电化学（中英文）2025，Vol.31Issue(5)：28-36,9.DOI:10.61558/2993-074X.3523
聚苝酰亚胺原子和电子结构的理论见解:光催化析氧活性的起源
Theoretical Insights into the Atomic and Electronic Structures of Polyperyleneimide:On the Origin of Photocatalytic Oxygen Evolution Activity
摘要
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 needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theo-retically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.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 calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H2O →*OH →*O →*OOH →*O2 with an overpotential of 0.81 V.Through an in-depth theoret-ical 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.关键词
光催化析氧反应/聚苝酰亚胺/原子结构/电子结构/反应路径Key words
Photocatalytic oxygen evolution/Polymeric perylene diimide/Atomic structure/Electronic structure/Reaction pathway引用本文复制引用
王亦清,林治,李明涛,沈少华..聚苝酰亚胺原子和电子结构的理论见解:光催化析氧活性的起源[J].电化学（中英文）,2025,31(5):28-36,9.基金项目
This work was supported by National Natural Science Foundation of China(No.523B2070,No.52225606). （No.523B2070,No.52225606）
