The discovery of naturally frustrated
Lewis pairs (FLPs) on wurtzite-structured
surfaces provides a shortcut to obtain dense and stable surface FLPs
without complex surface engineering. However, the catalytic performance
and potential applications in the catalysis of natural FLPs have not
been thoroughly investigated. Herein, the heterolytic dissociation
of hydrogen is studied at the natural FLPs of wurtzite-structured
GaN, ZnO, and SiC surfaces by using theoretical methods. Compared
with classical Lewis pairs (CLPs), the FLPs show lower activation
barriers ranging from 0.07 to 0.16 eV but higher reaction energies
in the heterolytic dissociation of hydrogen. By splitting the energy
into different items via a chemical–physical model, the optimal
substrate–surface interaction and the decreasing stability
of lone pair electrons on N atoms are recognized as the main reason
for the lower activation energy and the higher reaction energy at
FLPs, respectively. Because of the relatively favorable kinetics and
unfavorable thermodynamics in hydrogen dissociation, FLPs present
superior performance in the selective hydrogenation of acetylene to
ethylene, reflected by the lower activation energy by 0.89 eV in the
rate-determining step than CLPs. Overall, this study not only provides
mechanistic insights into the heterolytic dissociation of hydrogen
at FLPs but also unfolds the advantages of FLPs in hydrogenation reactions.