Abstract
In heterogeneous catalysis, bifunctional catalysts often outperform one-component catalysts. The activity is also strongly influenced by the morphology, size, and distribution of catalytic particles. For CO(2) hydrogenation, the size of the active copper area on top of the SrTiO(3) perovskite catalyst support can affect the activity, selectivity, and stability. Here, a detailed theoretical study of the effect of bifunctionality on an important chemical CO(2) transformation reaction, the reverse water gas shift (RWGS) reaction, is presented. Using density functional theory computation results for the RWGS pathway on three surfaces, namely, Cu(111), SrTiO(3), and the Cu/SrTiO(3) interface between both solid phases, we construct the energy landscape of the reaction. The adsorbate-adsorbate lateral interactions are taken into account for catalytic surfaces, which show a sufficient intermediate coverage. The mechanism, combining all three surfaces, is used in mesoscale kinetic Monte Carlo simulations to study the turnover and yield for CO production as a function of particle size. It is shown that the reaction proceeds faster at the interface. However, including copper and the support sites in addition to the interface accelerates the conversion even further, showing that the bifunctionality of the catalyst manifests in a more complex interplay between the phases than just the interface effect, such as the hydrogen spillover. We identify three distinct effects, the electronic, cooperative, and geometric effects, and show that the surrounded smaller Cu features on the set of supporting SrTiO(3) show a higher CO formation rate, resulting in a decreasing RWGS model trend with the increasing Cu island size. The findings are in parallel with experiments, showing that they explain the previously observed phenomena and confirming the size sensitivity for the catalytic RWGS reaction.