广西师范大学学报（自然科学版） ›› 2019, Vol. 37 ›› Issue (1): 165-172.doi: 10.16088/j.issn.1001-6600.2019.01.019

• 第二十四届全国信息检索学术会议专栏 • 上一篇    下一篇

团簇Ni3CoP催化析氢活性研究

李历红, 方志刚*, 赵振宁, 陈林, 韩建铭, 崔远东, 马填棋, 姜雨晨   

  1. 辽宁科技大学化学工程学院,辽宁鞍山114051
  • 收稿日期:2018-06-19 出版日期:2019-01-20 发布日期:2019-01-08
  • 通讯作者: 方志刚(1964—),男,辽宁鞍山人,辽宁科技大学教授,博士。E-mail:lnfzg@163.com
  • 基金资助:
    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(201710146000277, 201810146002, 201810146003);辽宁省大学生创新创业训练计划(201810146045, 201810146046, 201810146047)

Catalytic Properties of Cluster Ni3CoP in the Hydrogen Evolution Reaction

LI Lihong, FANG Zhigang*, ZHAO Zhenning, CHEN Lin, HAN Jianming, CUI Yuandong, MA Tianqi,JIANG Yuchen   

  1. School of Chemical Engineering, Liaoning University of Science and Technology, Anshan Liaoning 114501, China
  • Received:2018-06-19 Online:2019-01-20 Published:2019-01-08

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摘要： 基于密度泛函理论(density functional theory, DFT),在B3LYP/lanl2dz水平下对团簇Ni3CoP的初始构型进行单、三重态下的计算得到优化构型,依据前线轨道理论(frontier molecular orbital theory, FMO)着重通过分析前线轨道图以及比较前线轨道能级差对团簇Ni3CoP催化水析出氢气时的反应机理进行理论研究,结果表明:团簇Ni3CoP通过其最高占据分子轨道(highest occupied molecular orbital, HOMO)与水分子最低未占分子轨道(lowest unoccupied molecular orbital, HUMO)间的电子流动完成氢原子的吸附,且三重态构型在与水分子作用时,其β-HOMO轨道在反应中起主导作用。三重态构型在吸附氢原子后其促进解吸过程析出氢气的催化活性显著下降,而唯一的单重态构型1(1)不仅能在与水分子反应吸附氢原子的过程中展现出较好的催化效果,其在解吸过程中更是表现出了远好于其他三重态构型的催化能力。

关键词: 团簇Ni3CoP, 水解析氢, 催化活性, 前线轨道理论, 密度泛函理论

Abstract: Based on density functional theory (DFT), the primary structures of cluster Ni3CoP were optimized in singlet and triplet under B3LYP/lanl2dz level. According to the frontier molecular orbital theory (FMO), the mechanism of the hydrogen evolution reaction catalyzed by cluster Ni3CoP was studied theoretically from aspects of the frontier molecular orbital images and the difference between the frontier molecular orbital energy levels. Results showed that cluster Ni3CoP adsorbs H atom through electrons flowing from the highest occupied molecular orbital (HOMO) of cluster Ni3CoP to the lowest unoccupied molecular orbital (LUMO) of H2O. As for configurations in triplet, β-HOMO plays a prominent role in the reaction; however, their catalytic properties can descend apparently in the desorption of H atom to generate H2. Nevertheless, structure 1(1), the only configuration in singlet, can not only perform relatively good catalytic capability in adsorbing H atom from H2O but also improve the desorption process greatly compared with other configurations in triplet.

Key words: cluster Ni3CoP, water splitting for hydrogen, catalytic properties, frontier molecular orbital theory, density functional theory

中图分类号: 

  • O641.12
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