Performance and Solution Structures of Side-Chain-Bridged Oligo (Ethylene Glycol) Polymer Photocatalysts for Enhanced Hydrogen Evolution under Natural Light Illumination

IF 13 2区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Small Pub Date : 2023-10-06 DOI:10.1002/smll.202304743

Tse-Fu Huang, Jia-Jen Liu, Ze-Yu Lai, Je-Wei Chang, Ying-Rang Zhuang, Zi-Cheng Jiang, Chih-Li Chang, Wei-Cheng Lin, Yan-Heng Chen, Yi-Hsiang Wu, Yu-En Sun, Ting-An Luo, Yi-Kuan Chen, Jui-Chen Yen, Hung-Kai Hsu, Bo-Han Chen, Li-Yu Ting, Chia-Yeh Lu, Yu-Tung Lin, Ling-Yu Hsu, Tien-Lin Wu, Shang-Da Yang, An-Chung Su, U-Ser Jeng, Ho-Hsiu Chou

{"title":"Performance and Solution Structures of Side-Chain-Bridged Oligo (Ethylene Glycol) Polymer Photocatalysts for Enhanced Hydrogen Evolution under Natural Light Illumination","authors":"Tse-Fu Huang, Jia-Jen Liu, Ze-Yu Lai, Je-Wei Chang, Ying-Rang Zhuang, Zi-Cheng Jiang, Chih-Li Chang, Wei-Cheng Lin, Yan-Heng Chen, Yi-Hsiang Wu, Yu-En Sun, Ting-An Luo, Yi-Kuan Chen, Jui-Chen Yen, Hung-Kai Hsu, Bo-Han Chen, Li-Yu Ting, Chia-Yeh Lu, Yu-Tung Lin, Ling-Yu Hsu, Tien-Lin Wu, Shang-Da Yang, An-Chung Su, U-Ser Jeng, Ho-Hsiu Chou","doi":"10.1002/smll.202304743","DOIUrl":null,"url":null,"abstract":"Converting solar energy into hydrogen energy using conjugated polymers (CP) is a promising solution to the energy crisis. Improving water solubility plays one of the critical factors in enhancing the hydrogen evolution rate (HER) of CP photocatalysts. In this study, a novel concept of incorporating hydrophilic side chains to connect the backbones of CPs to improve their HER is proposed. This concept is realized through the polymerization of carbazole units bridged with octane, ethylene glycol, and penta-(ethylene glycol) to form three new side-chain-braided (SCB) CPs: PCz2S-OCt, PCz2S-EG, and PCz2S-PEG. Verified through transient absorption spectra, the enhanced capability of PCz2S-PEG for ultrafast electron transfer and reduced recombination effects has been demonstrated. Small- and wide-angle X-ray scattering (SAXS/WAXS) analyses reveal that these three SCB-CPs form cross-linking networks with different mass fractal dimensions (f) in aqueous solution. With the lowest f value of 2.64 and improved water/polymer interfaces, PCz2S-PEG demonstrates the best HER, reaching up to 126.9 µmol h−1 in pure water-based photocatalytic solution. Moreover, PCz2S-PEG exhibits comparable performance in seawater-based photocatalytic solution under natural sunlight. In situ SAXS analysis further reveals nucleation-dominated generation of hydrogen nanoclusters with a size of ≈1.5 nm in the HER of PCz2S-PEG under light illumination.","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0000,"publicationDate":"2023-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Small","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/smll.202304743","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

Abstract

Converting solar energy into hydrogen energy using conjugated polymers (CP) is a promising solution to the energy crisis. Improving water solubility plays one of the critical factors in enhancing the hydrogen evolution rate (HER) of CP photocatalysts. In this study, a novel concept of incorporating hydrophilic side chains to connect the backbones of CPs to improve their HER is proposed. This concept is realized through the polymerization of carbazole units bridged with octane, ethylene glycol, and penta-(ethylene glycol) to form three new side-chain-braided (SCB) CPs: PCz2S-OCt, PCz2S-EG, and PCz2S-PEG. Verified through transient absorption spectra, the enhanced capability of PCz2S-PEG for ultrafast electron transfer and reduced recombination effects has been demonstrated. Small- and wide-angle X-ray scattering (SAXS/WAXS) analyses reveal that these three SCB-CPs form cross-linking networks with different mass fractal dimensions (f) in aqueous solution. With the lowest f value of 2.64 and improved water/polymer interfaces, PCz2S-PEG demonstrates the best HER, reaching up to 126.9 µmol h⁻¹ in pure water-based photocatalytic solution. Moreover, PCz2S-PEG exhibits comparable performance in seawater-based photocatalytic solution under natural sunlight. In situ SAXS analysis further reveals nucleation-dominated generation of hydrogen nanoclusters with a size of ≈1.5 nm in the HER of PCz2S-PEG under light illumination.

Abstract Image

查看原文本刊更多论文

在自然光照下用于增强析氢的侧链桥接低聚（乙二醇）聚合物光催化剂的性能和溶液结构。

使用共轭聚合物（CP）将太阳能转化为氢能是解决能源危机的一个很有前途的方案。提高水溶性是提高CP光催化剂析氢速率的关键因素之一。在这项研究中，提出了一个新的概念，即引入亲水性侧链连接CP的主链，以提高其HER。这一概念是通过与辛烷、乙二醇和五（乙二醇）桥接的咔唑单元聚合形成三种新的侧链编织（SCB）CP来实现的：PCz2S OCt、PCz2S EG和PCz2S PEG。通过瞬态吸收光谱验证，PCz2S-PEG具有增强的超快电子转移能力和降低的复合效应。小角度和宽角度X射线散射（SAXS/WAXS）分析表明，这三种SCB-CP在水溶液中形成具有不同质量分形维数（f）的交联网络。PCz2S-PEG具有2.64的最低f值和改善的水/聚合物界面，表现出最佳的HER，在纯水性光催化溶液中达到126.9µmol h-1。此外，PCz2S-PEG在自然阳光下的海水基光催化溶液中表现出相当的性能。原位SAXS分析进一步揭示了在光照下PCz2S-PEG的HER中以成核为主的氢纳米团簇的产生，其尺寸约为1.5nm。

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

Small 工程技术-材料科学：综合

CiteScore

17.70

自引率

3.80%

发文量

1830

审稿时长

2.1 months

期刊介绍： Small serves as an exceptional platform for both experimental and theoretical studies in fundamental and applied interdisciplinary research at the nano- and microscale. The journal offers a compelling mix of peer-reviewed Research Articles, Reviews, Perspectives, and Comments. With a remarkable 2022 Journal Impact Factor of 13.3 (Journal Citation Reports from Clarivate Analytics, 2023), Small remains among the top multidisciplinary journals, covering a wide range of topics at the interface of materials science, chemistry, physics, engineering, medicine, and biology. Small's readership includes biochemists, biologists, biomedical scientists, chemists, engineers, information technologists, materials scientists, physicists, and theoreticians alike.