Bay‐Monosubstitution with Electron‐Donating Group as an Efficiently Strategy to Functionalize Perylene Imide Polymer for Enhancing Photocatalytic Oxygen Evolution Activity. (22nd August 2022)

• Record Type: Journal Article
• Authors: Zhang, Jie; Wang, Zejin; Shi, Jinyan; Zhu, Wenbo; Yang, Le; Wang, Ying; Zou, Zhigang
• Is Part Of: Advanced functional materials. Volume 32:Number 43(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-22
• Subjects: oxygen production -- perylene imide polymer -- photocatalysis -- substituents; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.202205895
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract: It is still a challenge to develop an organic conjugated photocatalyst with a high O2 evolution rate. Functionalization organic polymer photocatalysts is an effective way to enhance photocatalytic performance. In this study, a series of perylene imide polymers (PDIs) are prepared by introducing different number of phenyl groups at bay position of PDI, and the influence of the number of substituents on charge separation and photocatalytic activity is investigated. It reveals that monosubstituted PDI exhibits the highest O2 evolution rate of 2524.88 µmol g –1 h –1 under visible light illumination without any cocatalyst. The excellent performance ascribes to the push–pull intramolecular charge transfer and the high crystallinity, which significantly promote separation and transfer of photoinduced charge. However, the O2 evolution rate dramatically drops with the number of substituent groups increase because introducing more groups at the bay position of PDI decreased charge local excitation of the PDI core and occupied the O2 evolution active site. In addition, it is found that increasing the number of electron–donor substituent groups would seriously destroy the crystallinity, leading to a decrease in the O2 evolution rate. This study highlights a reasonably structural modification strategy to enhance the O2 evolution rate of the PDI polymer by electron‐donating group monosubstitution. Abstract : Bay position substituted perylene imide polymers (PDIs) are synthesized by introducing electron‐donating groups on the PDI core. Monosubstituted PDI exhibits the highest O2 evolution rate of 2524.88 µmol g ‐1 h ‐1 under visible light illumination without any cocatalyst. Introducing a phenyl group at the bay position of PDI can increase π‐electron delocalization, promote charge separation/transfer, and reduce the energy barrier for rate determining step.