CS和COS在γ-AlO表面吸附的密度泛函理论研究.doc

CS2和COS在γ-Al2O3表面吸附的密度泛函理论研究 5 10 15 20 25 30 35 40  摘要煤气中的有机含硫化合物 CS2 和 COS 对环境及后续的反应带来很大的危害Al2O3 是广泛使用的脱硫剂小分子在固体表面的吸附是研究气固反应的基础采用量子化学密度 泛函理论方法研究了 CS2 和 COS 在 γ-Al2O3 110 表面的吸附结果表明 CS2 的最稳定的构型 为 CS2 的三个原子分别与表面的 Al-O-Al 键中的三个原子作用形成了 COS2 2-物种此构 型的吸附能为 10798 kJ·mol-1COS 以 S-C 键与表面的一个 Al-O 键作用时最稳定吸附能 为 9999 kJ·mol-1通过分波态密度和小分子吸附前后净电荷的变化可知在这两个构型中 小分子与表面有很强的相互作用 关键词物理化学吸附CS2COSγ-Al2O3 表面 中图分类号O064732 Density functional theory study on the adsorption of CS2 and COS on the γ-Al2O3 surface WANG Baojun1 LING Lixia2 SONG Jiajia1 NIU Xiaoqi1 1 Key Laboratory of Coal Science and Technology Minisitry of Education and Shanxi Province Taiyuan University of Technology TaiYuan 030024 2 Research Institute of Special Chemicals Taiyuan University of Technology TaiYuan 030024 Abstract CS2 and COS are organic sulfur-containing compounds that often appears in coal gas Trace of CS2 and COS not only affects the environment but also provides economic problems within the down stream processes Al2O3 is a widely used desulfurizer Adsorption of molecules on surfaces is a fundamental step for the chemical reaction between gaseous and solid states The adsorption of CS2 and COS on the γ-Al2O3 110 surface has been studied using the density functional theory method It can be concluded that the most stable adsorption configuration for CS2 is three atoms in CS2 interacting with the Al-O-Al bond respectively and a COS2 2- species is formed The adsorption energy is 10798 kJ·mol-1 the most stable adsorption structure for COS is that the S-C bond in COS interacting with the Al-O bond in Al2O3 with an adsorption energy of 9999 kJ·mol-1 The partial density of state and Mulliken net charge show that there is a strong interaction between small molecules and theγ-Al2O3 110 surface Keywords Physical chemistry adsorption CS2 COS γ-Al2O3 surface 0 引言 CS2 和 COS 是一类广泛存在于焦炉气水煤气天然气中的有机含硫化合物[12]若将 这些气体作为原料气将导致甲醇尿素等合成化工生产过程中催化剂中毒[34]未经处理 的 CS2 排放到空气中会通过光化学反应形成酸雨因此CS2 和 COS 的脱除是一个值得 关注的话题 Al2O3 是将 CS2 和 COS 通过水解脱