The conversion of cis-2-butene with deuterium over a well-defined Pd/Fe3O4 model catalyst was studied by isothermal pulsed molecular beam (MB) experiments under ultra high vacuum conditions. This study focuses on the processes related to dissociative hydrogen adsorption and diffusion into the subsurface of Pd nanoparticles and their influence on the activity and selectivity toward competing cis–transisomerization and hydrogenation pathways. The reactivity was studied both under steady state conditions and in the transient regime, in which the reaction takes place on a D-saturated catalyst, over a large range of reactant pressures and reaction temperatures. We show that large olefin coverages negatively affect the abundance of D species, as indicated by a reduction of both reaction rates under steady state conditions as compared to the transient reactivity on the catalyst pre-saturated with D2. Limitations in D availability during the steady state lead to a very weak dependence of both reaction rates on the olefin pressure. In contrast, when the surface is initially saturated with D, the transient reaction rates of both pathways exhibit positive kinetic orders on the butene pressure. Cis–transisomerization and hydrogenation show kinetic orders of +0.7 and +1.0 on the D2 pressure, respectively. Increasing availability of D noticeably shifts the selectivity toward hydrogenation. These observations together with the analysis of the transient reaction behavior suggest that the activity and selectivity of the catalyst is strongly controlled by its ability to build up and maintain a sufficiently high concentration of D species under reaction conditions. The temperature dependence of the reaction rates indicates that higher activation energies are required for the hydrogenation pathway than for the cis–transisomerization pathway, implying that different rate limiting steps are involved in the competing reactions.
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