Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO2(111)

• Published in: The journal of physical chemistry letters Vol. 8; no. 23; pp. 5810 - 5814
• Main Authors: Sutton, Jonathan E, Danielson, Thomas, Beste, Ariana, Savara, Aditya
• Format: Journal Article
• Language: English
• Published: American Chemical Society 07.12.2017
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.7b02683

Upgrading of primary alcohols by C–H bond breaking currently requires temperatures of >200 °C. In this work, new understanding from simulation of a temperature-programmed reaction study with methanol over a CeO2(111) surface shows C–H bond breaking and the subsequent desorption of formaldehyde, even below room temperature. This is of particular interest because CeO2 is a naturally abundant and inexpensive metal oxide. We combine density functional theory and kinetic Monte Carlo methods to show that the low-temperature C–H bond breaking occurs via disproportionation of adjacent methoxy species. We further show from calculations that the same transition state with comparable activation energy exists for other primary alcohols; with ethanol, 1-propanol, and 1-butanol explicitly calculated. These findings indicate a promising class of transition states to search for in seeking low-temperature C–H bond breaking over inexpensive oxides.