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Abstract

The preferential oxidation of CO in H₂-rich mixtures (COPrOx) is a major catalytic reaction utilized for hydrogen purification. In the exploration of alternatives to noble metals, cobalt-based catalysts appear to be a very promising choice. The activity and stability of cobalt in the COPrOx reaction can be improved by the addition of transition metals and manganese is maybe the most prominent among them. Yet, the arrangement of the two components in the catalytically active state is largely unknown, which hinders in-depth understanding of the manganese promotion effect. Here, we compare pure and Mn-modified cobalt catalysts and correlate their structural and chemical characteristics with their COPrOx performance. The Mn-promoted cobalt catalyst is significantly more active than pure cobalt especially at intermediate reaction temperatures (around 200 °C). The addition of Mn improves the structural stability of the catalyst and helps to maintain higher specific surface areas. Chemical and microstructural analysis using various operando and in situ techniques revealed that Mn promotes CO conversion by partially stabilizing CoO phase during reaction conditions. It is also suggested that at high temperature, Mn suppress CO methanation reaction but promotes H₂ oxidation. Apart of the particular interest in COPrOx reaction, in a general context, this work shows how the spatial distribution of the different catalyst components at nanoscopic level, may affect the surface chemistry and consequently control the reactivity.