噻吩在Au13和Pt13团簇上加氢脱硫的反应机理比较.pdfVIP

文章编号: 0253-2409(2016)08-0961-09 Received: 2016-03-15; Revised: 2016-04-25. *Corresponding author. Tel: +86 E-mail: jchx@ zjut. edu. cn. The project was supported by the National Natural Science Foundation of China . 国家自然科学基金资助 噻吩在 Au13 和 Pt13 团簇上加氢脱硫的反应机理比较 蒋军辉, 曹勇勇, 倪哲明*, 张连阳 (浙江工业大学 化学工程学院, 浙江 杭州 310014) 摘 要: 采用密度泛函理论研究了噻吩在立方正八面体的 M13(M=Au、Pt)团簇上的吸附和加氢脱硫行为。 结果表明,噻吩以 环吸附于 Au13上的 Hol-tri位或 Pt13上的 Hol-quadr位时最稳定,且 Pt13上的吸附稳定性更高。 在 M13催化体系中,按间接加氢 脱硫机理,反应可能依顺式加氢的方式进行;其中,C-S键断裂开环所需的活化能最高,是反应的限速步骤;按直接加氢脱硫 机理,HS加氢所需活化能最高,是反应的限速步骤。 同时该机理总体所需活化能较间接加氢脱硫机理更低,是更为合理的脱 硫机理。 噻吩加氢脱硫过程中,Au13体系为放热反应,而 Pt13体系为吸热反应,并且 Au13体系加氢所需活化能更低;因此,Au13 更有利于噻吩加氢脱硫反应的进行。 关键词: 噻吩; 加氢脱硫; 吸附; Au13团簇; Pt13团簇; 密度泛函理论 中图分类号: O641 文献标识码: A Comparison of reaction mechanism of thiophene hydrodesulfurization on Au13 and Pt13 clusters JIANG Jun-hui, CAO Yong-yong, NI Zhe-ming*, ZHANG Lian-yang (College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China) Abstract: The behaviors of thiophene adsorption and hydrodesulfurization on cubic octahedral M13(M = Au, Pt) clusters were investigated by density functional theory. The results show that the adsorption energy of thiophene on Pt13 is higher than that on Au13; on the Au13 cluster, the Hol-tri site is most stable for the thiophene adsorption with ring, whereas on the Pt13 cluster, the Hol-quadr site is most stable. By the indirect desulfurization mechanism, the desulfurization is achieved probably via the cis-hydrogenation; the removal of C-S is the rate-determining step. By the direct desulfurization mechanism, the HS hydrogenation turns to be the rate-determining step. The desulfurization is most likely via the direct desulfurization mechanism, which exhibits much lower activation energy than the indirect desulfurization mechanism. The energy change for thiophene desulfurization on the Au13 cluster is exothermic, whereas on the Pt13 cluster it is endothermic; as a result, the hydrodesulfuri