分子模拟与理论计算.ppt

Group of Porous Materials Catalysis Group of Porous Materials Catalysis 分子模拟与理论计算在多相催化研究中的应用 王建国 焦海军 李永旺 中科院山西煤化所 iccjgw@sxicc.ac.cn 研究背景 骨干成员 吸附 吸附热 吸附平衡常数 吸附等温线 吸附位 扩散（MD/MC） 路径、机理（构形扩散？） 扩散系数与孔道结构关系 形状选择反应 模扳剂的选择与作用 吸附 吸附热 吸附平衡常数（K） 吸附等温线 吸附位置 扩散路径及与孔道关系 分子筛中吸附的隔离效应 Nature of the traffic control shape selectivity ? 骨架结构与催化中心位置 表面酸强度与分布 物理吸附or化学吸附 扩散机理与活化能（D） 反应路径与过渡态（k） 分子筛的结构 取代位置及平衡质子在MOR中的位置 H2O, NH3在B, Al, Ga, Fe-MOR中的吸附 量子力学和分子力学组合方法 基本思想：把整个体系分割成三个区域 兼具量子力学的精确性和分子力学的高效性 N与质子酸中心间氢键作用 N:与电荷平衡离子间作用 Pyridine中H与骨架O间作用 Pyridine芳环与电荷平衡离子间作用 ZSM-5 的两类孔道及其交叉位 致 谢 中国科学院 国家科技部 山西煤化所 国家自然科学基金委 德国洪堡基金会 Work in progress of publication (1) Thiophene HDS Work in progress of publication (1) Thiophene will be first hydrogenated into 2,5-dihydrothiophene, from which Butadiene will be eliminated directly via a intramolecular way. Therefore, butadiene is the ONLY logical HSD product. Tetrahydrothiophene will be first dehydrogenated into 2,5-dihydrothiophene, and then go to butadiene, as found experimentally Work in progress of publication (2) CO adsorption on the Fe(111) surface Work in progress of publication (3) At 1/3 and 1/2 ML coverage, the shallow-hollow adsorption is the most stable site, while both shallow-hollow and bridge adsorption can coexist at 1 ML. Energetically, the bridge site rather than the suggested deep-hollow represents the reasonable adsorption configuration. In contrast, bent CO on-top and triply capping adsorption are the most favored forms at 2 ML. CO adsorption on the MoS2 surface Work in progress of publication (4) The adsorption energy of high coverage shows the additivity as compared with that of one CO ad-sorption, and there is no significant repulsive interaction between the end-on adsorbed CO probes. No bridged CO ad-sorption is favored energetically and this might explain the catalytic ability of MoS2 for C1 products instead of higher hydrocarbons and alcohols. * * 计算化学虚拟实