Efficient dehydrogenation of formic acid using Al12N12 nanocage: A DFT study

• The dehydrogenation reaction of HCOOH on Al12N12 is studied.
• The formate group is the dominant surface species after the Al12N12 surface is exposed to HCOOH.
• For the dissociative adsorption configuration on the Al12N12 surface, the rate-determining step is the CH bond breaking.

We have studied the adsorption and decomposition of formic acid (HCOOH) on the surface of Al12N12 fullerene-like nanocage using density functional theory. Different adsorption modes were found for HCOOH on the Al12N12, i.e. molecular and dissociative monodentate or bidentate adsorption. Three reaction pathways were proposed to understand gas-phase HCOOH decomposition on the Al12N12 nanocage. Our results reveal that for the decomposition of HCOOH into CO2 and H2, the most favorable pathway should be the CH bond activation reaction. The reaction energies and the activation barriers obtained here suggest that for the dissociative adsorption configuration on the Al12N12 surface, the rate-determining step is the CH bond breaking.