The steam reforming of ethanol on
a Ni-based CeO2-supported catalyst was studied using in
situ X-ray diffraction (XRD), operando diffuse reflectance infrared
Fourier transform spectroscopy (DRIFTS), and mass spectroscopy (MS)
with a focus on the structural characterization of the catalysts,
chemical identification of the reaction pathway, and understanding
of the interaction between Ni and the CeO2 support. Ethoxy,
acetate, carbonate, and hydroxyl species are identified by DRIFTS
as surface intermediates that appear during the reaction process.
The oxidation of ethoxy to acetate and the decomposition of acetate
are two key steps in the steam reforming process. The CeO2 support facilitates the oxidation of ethoxy to acetate below 350
°C. Above 350 °C, the Ni metal catalyzes dissociation of
the C–C bond in acetate to form carbonate and methyl, something
that the CeO2 support is not able to do. The Ce(III) sites
produced by the reduction of ceria in ethanol help to dissociate water
forming the surface hydroxyl groups, which react with the methyl groups
to produce CO2 and inhibited the methyl groups’
progress to CH4. Post-reaction transmission electron microscopy
(TEM) images of the Ni/CeO2 catalyst reveal two types of
carbon configurations: encapsulating carbon and filamentous carbon.
A water-rich atmosphere favors formation of carbon filaments, which
do not deactivate the catalyst.