Non‐Dissociative Activation of Chemisorbed Dinitrogen on One or Two Vanadium Atoms Supported by a Mo₆S₈ Cluster

Abstract

Adsorption of N₂ on Mo₆ S₈ ^q _V_x clusters (x=0, 1, 2; q=0, ±1) were systematically studied by density functional theory calculations with dispersion corrections. It was found that the N₂ can be chemisorbed and undergo non-dissociative activation on single or double metal atoms. The adsorption and activation are influenced by metal types (V or Mo), N₂ coordination modes and charge states of the clusters. Particularly, anionic Mo₆ S₈ ^- _V₂ clusters have remarkable ability to fix and activate N₂ . In Mo₆ S₈ ^- _V₂ , two V atoms prefer to adsorb on two adjacent S-Mo-S hollow sites, leading to the formation of a supported V…V unit. The N₂ is bridged side-on coordinated with these two V atoms with high adsorption energy and significant charge transfer. The bond order, bond length and vibration frequency of the adsorbed N₂ are close to those of a N-N single bond.