摘要
为探究过渡金属磷酸盐材料NiPS_(3)的催化活性并分析其催化作用机理,根据拓扑学原理和密度泛函理论,以团簇NiPS_(3)为局域模型,在B3LYP/def2-tzvp水平下,利用Gaussian09对团簇NiPS_(3)的初始构型进行了优化和分析。通过分析团簇NiPS_(3)的态密度图及HOMO和LUMO轨道图发现,费米能级左侧峰值和面积略大于右侧且HOMO轨道图中的离域面积大于LUMO轨道图,说明团簇NiPS_(3)具有一定的得失电子能力,且失电子能力大于得电子能力。利用前线轨道理论和库普曼斯定理对团簇NiPS_(3)各个优化构型进行分析发现,S原子附近的离域空间面积较大,对HOMO和LUMO轨道的贡献作用最大,说明S原子最有可能成为团簇NiPS_(3)的潜在催化活性位点。构型5;的能隙差最小,电离势最小,电子亲和能和电负性相对较大,且亲电指数最大,说明其催化活性最强。
In order to explore the catalytic activity of transition metal phosphate material NiPS_(3)and analyze its catalytic mechanism,based on the topological theory and density functional theory, taking cluster NiPS_(3)as the local model, the initial configuration of cluster NiPS_(3)was optimized and analyzed by Gaussian09 at B3LYP/def2-tzvp level. By analyzing the state density and HOMO and LUMO plots of cluster NiPS_(3), it is found that the peak value and area of the left Fermi level are slightly larger than that of the right and the delocalization area of HOMO orbital diagram is larger than that of LUMO orbital diagram, indicating that cluster NiPS_(3)has a certain ability to gain and lose electrons, and the ability to lose electrons is greater than the ability to gain electrons. Based on the frontier orbital theory and Koopmans’ theorem, the optimal configurations of cluster NiPS_(3)were analyzed. It is found that the delocalization space near S atom is larger and contributes the most to HOMO and LUMO orbitals, indicating that S atom is the most likely potential catalytic active site of cluster NiPS_(3). Configuration 5;has the smallest energy gap, the smallest ionization potential,the largest electron affinity and electronegativity, and the largest electrophilic index, indicating that it has the strongest catalytic activity.
作者
宋静丽
方志刚
曾鑫渔
朱依文
毛智龙
刘立娥
魏代霞
SONG Jingli;FANG Zhigang;ZENG Xinyu;ZHU Yiwen;MAO Zhilong;LIU Li’e;WEI Daixia(School of Chemical Engineering,University of Science and Technology Liaoning,Anshan 114051,Liaoning,China)
出处
《天然气化工—C1化学与化工》
CAS
北大核心
2022年第2期76-82,115,共8页
Natural Gas Chemical Industry
基金
国家自然科学基金重点项目(51634004)
国家级大学生创新创业训练计划(202110146027,202010146009,202010146016)
辽宁省大学生创新创业训练计划项目(202110146049,202110146052,202110146030,202110146055,202110146040,202110146056)。
