Hydroxyl improving the activity, selectivity and stability of supported Ni single atoms for selective semi-hydrogenation

Atomically dispersed metal catalysts with high atomic utilization and selectivity have been widely studied for acetylene semi-hydrogenation in excess ethylene among others. Further improvements of activity and selectivity, in addition to stability and loading, remain elusive due to competitive adsorption and desorption between reactants and products, hydrogen activation, partial hydrogenation etc. on limited site available. Herein, comprehensive density functional theory calculations have been used to explore the new strategy by introducing an appropriate ligand to stabilize the active single atom, improving the activity and selectivity on oxide supports. We find that the hydroxyl group can stabilize Ni single atoms significantly by forming Ni(1)(OH)(2) complexes on anatase TiO(2)(101), whose unique electronic and geometric properties enable high performance in acetylene semi-hydrogenation. Specifically, Ni(1)(OH)(2)/TiO(2)(101) shows favorable acetylene adsorption and promotes the heterolytic dissociation of H(2) achieving high catalytic activity, and it simultaneously weakens the ethylene bonding to facilitate subsequent desorption showing high ethylene selectivity. Hydroxyl stabilization of single metal atoms on oxide supports and promotion of the catalytic activity are sensitive to transition metal and the oxide supports. Compared to Co, Rh, Ir, Pd, Pt, Cu, Ag and Au, and anatase ZrO(2), IrO(2) and NbO(2) surfaces, the optimum interactions between Ni, O and Ti and resulted high activity, selectivity and stability make Ni(1)(OH)(2)/TiO(2)(101) a promising catalyst in acetylene hydrogenation. Our work provides valuable guidelines for utilization of ligands in the rational design of stable and efficient atomically dispersed catalysts.