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Topological quantum catalyst: Dirac nodal line states and a potential electrocatalyst of hydrogen evolution in the TiSi family

拓扑量子催化: TiSi家族的拓扑节线态和潜在催化析氢性能

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Abstract

Topological nodal line (DNL) semimetals, a closed loop of the inverted bands in its bulk phases, result in the almost flat drumhead-like non-trivial surface states (DNSSs) with an unusually high electronic density near the Fermi level. High catalytic active sites generally associated with high electronic densities around the Fermi level, high carrier mobility and a close-to-zero free energy of the adsorbed state of hydrogen (ΔGH*≈0) are prerequisite to design alternative of precious platinum for catalyzing electrochemical hydrogen production from water. By combining these two aspects, it is natural to consider if the DNLs are a good candidate for the hydrogen evolution reaction (HER) or not because its DNSSs provide a robust platform to activate chemical reactions. Here, through first-principles calculations we reported a new DNL TiSi-type family, exhibiting a closed Dirac nodal line due to the linear band crossings in k y =0 plane. The hydrogen adsorbed state on the surface yields ΔGH* to be almost zero and the topological charge carries participate in HER. The results highlight a new routine to design topological quantum catalyst utilizing the topological DNL-induced surface bands as active sites, rather than edge sites-, vacancy-, dopant-, strain-, or heterostructure-created active sites.

摘要

拓扑节线半金属具有体能带反转形成的闭合环状狄拉克节线. 体狄拉克节线投影到某些表面会形成闭合的圈, 圈内会出现受拓扑保护的能量色散非常小的鼓膜状表面态, 导致在费米能级具有高的电子密度. 目前, 为寻求贵金属铂的替代物, 新的析氢反应催化剂需要具有高电子密度的催化活性位置, 高的载流子移动性和恰当的热力学稳定性(ΔG≈0). 由鉴于此, 我们考虑具有稳定拓扑非平庸表面态的狄拉克节线半金属是否可以作为析氢催化的平台. 基于第一性原理计算, 我们提出TiSi型拓扑节线态半金属新家族. 在其倒空间k y =0面, 反转的两条能带相交形成闭合的狄拉克节线环. 氢吸附过程计算表明, 拓扑狄拉克节线完整投影的(010)表面氢吸附自由能ΔG几乎为0. 并且,拓扑电荷载流子也参与到了析氢过程. 综上, 我们提出拓扑狄拉克节线系统可以利用其鼓膜类拓扑表面态作为拓扑量子催化的平台, 并认为TiSi家族材料有望成为析氢反应的催化剂, 这种催化设计路线主要利用拓扑节线材料非平庸鼓膜类表面态作为催化活性位置, 与以往传统通过缺陷、界面修饰和构筑等调控催化剂存在本质不同.

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Acknowledgements

This work was supported by the National Science Fund for Distinguished Young Scholars (51725103), the National Natural Science Foundation of China (51671193 and 51474202), and the Science Challenging Project (TZ2016004). All calculations have been performed on the high-performance computational cluster in Shenyang National University Science and Technology Park and the National Supercomputing Center in Guangzhou (TH-2 system) with special program for applied research of the NSFC-Guangdong Joint Fund (the second phase) (U1501501).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Shenyang National Laboratory for Materials Science, the Institute of Metal Research, Chinese Academy of Sciences, School of Materials Science and Engineering, University of Science and Technology of China, Shenyang, 110016, China

    Jiangxu Li  (李江旭), Hui Ma  (马会), Qing Xie  (谢庆), Shaobo Feng  (封少波), Sami Ullah, Ronghan Li  (李荣汉), Dianzhong Li  (李殿中), Yiyi Li  (李依依) & Xing-Qiu Chen  (陈星秋)

  2. Environmental Corrosion Center, the Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China

    Hui Ma  (马会) & Junhua Dong  (董俊华)

  3. University of Chinese Academy of Sciences, Beijing, 100049, China

    Qing Xie  (谢庆) & Sami Ullah

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  1. Jiangxu Li  (李江旭)
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Corresponding author

Correspondence to Xing-Qiu Chen  (陈星秋).

Additional information

Author contributions Chen XQ designed and supervised the project. Li J, Xie Q, Li R, Ullah S performed the DFT calculations of structural optimizations, electronic structures for all compounds. Li J performed the calculations of tight-binding modeling and surface states for DNLs. Ma H and Li J performed the calculations of hydrogen evolution reaction. Chen XQ analyzed results and wrote the paper with the inputs from Li J, Ma H, Ullah S, Li R. All authors including Li D, Dong J, Feng S and Li Y discussed the results and commented on the manuscript.

Conflict of interest The authors declare no conflict of interest.

Supplementary information The computational details, parameters, and any associated references are available in the supplementary material.

Jiangxu Li received his BSc degree from the Central South University in 2015. Now, he is a PhD candidate under the supervision of Prof. Xing-Qiu Chen at the Institute of Metal Research, Chinese Academy of Sciences, School of Materials Science and Engineering, University of Science and Technology of China. His research interest focuses on topological material design.

Hui Ma received her BSc degree from Hebei University of Technology in 2013. Now, she is a PhD candidate under the supervision of Prof. Junhua Dong and Prof. Xing-Qiu Chen at the Institute of Metal Research, Chinese Academy of Sciences, School of Materials Science and Engineering, University of Science and Technology of China. Her research interest focuses on electrochemical corrosion and catalysis.

Xing-Qiu Chen obtained his PhD degree in computational materials science at the University of Vienna in 2004 and completed his postdoctoral studies at Vienna Center of Computational Materials Science and Oak Ridge National Laboratory from 2005 to 2010. He is currently a professor at Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, funded by Hundred Talent Project and by the National Science Fund of Distinguished Young Scholars. His main scientific interests focus on the computational design of alloys including high-performance structural alloys, topological metals and alloys as well as the explorations of their potential applications.

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Topological quantum catalyst: Dirac nodal line states and a potential electrocatalyst of hydrogen evolution in the TiSi family

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Li, J., Ma, H., Xie, Q. et al. Topological quantum catalyst: Dirac nodal line states and a potential electrocatalyst of hydrogen evolution in the TiSi family. Sci. China Mater. 61, 23–29 (2018). https://doi.org/10.1007/s40843-017-9178-4

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