Spatial Confinement as an Effective Strategy for Improving the Catalytic Selectivity in Acetylene Hydrogenation

While control over chemical reactions is largely achieved by altering the intrinsic properties of catalysts, novel strategies are constantly being proposed to improve the catalytic performance in an extrinsic way. Since the fundamental chemical behavior of molecules can remarkably change when their molecular scale is comparable to the size of the space where they are located, creating spatially confined environments around the active sites offers new means of regulating the catalytic processes. We demonstrate through first-principles calculations that acetylene hydrogenation can exhibit significantly improved selectivity within the confined sub-nanospace between two-dimensional (2D) monolayers and the Pd(111) substrate. Upon intercalation of molecules, the lifting and undulation of a 2D monolayer on Pd(111) influence the adsorption energies of intermediates to varying extents, which, in turn, changes the energy profiles of the hydrogenation reactions. Within the confined sub-nanospace, the formation of ethane is always unfavorable, demonstrating effective suppression of the unwanted overhydrogenation. Moreover, the catalytic properties can be further tuned by altering the coverage of the adsorbates as well as strains within the 2D monolayer. Our results also indicate that for improving the selectivity, the strategy of spatial confinement could not be combined with that of single-atom catalysis, since the reactant molecules cannot enter the sub-nanospace due to the too weak adsorbate-substrate interaction. This work sheds new light on designing novel catalysts with extraordinary performance for the selective hydrogenation of acetylene.