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J Phys Chem B. 2018 Jan 18;122(2):548-554. doi: 10.1021/acs.jpcb.7b04681. Epub 2017 Aug 14.

Structure of the Clean and Oxygen-Covered Cu(100) Surface at Room Temperature in the Presence of Methanol Vapor in the 10-200 mTorr Pressure Range.

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Paulson School of Engineering and Applied Sciences, Harvard University , Cambridge, Massachusetts 02138, United States.
Department of Materials Science and Engineering, University of California , Berkeley, California 94720, United States.


Using ambient pressure X-ray photoelectron spectroscopy (APXPS) and high pressure scanning tunneling microscopy (HPSTM), we show that in equilibrium with 0.01-0.2 Torr of methanol vapor, at room temperature, the Cu(100) surface is covered with methoxy species forming a c(2 × 2) overlayer structure. In contrast, no methoxy is formed if the surface is saturated with an ordered oxygen layer, even when the methanol pressure is 0.2 Torr. At oxygen coverages below saturation, methanol dissociates and reacts with the atomic oxygen, producing methoxy and formate on the surface, and formaldehyde that desorbs to the gas phase. Unlike the case of pure carbon monoxide and carbon dioxide, methanol does not induce the restructuring of the Cu(100) surface. These results provide insight into catalytic anhydrous production of aldehydes.


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