Acetic acid conversion to ketene on Cu2O(1 0 0): Reaction mechanism deduced from experimental observations and theoretical computations
Journal article, 2021

Ketene, a versatile reagent in production of fine and specialty chemicals, is produced from acetic acid. We investigate the synthesis of ketene from acetic acid over the (3,0;1,1) surface of Cu2O(1 0 0) through analysis of the adsorption and desorption characteristics of formic and acetic acids. The results allow us to establish a reaction mechanism for ketene formation. Observations from x-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy, and temperature programmed desorption (TPD), supported by a comparison with formic acid results, suggest that acetic acid reacts with Cu2O through deprotonation to form acetate species coordinated to copper sites and hydroxylation of nearby surface oxygen sites. For formic acid the decomposition of adsorbed formate species results in desorption of CO2 and CO while, for acetic acid, high yields of ketene are observed at temperature >500 K. Modeling by density functional theory (DFT) confirms the strong interaction of acetic acid with the (3,0;1,1) surface and the spontaneous dissociation into adsorbed acetate and hydrogen atom species, the latter forming an OH-group. In an identified reaction intermediate ketene binds via all C and O atoms to Cu surface sites, in agreement with interpretations from XPS. In the vicinity of the adsorbate the surface experiences a local reorganization into a c(2 × 2) reconstruction. The total computed energy barrier for ketene formation is 1.81 eV in good agreement with the 1.74 eV obtained from TPD analysis. Our experimental observations and mechanistic DFT studies suggests that Cu2O can operate as an efficient catalyst for the green generation of ketene from acetic acid.

Heterogeneous catalysis

Scanning tunneling microscopy

Density functional theory


X-ray photoelectron spectroscopy

Acetic acid


H. Tissot

Royal Institute of Technology (KTH)

J. Halldin Stenlid

AlbaNova University Center

C. Wang

Royal Institute of Technology (KTH)

M. Panahi

Koç University

S. Kaya

Koç University

T. Brinck

Royal Institute of Technology (KTH)

Yasmine Sassa

Chalmers, Physics, Materials Physics

Fredrik O.L. Johansson

Uppsala University

Jonas Weissenrieder

Royal Institute of Technology (KTH)

Journal of Catalysis

0021-9517 (ISSN) 1090-2694 (eISSN)

Vol. 402 154-165

Realization of Novel Low‐Dimensional Skyrmion Systems

Swedish Research Council (VR) (2017-05078), 2019-06-01 -- 2021-12-31.

Subject Categories

Inorganic Chemistry

Other Chemistry Topics

Organic Chemistry

Areas of Advance

Materials Science



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