Theoretical Investigations on the Structures and the Chemical Bonding of NbMoSn-/0 (n=3~7) Clusters

doi:10.6023/A16110578

Abstract

Recently, transition metal sulfides (TMS) have played an important role in many catalytic reactions. In particular, they are widely used in the petrochemical industry, such as the hydrodesulfurization (HDS) and the hydrodenitrogenation (HDN) processes. In this work, density functional theory (DFT) and coupled cluster theory[CCSD(T)] calculations were used to study the niobium-mixed di-nuclear molybdenum sulfide clusters NbMoS_n^-/0(n=3~7). In our calculations, their ground-state structures were determined and the effects of doping metal, adjusting the sulfur content (n) and changing the charge states of clusters were discussed on the geometries, electronic structures and chemical bonding of NbMoS_n^-/0(n=3~7). NbMoS_n^-/0(n=3~7) clusters can be viewed as linking different sulfur ligands to the NbMoS₂ four-membered rings. Among them, diverse poly-sulfur ligands, such as bridging S₂, terminal S₂ and terminal S₃ groups, emerged in the sulfur-rich clusters. Generalized Koopmans' Theorem was employed to predict the vertical detachment energies (VDEs), and simulate the corresponding anionic photoelectron spectra (PES). The first VDEs (VDE_1st) of NbMoS_n^-(n=3~6) increased gradually as a function of n, and then decreased suddenly when the sulfur content (n) reached 7. The VDE_1st reached the maximum by 4.69 eV when the sulfur content equaled to 6. The driving forces (-ΔG) of the reduction reactions between NbMoS_n^-/0(n=3~7) and H₂ were evaluated. The NbMoS₇^- anion with the terminal S₂^2- group yielded the negative value of ΔG, which indicated that the reaction is thermodynamically favored even at the room temperature. We predicted that doping niobium into the molybdenum sulfides may improve the emergence of S₂ group which may be helpful in producing the coordinatively unsaturated sites (CUS) under the H₂/H₂S atmosphere. Molecular orbital analyses are performed to improve our understanding on the structural evolution and the chemical bonding of NbMoS_n^-/0(n=3~7) clusters.

Key words: transition metal sulfide cluster, density functional theory, structural evolution, simulation of photoelectron spectrum

Cite this article

Wang Bin, Wang Jianfu, Zhang Xiaofei, Chen Wenjie, Zhang Yongfan, Huang Xin. Theoretical Investigations on the Structures and the Chemical Bonding of NbMoS_n^-/0 (n=3~7) Clusters[J]. Acta Chim. Sinica, 2017, 75(3): 307-320.

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二核铌钼硫簇NbMoS_n^-/0(n=3~7)掺杂体系的结构与成键性质的理论研究