RESUMO
Catalysts with heteronuclear metal active sites may have high performance in the nitrogen reduction reaction (NRR), and the in-depth understanding of the reaction mechanisms is crucial for the design of related catalysts. In this work, the dissociative adsorption of N2 on heteronuclear trimetallic MFe2 and M2 Fe (M=V, Nb, and Ta) clusters was studied with density functional theory calculations. For each cluster, two reaction paths were studied with N2 initially on M and Fe atoms, respectively. Mayer bond order analysis provides more information on the activation of N-N bonds. M2 Fe is generally more reactive than MFe2 . The coordination mode of N2 on three metal atoms can be end-on: end-on: side-on (EES) for both MFe2 and M2 Fe. In addition, a unique end-on: side-on: side-on (ESS) coordination mode was found for M2 Fe, which leads to a higher degree of N-N bond activation. Nb2 Fe has the highest reactivity towards N2 when both the transfer of N2 and the dissociation of N-N bonds are taken into account, while Ta-containing clusters have a superior ability to activate the N-N bond. These results indicate that it is possible to improve the performance of iron-based catalysts by doping with vanadium group metals.