Theoretical Insights into the Atomic and Electronic Structures of polyperyleneimide: On the Origin of Photocatalytic Oxygen Evolution Activity

Authors

Yiqing Wang, International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, China.
Zhi Lin, International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, China.
Mingtao Li, International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, China.
Shaohua Shen, International Research Center for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, China.

Document Type

Article

Corresponding Author(s)

Shaohua Shen(shshen_xjtu@mail.xjtu.edu.cn)

Abstract

Polymeric perylene diimide (PDI) has been evidenced as a good candidate for photocatalytic water oxidation, yet the origin of the photocatalytic oxygen evolution activity remains unclear and need further exploration. Herein, with crystal and atomic structures revealed from the X-ray diffraction pattern, the electronic structure is theoretically illustrated by the first-principles density functional theory calculations, suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution. It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis. The reaction free energy changes calculations reveal that the oxygen evolution reaction should follow the pathway of H₂O → *OH → *O → *OOH → *O₂ with an overpotential of 0.81 V. Through an in-depth theoretical computational analysis in the atomic and electronic structures, the origin of photocatalytic oxygen evolution activity for PDI is well illustrated, which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.

Graphical Abstract

Keywords

Photocatalytic oxygen evolution, Polymeric perylene diimide, Atomic structure, Electronic structure, Reaction pathway

DOI

10.61558/2993-074X.3523

Online Date

2-8-2025

Recommended Citation

Yiqing Wang , Zhi Lin , Mingtao Li and Shaohua Shen. Theoretical Insights into the Atomic and Electronic Structures of Polyperyleneimide: On the Origin of Photocatalytic Oxygen Evolution Activity[J]. Journal of Electrochemistry, doi: 10.61558/2993-074X.3523.