基于团簇MMoS_(4)(M=Ni,Co,Fe)催化析氢的密度泛函理论研究  

Density functional theory study on catalytic hydrogen evolution of cluster-based MMoS_(4)(M=Ni,Co,Fe)

作　　者：宋嘉 方志刚[1] 王智瑶 宋静丽 刘立娥 吴庭慧 SONG Jia;FANG Zhigang;WANG Zhiyao;SONG Jingli;LIU Li'e;WU Tinghui(School of Chemical Engineering,University of science and Technology Liaoning,Anshan 114051,China)

机构地区：[1]辽宁科技大学化学工程学院,辽宁鞍山114051

出　　处：《材料科学与工艺》2025年第2期67-74,共8页Materials Science and Technology

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项目(202210146008,202210146011)。

摘　　要：为探究团簇MMoS_(4)内部的催化析氢机理及性能,本研究以密度泛函理论为基础,在B3LYP/def2tzvp水平下运用Gaussian09软件分别在1、2、3、4重态下对团簇MMoS_(4)的初始构型进行优化计算,得到8种稳定构型,其中的5种稳定构型在吸附氢原子后能够稳定存在。对团簇MMoS_(4)的HOMO轨道图与水分子的LUMO轨道图、构型的前线轨道能级差以及结合能等进行了分析比较,结果表明:第1步析氢反应时,构型2^((2))、2^((4))、3^((3))表现出更好的催化活性,表明其在与水分子发生反应时易于吸附氢原子,电子能够更好地完成转移;在第2步解吸反应时,水中氢原子均吸附在团簇的Mo原子上,表明Mo原子是团簇析氢反应过程中的潜在活性位点,构型2^((2))、3^((2))在第2步解吸反应时展现出优异的析氢性能并更快地将氢气析出;综合分析认为,在团簇MMoS_(4)中构型2^((2))的催化析氢能力最佳。To investigate the catalytic hydrogen evolution mechanism and performance within the MMoS_4 clusters,this study is based on density functional theory.Using the Gaussian09 software at the B3LYP/def2tzvp level,optimization calculations were performed on the initial configurations of MMoS_4 clusters in their singlet,doublet,triplet,and quartet states,resulting in eight stable configurations,of which five remained stable after hydrogen adsorption.The HOMO orbital maps of the MMoS_4 clusters were compared with the LUMO orbital maps of water molecules,as well as the frontier orbital energy level differences and binding energies of different configurations.The results indicated that in the first hydrogen evolution step,configurations 2^((2)),2^((4)),and 3^((3))exhibited superior catalytic activity,suggesting their enhanced ability to adsorb hydrogen atoms and facilitate electron transfer during interactions with water molecules.In the second desorption step,hydrogen atoms were found to be adsorbed on the Mo atoms of the clusters,indicating that Mo atoms are potential active sites during the hydrogen evolution process.Configurations 2^((2))and 3^((2))demonstrated excellent hydrogen evolution performance and a faster release of hydrogen in the second desorption step.Collectively,the analysis suggests that configuration 2^((2))exhibits the best catalytic hydrogen evolution capability within the MMoS_4 clusters.

关 键 词：析氢 密度泛函理论 能级差 HOMO、LUMO图 前线轨道理论 

分 类 号：O641.12[理学—物理化学]