Citation: Jingkun Yu, Xue Yong, Ang Cao, Siyu Lu. 双层单原子催化剂用于促进高活性和选择性电催化硝酸盐还原制氨[J]. Acta Physico-Chimica Sinica, ;2024, 40(6): 230701. doi: 10.3866/PKU.WHXB202307015 shu

双层单原子催化剂用于促进高活性和选择性电催化硝酸盐还原制氨

Jingkun Yu ¹ ,
Xue Yong ^2,, ,
Ang Cao ³ ,
Siyu Lu ^1,,

1.
Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China;
2.
Department of Chemistry, University of Sheffield, Sheffield, S37HF, UK;
3.
Department of Physics, Technical University of Denmark, Kongens Lyngby 2800, Denmark

Corresponding author: Xue Yong, Siyu Lu,
Received Date: 6 July 2023
Revised Date: 22 August 2023
Accepted Date: 23 August 2023

Fund Project: This work was supported by the National Natural Science Foundation of China (51973200, 52122308) and the National Supercomputing Center in Zhengzhou, China. X.Y. would like to acknowledge Levhelum Trut.

高效、高选择性的单原子催化剂（SACs）在电催化硝酸盐还原制氨过程中具有重要作用。然而，由于中间体、金属活性中心和配位环境之间复杂的竞争性电子相互作用，仍然面临挑战。本研究采用密度泛函理论（DFT）计算，对27种SACs以及双层SACs （BSACs）进行了系统研究，通过轴向d–d轨道杂化提高了从SACs到BSACs的电催化硝酸盐还原反应（NO₃RR）的活性和选择性。考虑到可能的O端、N端、NO端和NO二聚体途径，计算结果显示，在单层SACs中，Ti-Pc和V-Pc分别具有优异的极限电位（U_L），分别为-0.24和-0.48 V。形成能、溶解势以及从头算分子动力学结果表明，在反应条件下，这些催化剂非常稳定。在这些单层TM-Pc中，它们的d带能级和占据数受到d_xz/d_yz和p_z轨道杂化的影响。其轴向d_z²轨道的可用性通过形成d_z²–d_z²相互作用来进一步调整d带和反应性。在此基础上，以Ti-Pc和V-Pc为底物，通过形成轴向d–d轨道杂化来构建BSACs，为调节NO₃RR催化性能提供了一种独特的新途径。重要的是，我们发现d带中心（ε_d）、d_xz+d_yz轨道的占据数和U_L之间存在二维火山关系，用于描述它们的NO₃RR催化性能。最佳的BSACs应该同时具备适当的ε_d和d_xz+d_yz占用数。Ti-Mo和Ti-Ta被确定为出色的NO₃RR催化剂，其U_L均降低至-0.13 V。而d_z²–d_z²轨道之间的杂化则增强了双层金属之间的电荷转移和结构稳定性。缺乏相邻的金属位点将导致生成NO₂、NO和N₂的能垒较高，从而抑制副产物生成。最终，本研究揭示了在SACs和BSACs上对硝酸盐还原进行合理优化的方法，可为改进电催化剂的设计提供指导。
- Nitrate reduction,
- First-principles calculation,
- Single-atom catalysts,
- Bilayer single-atom catalysts,
- Axial orbital hybridization
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