摘要：Density functional theory (DFT) calculation with numerical atomic functions is used to study oxygen effects on MoS2 hydrotreating active sites. The optimal form of oxygen on active sites is first investigated by experimentation and calculation. Then, the fine structures of a MoS2 nanocluster (S-Mo-S) and an oxygen containing MoS2 nanocluster (O-Mo-S) under reaction conditions, as well as their hydrodesulfurization (HDS) selectivity towards thiophene, are calculated. The results show that bent MoS2 nanoclusters in supported hydrotreating catalysts are more thermodynamically stable when oxygen is substituted for sulfur on the basal plane. Oxygen also reduces the electron density and unoccupied d-orbital energy levels of Mb atoms. The S atoms on the Mo-edge are also more readily substituted by H on O-Mo-S. During thiophene HDS, O-Mo-S has a stronger thiophene adsorption ability than S-Mo-S. Hydrogen transfer has a higher energy requirement along the Mo-edge on O-Mo-S than on S-Mo-S. The hydrogenation saturation activity to C=C is lower on the Mo-edge of O-Mo-S than of S-Mo-S, whereas the hydrogenolysis activity at the C-S bond is promoted by oxygen. It is predicted that the oxygen can increase the hydrogenolysis selectivity of a MoS2 active nanocluster. (C) 2016 Elsevier Ltd. All rights reserved.

关键字：DFT calculation MoS2 Oxygen effects Thiophene HDS

ISSN号：0016-2361

卷、期、页：卷: 194 页: 63-74

发表日期：2017-04-15

期刊分区（SCI为中科院分区）：二区

收录情况：SCI（科学引文索引印刷版）,ESI（基本科学指标数据库）,EI（工程索引）,SCIE（科学引文索引网络版）

发表期刊名称：FUEL

通讯作者：丁思佳,蒋淑娇,周文武

第一作者：周亚松,魏强

论文类型：期刊论文

论文概要：丁思佳,蒋淑娇,周亚松,魏强,周文武，Oxygen effects on the structure and hydrogenation activity of the MoS2 active site: A mechanism study by DFT calculation，FUEL，2017，卷: 194 页: 63-74

论文题目：Oxygen effects on the structure and hydrogenation activity of the MoS2 active site: A mechanism study by DFT calculation