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Simulated Temperature Programmed Desorption of Acetaldehyde on CeO2(111): Evidence for the Role of Oxygen Vacancy and Hydrogen Transfer

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A Correction to this article was published on 27 February 2019

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Abstract

The temperature programmed desorption of acetaldehyde adsorbed on partially reduced CeO2(111) has been studied in detail using microkinetic modeling based on self-consistent, periodic density functional theory calculations at the GGA-PW91+U level. Previous experimental studies (Chen et al. J. Phys. Chem. C 115: 3385, 2011; Calaza et al. J. Am. Chem. Soc. 134: 18034, 2012) have shown that, whereas on fully oxidized CeO2(111) acetaldehyde desorbs molecularly with a peak temperature of 210 K, the polymerization and enolization of acetaldehyde dominate the surface reactivity on partially reduced CeO2(111), resulting in acetaldehyde desorption at higher temperatures. Here we propose a comprehensive reaction mechanism that is consistent with the spectroscopic evidence of the identities of the surface intermediates and with the observed desorption activities, including the formation of ethylene and acetylene. Besides acetaldehyde (CH3CHO) and its enolate (CH2CHO), several other C2H x O species are proposed as key intermediates which are not seen spectroscopically, including ethoxy (CH3CH2O), ethyleneoxy (CH2CH2O), and formylmethylene (CHCHO). Our study suggests that oxygen vacancies play the critical role of activating the carbonyl bond and thereby facilitating β C–H bond scissions in acetaldehyde, leading to enolization, intermolecular hydrogen transfer, deoxygenation, and potentially C–C coupling reactions.

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  • 27 February 2019

    The original version of this article unfortunately contained an error in Fig.��6. The authors would like to correct the error with this erratum. The errors were due to the missing of a factor of 2 in the rate expression for the surface coverage of atomic H when it desorbs as H2, and to incorrect settings for some of the initial coverages, in the microkinetic model. A corrected version is shown here as Fig.��6, with the same caption as before.

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Acknowledgments

This work was supported by the Louisiana Experimental Program to Stimulate Competitive Research (EPSCoR) Program, funded by the National Science Foundation and the Louisiana Board of Regents Support Fund, and has used high performance computational resources provided by Louisiana State University, the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, which is a U.S. Department of Energy (US-DOE), Office of Science User Facility, and the National Energy Research Scientific Computing Center, which is supported by the Office of Science of US-DOE under Contract No. DE-AC02-05CH11231.

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  1. Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA, 70803, USA

    Chuanlin Zhao & Ye Xu

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  1. Chuanlin Zhao
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Correspondence to Ye Xu.

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Zhao, C., Xu, Y. Simulated Temperature Programmed Desorption of Acetaldehyde on CeO2(111): Evidence for the Role of Oxygen Vacancy and Hydrogen Transfer. Top Catal 60, 446–458 (2017). https://doi.org/10.1007/s11244-016-0703-y

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