Issue 9, 2020

Dual Lewis site creation for activation of methanol on Fe3O4(111) thin films

Abstract

Despite a wide application in heterogeneous catalysis, the surface termination of Fe3O4(111) remains controversial. Herein, a surface with both Lewis acid and base sites is created through formation of an Fe3O4(111) film on α-Fe2O3(0001). The dual functionality is generated from a locally nonuniform surface layer of O adatoms and Fetet1 sites. This reactive layer is reproducibly formed even in oxygen-free environments because of the high mobility of ions in the underlying α-Fe2O3(0001). The atomic structure of the Fe3O4(111) surface was identified by scanning tunneling microscopy (STM) and density functional theory (DFT) using the registry of the overlayers with the surface and the distinct electronic structure of oxygen adatom (Oad) and uncovered lattice Fetet1. The surface is dominated by the interface of Oad and Fetet1, a Lewis acid–base pair, which favors methanol dissociation at room temperature to form methoxy. Methoxy is further oxidized to yield formaldehyde at 700 K in temperature programmed reaction spectra, corresponding to an approximate activation barrier of 179 kJ mol−1. The surface termination of Fe3O4(111) is fully recovered by rapid heating to 720 K in vacuum, demonstrating the high mobility of ions in this material. The work establishes a clear fundamental understanding of a unique magnetite surface and provides insights into the origin of selective oxidation of alcohols on magnetite-terminated catalysts.

Graphical abstract: Dual Lewis site creation for activation of methanol on Fe3O4(111) thin films

Supplementary files

Article information

Article type
Edge Article
Submitted
04 Dec 2019
Accepted
23 Jan 2020
First published
24 Jan 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 2448-2454

Dual Lewis site creation for activation of methanol on Fe3O4(111) thin films

F. Xu, W. Chen, C. A. Walenta, C. R. O'Connor and C. M. Friend, Chem. Sci., 2020, 11, 2448 DOI: 10.1039/C9SC06149E

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