Polythiophene Block Copolymer–Perylene Diimide-Based Electron Donor–Acceptor Double-Cable Polymer and Its Potential as an All-Organic Photocatalyst for Artificial Photosynthesis of H2O2

IF 5.5 3区材料科学 Q2 CHEMISTRY, PHYSICAL

ACS Applied Energy Materials Pub Date : 2025-09-05 DOI:10.1021/acsaem.5c02208

Faseeh Akbar, , , Sana Iqbal, , , Arwa Sohail, , , Senem Çitoğlu, , , Hatice Duran, , and , Basit Yameen*,

{"title":"Polythiophene Block Copolymer–Perylene Diimide-Based Electron Donor–Acceptor Double-Cable Polymer and Its Potential as an All-Organic Photocatalyst for Artificial Photosynthesis of H2O2","authors":"Faseeh Akbar, , , Sana Iqbal, , , Arwa Sohail, , , Senem Çitoğlu, , , Hatice Duran, , and , Basit Yameen*, ","doi":"10.1021/acsaem.5c02208","DOIUrl":null,"url":null,"abstract":"Enhancing the light energy harvesting and conversion capabilities of all-organic photoactive materials is of significant scientific interest. Herein, we report the synthesis of a photoactive double-cable polymer (DCP) consisting of a polythiophene (PTh) block copolymer electron donor (D) conjugated to a perylene diimide (PDI) electron acceptor (A). GRIM polymerization and postsynthetic modifications are employed to synthesize the block copolymer [P3HT-b-poly(3-HT-co-PTh/PDI)] consisting of a poly-3-hexylthiophene (P3HT) block and a block comprising of randomly distributed repeat units bearing hexyl and PDI groups. Besides 1H NMR, ATR-FTIR, UV/visible, and fluorescence spectroscopic characterizations, AFM and XRD analyses are performed to reveal self-assembly and crystallinity behaviors. Compared to P3HT, PDI, and their physical hybrid (P3HT–PDI-PH), the P3HT-b-poly(3-HT-co-PTh/PDI) shows superior D–A electronic communication, higher (photo)electrochemical current, faster electrochemical kinetics, and lower charge transfer resistance. The photocatalytic performance of all photocatalysts in the artificial photosynthesis of H2O2 is demonstrated over 10 photocatalytic cycles. Comparing the results from the highest H2O2 producing cycles, the photocatalytic performance of P3HT-b-poly(3HT-co-Th/PDI) is ∼2.1, ∼3.2, and ∼1.9 times superior compared to that of P3HT, PDI, and P3HT–PDI-PH, respectively. In summary, this work contributes to the development of organic semiconducting polymer-based photoactive materials for application in light energy harvesting and conversion technologies.","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 18","pages":"13861–13876"},"PeriodicalIF":5.5000,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Energy Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsaem.5c02208","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

Abstract

Enhancing the light energy harvesting and conversion capabilities of all-organic photoactive materials is of significant scientific interest. Herein, we report the synthesis of a photoactive double-cable polymer (DCP) consisting of a polythiophene (PTh) block copolymer electron donor (D) conjugated to a perylene diimide (PDI) electron acceptor (A). GRIM polymerization and postsynthetic modifications are employed to synthesize the block copolymer [P3HT-b-poly(3-HT-co-PTh/PDI)] consisting of a poly-3-hexylthiophene (P3HT) block and a block comprising of randomly distributed repeat units bearing hexyl and PDI groups. Besides ¹H NMR, ATR-FTIR, UV/visible, and fluorescence spectroscopic characterizations, AFM and XRD analyses are performed to reveal self-assembly and crystallinity behaviors. Compared to P3HT, PDI, and their physical hybrid (P3HT–PDI-PH), the P3HT-b-poly(3-HT-co-PTh/PDI) shows superior D–A electronic communication, higher (photo)electrochemical current, faster electrochemical kinetics, and lower charge transfer resistance. The photocatalytic performance of all photocatalysts in the artificial photosynthesis of H₂O₂ is demonstrated over 10 photocatalytic cycles. Comparing the results from the highest H₂O₂ producing cycles, the photocatalytic performance of P3HT-b-poly(3HT-co-Th/PDI) is ∼2.1, ∼3.2, and ∼1.9 times superior compared to that of P3HT, PDI, and P3HT–PDI-PH, respectively. In summary, this work contributes to the development of organic semiconducting polymer-based photoactive materials for application in light energy harvesting and conversion technologies.

Abstract Image

查看原文本刊更多论文

聚噻吩嵌段共聚物-苝二酰亚胺基电子给受体双缆聚合物及其作为H2O2人工光合作用全有机光催化剂的潜力

提高全有机光活性材料的光能收集和转换能力具有重要的科学意义。本文报道了一种由聚噻吩（PTh）嵌段共聚物电子给体(D)与苝二酰亚胺（PDI）电子受体(a)共轭而成的光活性双缆聚合物（DCP）的合成。采用GRIM聚合和合成后改性方法合成了嵌段共聚物[P3HT-b-poly(3-HT-co-PTh/PDI)]，该嵌段共聚物由聚3-己基噻吩（P3HT）嵌段和随机分布的含有己基和PDI基团的重复单元组成。除了1H NMR、ATR-FTIR、UV/可见光和荧光光谱表征外，还进行了AFM和XRD分析来揭示自组装和结晶度行为。与P3HT、PDI和它们的物理混合物（P3HT - PDI- ph）相比，P3HT-b-poly（3-HT-co-PTh/PDI）具有更好的D-A电子通信性能、更高的（光电）电化学电流、更快的电化学动力学和更低的电荷转移电阻。所有光催化剂在H2O2人工光合作用中的光催化性能在10个光催化循环中得到了验证。比较最高H2O2生成周期的结果，P3HT-b-poly（3HT-co-Th/PDI）的光催化性能分别是P3HT、PDI和P3HT- PDI- ph的2.1倍、3.2倍和1.9倍。综上所述，这项工作有助于开发用于光能收集和转换技术的有机半导体聚合物光活性材料。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

ACS Applied Energy Materials Materials Science-Materials Chemistry

CiteScore

10.30

自引率

6.20%

发文量

1368

期刊介绍： ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.