Synergistic Effects in the Activity of Nano‐Transition‐Metal Clusters Pt12M (M=Ir, Ru or Rh) for NO Dissociation

The dissociation of environmentally hazardous NO through dissociative adsorption on metallic clusters supported by oxides, is receiving growing attention. Building on previous research on monometallic M13 clusters [The Journal of Physical Chemistry C 2019, 123 (33), 20314-20318], this work considers bimetallic Pt12 M (M=Rh, Ru or Ir) clusters. The adsorption energy and activation energy of NO dissociation on the clusters have been calculated in vacuum using Kohn-Sham DFT, while their trends were rationalized using reactivity indices such as molecular electrostatic potential and global Fermi softness. The results show that doping of the Pt clusters lowered the adsorption energy as well as the activation energy for NO dissociation. Furthermore, reactivity indices were calculated as a first estimate of the performance of the clusters in realistic amorphous silica pores (MCM-41) through ab initio molecular dynamics simulations.