Trimetallic clusters in the sumanene bowl for dinitrogen activation

Abstract

It is of great importance to find catalysts for the nitrogen reduction reaction (NRR) with high stability and reactivity. A series of M₃ clusters (M = Ti, Zr, V, and Nb) supported on sumanene (C₂₁H₁₂) were designed as potential catalysts for the NRR by taking advantage of the high reactivity of trimetallic clusters and the unique geometric and electronic properties of sumanene, a bowl-like organic molecule. Detailed mechanisms of NN bond cleavage on C₂₁H₁₂–M₃ were investigated by DFT calculations and compared with those on bare M₃ clusters. M₃ in the sumanene bowl is very stable with large binding energies, which prohibits the cohesion of M₃ into M₆. In the bowl, M₃ has a (quasi-) equilateral triangle structure with lengthened M–M bonds, which is particularly beneficial to the N₂ transfer process on Ti₃ and V₃ clusters. The N–N bond can be dissociated by both M₃ and C₂₁H₁₂–M₃ clusters without the overall energy barriers. A blurring effect is found in which some geometric and electronic properties of different metal types become similar when M₃ is supported on the substrate. Our work demonstrates that sumanene is a suitable substrate to support M₃ in the activation of N₂ with enhanced stability and maintained a high level of reactivity compared to bare M₃.