Molecular-Level
Understanding of CeO<sub>2</sub> as
a Catalyst for Partial Alkyne Hydrogenation
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Abstract
The unique catalytic properties of
ceria for the partial hydrogenation
of alkynes are examined for acetylene hydrogenation. Catalytic tests
over polycrystalline CeO<sub>2</sub> at different temperatures and
H<sub>2</sub>/C<sub>2</sub>H<sub>2</sub> ratios reveal ethylene selectivities
in the range of 75–85% at high degrees of acetylene conversion
and hint at the crucial role of hydrogen dissociation on the overall
process. Density-functional theory is applied to CeO<sub>2</sub>(111)
in order to investigate reaction intermediates and to calculate the
enthalpy and energy barrier for each elementary step, taking into
account different adsorption geometries and the presence of potential
isomers of the intermediates. At a high hydrogen coverage, β-C<sub>2</sub>H<sub>2</sub> radicals adsorbed on-top of surface oxygen atoms
are the initial reactive species forming C<sub>2</sub>H<sub>3</sub> species effectively barrierless. The high alkene selectivity is
owed to the lower activation barrier for subsequent hydrogenation
leading to gas-phase C<sub>2</sub>H<sub>4</sub> compared to that for
the formation of β-C<sub>2</sub>H<sub>4</sub> radical species.
Moreover, hydrogenation of C<sub>2</sub>H<sub>5</sub> species, if
formed, must overcome significantly large barriers. Oligomers are
the most important byproduct of the reaction and they result from
the recombination of chemisorbed C<sub>2</sub>H<sub><i>x</i></sub> species. These findings rationalize for the first time the
applicability of CeO<sub>2</sub> as a catalyst for olefin production
and potentially broaden its use for the hydrogenation of polyunsaturated
and polyfunctionalized substrates containing triple bonds