Construction of frustrated Lewis pairs on carbon nitride nanosheets for catalytic hydrogenation of acetylene

Abstract

Here, we studied Al or B atom-doped carbon nitride (g-C₃N₄ and C₂N) as catalysts for H₂ activation and acetylene hydrogenation using density functional theory calculations. The Al or B could be assembled with the surface N atoms of carbon nitride to form diverse frustrated Lewis pairs (FLPs). The results show that Al–N FLPs had lower barriers of H₂ activation in comparison with B–N FLPs. The heterolytic H₂ dissociation catalyzed by Al–N FLPs led to the formation of Al–H and N–H species. The Al–H species were highly active in the first hydrogenation of acetylene to C₂H₃*, yielding a mild barrier, while in the second hydrogenation step, the reaction between C₂H₃ and the H of N–H species caused a relatively high barrier. Electronic structure analysis demonstrated the electron transfer in the heterolytic H₂ cleavage and explained the activity differences in various FLPs. The results suggest that Al with the surface N of carbon nitride can act as an FLP to catalyze the H₂ activation and acetylene hydrogenation, thus providing a new strategy for the future development of noble metal-free hydrogenation catalysts.