Abstract

AbstractCO disproportionation produces carbon deposits that cover active sites and induce catalyst deactivation. However, understanding of this detrimental reaction on reduced ceria is deficient. Herein, the reversibility and reaction mechanism of CO disproportionation on reduced ceria are investigated. The reversibility of the CO disproportionation was studied by CO pulse, isotopic oxygen tracer, thermal analysis, and CO2 pulse experiments. In situ diffuse‐reflectance infrared Fourier transform spectra indicate that the CO bond of the CO molecule on Ce3+ ion is weakened. With CO bond dissociation, asymmetrical inorganic carboxylate species are formed. These species are the key reaction intermediates in CO disproportionation and are further converted to produce CO2. EPR experiments indicate that the unpaired electrons produced by the reduction weaken the CO bond through back‐donation of electrons.

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