Catalytic
performance is known to be influenced by several factors,
with the catalyst surface oxidation state being the most prominent
of all. However, in the great majority of industrial heterogeneous
catalytic reactions the oxidation state of the active sites is a subject
of intense debate. Preferential oxidation of carbon monoxide in hydrogen-rich
mixtures (COPrOx) is an important heterogeneous catalytic reaction
involved in the purification of hydrogen. In the search for an economically
affordable catalyst for this reaction, cobalt appears as one of the
most promising materials. Therefore, it is essential to distinguish
if a certain surface state of cobalt exists that favors the reaction
more than the others. Here we directly compare the activity of CoO
and Co3O4 phases by combining ex situ and operando
analytical methods with first-principles modeling. CoO is identified
as the most favored cobalt surface oxidation state for the COPrOx
process, providing a critical element for the rational design of efficient
and durable COPrOx catalysts.
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