Yongchao Hao , Jun Zhao , Hongfang Li , Min Li , Guiquan Guo , Jiangyu Zhang , Fengyan Fu
{"title":"通过侧链工程调节苯并双噻唑基线性共轭聚合物的亲水性以改善光催化析氢","authors":"Yongchao Hao , Jun Zhao , Hongfang Li , Min Li , Guiquan Guo , Jiangyu Zhang , Fengyan Fu","doi":"10.1016/j.jphotochem.2025.116530","DOIUrl":null,"url":null,"abstract":"<div><div>Photocatalytic hydrogen evolution through water splitting using conjugated polymer catalysts presents a promising prospect for sustainable energy production, however, challenges in charge carrier dynamics and interfacial reactivity limit practical implementation of conjugated polymers. This study systematically investigates the role of hydrophilic side-chain engineering in optimizing photocatalytic performance by designing structurally homologous benzobisthiazole-based linear conjugated polymers, B-PBT (butyl side chains) and O-PBT (oligoethylene glycol side chains), with matched light absorption spectra and morphologies. Structural characterization confirmed identical conjugated backbones and semi-crystalline features, while morphological analysis revealed analogous flake-like architectures for both polymers. Despite comparable light absorption ranges, O-PBT exhibited a 7-fold higher hydrogen evolution rate than B-PBT under visible light, attributed to hydrophilic modulation. Contact angle measurements (34.0° for O-PBT v.s. 59.5° for B-PBT) and photoelectrochemical analyses demonstrated enhanced interfacial water affinity, suppressed charge recombination and reduced charge-transfer resistance in O-PBT. This work decouples hydrophilicity effects from light-absorptive and morphological factors, establishing side-chain engineering as a critical strategy for optimizing interfacial reactivity and charge dynamics in organic photocatalysts.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116530"},"PeriodicalIF":4.7000,"publicationDate":"2025-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Side chain engineering for modulating hydrophilicity of benzobisthiazole-based linear conjugated polymer to improve the photocatalytic hydrogen evolution\",\"authors\":\"Yongchao Hao , Jun Zhao , Hongfang Li , Min Li , Guiquan Guo , Jiangyu Zhang , Fengyan Fu\",\"doi\":\"10.1016/j.jphotochem.2025.116530\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Photocatalytic hydrogen evolution through water splitting using conjugated polymer catalysts presents a promising prospect for sustainable energy production, however, challenges in charge carrier dynamics and interfacial reactivity limit practical implementation of conjugated polymers. This study systematically investigates the role of hydrophilic side-chain engineering in optimizing photocatalytic performance by designing structurally homologous benzobisthiazole-based linear conjugated polymers, B-PBT (butyl side chains) and O-PBT (oligoethylene glycol side chains), with matched light absorption spectra and morphologies. Structural characterization confirmed identical conjugated backbones and semi-crystalline features, while morphological analysis revealed analogous flake-like architectures for both polymers. Despite comparable light absorption ranges, O-PBT exhibited a 7-fold higher hydrogen evolution rate than B-PBT under visible light, attributed to hydrophilic modulation. Contact angle measurements (34.0° for O-PBT v.s. 59.5° for B-PBT) and photoelectrochemical analyses demonstrated enhanced interfacial water affinity, suppressed charge recombination and reduced charge-transfer resistance in O-PBT. This work decouples hydrophilicity effects from light-absorptive and morphological factors, establishing side-chain engineering as a critical strategy for optimizing interfacial reactivity and charge dynamics in organic photocatalysts.</div></div>\",\"PeriodicalId\":16782,\"journal\":{\"name\":\"Journal of Photochemistry and Photobiology A-chemistry\",\"volume\":\"469 \",\"pages\":\"Article 116530\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-05-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Photochemistry and Photobiology A-chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1010603025002709\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Photochemistry and Photobiology A-chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1010603025002709","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Side chain engineering for modulating hydrophilicity of benzobisthiazole-based linear conjugated polymer to improve the photocatalytic hydrogen evolution
Photocatalytic hydrogen evolution through water splitting using conjugated polymer catalysts presents a promising prospect for sustainable energy production, however, challenges in charge carrier dynamics and interfacial reactivity limit practical implementation of conjugated polymers. This study systematically investigates the role of hydrophilic side-chain engineering in optimizing photocatalytic performance by designing structurally homologous benzobisthiazole-based linear conjugated polymers, B-PBT (butyl side chains) and O-PBT (oligoethylene glycol side chains), with matched light absorption spectra and morphologies. Structural characterization confirmed identical conjugated backbones and semi-crystalline features, while morphological analysis revealed analogous flake-like architectures for both polymers. Despite comparable light absorption ranges, O-PBT exhibited a 7-fold higher hydrogen evolution rate than B-PBT under visible light, attributed to hydrophilic modulation. Contact angle measurements (34.0° for O-PBT v.s. 59.5° for B-PBT) and photoelectrochemical analyses demonstrated enhanced interfacial water affinity, suppressed charge recombination and reduced charge-transfer resistance in O-PBT. This work decouples hydrophilicity effects from light-absorptive and morphological factors, establishing side-chain engineering as a critical strategy for optimizing interfacial reactivity and charge dynamics in organic photocatalysts.
期刊介绍:
JPPA publishes the results of fundamental studies on all aspects of chemical phenomena induced by interactions between light and molecules/matter of all kinds.
All systems capable of being described at the molecular or integrated multimolecular level are appropriate for the journal. This includes all molecular chemical species as well as biomolecular, supramolecular, polymer and other macromolecular systems, as well as solid state photochemistry. In addition, the journal publishes studies of semiconductor and other photoactive organic and inorganic materials, photocatalysis (organic, inorganic, supramolecular and superconductor).
The scope includes condensed and gas phase photochemistry, as well as synchrotron radiation chemistry. A broad range of processes and techniques in photochemistry are covered such as light induced energy, electron and proton transfer; nonlinear photochemical behavior; mechanistic investigation of photochemical reactions and identification of the products of photochemical reactions; quantum yield determinations and measurements of rate constants for primary and secondary photochemical processes; steady-state and time-resolved emission, ultrafast spectroscopic methods, single molecule spectroscopy, time resolved X-ray diffraction, luminescence microscopy, and scattering spectroscopy applied to photochemistry. Papers in emerging and applied areas such as luminescent sensors, electroluminescence, solar energy conversion, atmospheric photochemistry, environmental remediation, and related photocatalytic chemistry are also welcome.