CO2 hydrogenation to formic acid on Ni(110)

Hydrogen (H) in the subsurface of transition-metal surfaces exhibits unique reactivity for heterogeneously catalyzed hydrogenation reactions. Here, we explore the potential of subsurface H for hydrogenating carbon dioxide (CO2) on Ni(110). The energetics of surface and subsurface H reacting with surface CO2 to form formate, carboxyl, and formic acid on Ni(110) is systematically studied using self-consistent, spin-polarized, periodic density functional theory (DFT-GGA-PW91) calculations. We show that on Ni(110), CO2 can be hydrogenated to formate by surface H. However, further hydrogenation of formate to formic acid by surface H is hindered by a larger activation energy barrier. The relative energetics of hydrogenation barriers is reversed for the carboxyl-mediated route to formic acid. We suggest that the energetics of subsurface H emerging to the surface is suitable for providing the extra energy needed to overcome the barrier to formate hydrogenation. CO2 hydrogenation to formic acid could take place on Ni(110) when subsurface H is available to react with CO2. Additional electronic-structure based dynamic calculations would be needed to elucidate the detailed reaction paths for these transformations.