Toward a More Rational Design of the Direct Synthesis of Aniline: A Density Functional Theory Study

[Image: see text] Plane-wave density functional theory (PW-DFT) calculations have been used to investigate the direct amination of benzene catalyzed by a Ni(111) surface to explore the reaction intermediates and to understand the role of nickel in this reaction. Adsorption structures, sites, energetics, and proposed reaction pathways relevant to the amination of benzene on the Ni(111) surface were investigated using the spin-polarized slab model with the Perdew–Burke–Ernzerhof functional. The dispersion-corrected DFT-D3 was used to examine the effect of van der Waals interactions on the adsorption energy. Detailed discussion of the adsorption behaviors of NH, NH(2), C(6)H(5), C(6)H(5)NH(2), and C(6)H(5)NH on the Ni(111) surface is provided. Imide and benzene were predicted to be the most predominant adsorbed species on the Ni(111) surface, and a reaction process involving a surface-bound anilide as an intermediate was predicted to be more thermodynamically favorable than other reaction pathways. The electronic interactions and vibrational frequencies of isolated and adsorbed molecules were also investigated.