heterogeneity of iron speciation found on other Fe-zeolites, with Fe2O3 being the only identifiable phase other than α-Fe formed in Fe-CHA. The α-Fe site is formed in the d6r composite building unit, which occurs frequently across synthetic and natural zeolites. Finally, through a comparison between α-Fe in Fe-CHA and Fe-*BEA, the topology's 6MR geometry is found to influence the structure, the ligand fiel...Continue Reading

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Citations

May 30, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Samuel RaynesRussell A Taylor
Nov 4, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Max L BolsBert F Sels
Jan 13, 2021·Chemical Communications : Chem Comm·Ozgun Memioglu, Bahar Ipek
Jun 16, 2021·Chemical Society Reviews·Pablo Del CampoAvelino Corma
Apr 17, 2020·ACS Applied Materials & Interfaces·Ying-Juan HaoFa-Tang Li
Aug 27, 2021·Science·Benjamin E R SnyderEdward I Solomon
Sep 28, 2021·Journal of the American Chemical Society·Max L BolsMichiel Dusselier
Oct 7, 2021·Advanced Materials·Qiming SunJihong Yu
Jan 26, 2022·Chemical Reviews·Hannah M RhodaEdward I Solomon

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