Metal-Free Reduction of NO over a Fullerene-like Boron Nitride Nanocluster: A Mechanistic Study by DFT Calculations

摘要

Density functional theory calculations are performed to investigate how the incorporation of a C atom into B_(12)N_(12) fullerenelike nanocluster modifies its catalytic activity towards the reduction of nitric oxide (NO) in the presence of CO molecule. The most stable adsorption configurations, adsorption energies, binding distances and net charge transfers are obtained to understand the impact of NO and CO molecules on the electronic properties of B_(12)N_(12) and B_(11)N_(12)C nanoclusters. Our results suggest a dimer mechanism for the reduction of NO over both surfaces. First, two NO molecules are attached together to form (NO)2 dimer. Then, (NO)2 is dissociated into N2O molecule and an activated O atom (O*). The O* is then removed by a CO or NO molecule, due to a small activation energy. The results indicate that the C-doping can significantly decrease the activation energies needed for the reduction of NO over B_(12)N_(12).