{"title":"柔性,不熔融的砜功能化聚合物,具有增强的活性位点进入光催化牺牲析氢","authors":"Tse-Fu Huang, Kuei-Jhong Lin, Ying-Rang Zhuang, Yu-En Sun, Wei-Cheng Lin, Chun-Hao Li, Chien-Cheng Lin, En-Chi Chang, Chih-Li Chang, Yung-Ching Liu, Ling-Yu Hsu, Bing-Heng Li, Wan-Ling Chang, Pimjai Pimbaotham, Cheng-Yun Bai, Wei-Hsiang Huang, Dung Chau Kim Hoang, Khanh Do Gia Huynh, Yi-Chan Huang, Chao-Yan Chung, Mohamed M. Elsenety, Chia-An Chang, Hsin-Ni Huang, Siriporn Jungsuttiwong, Chih-Wen Pao, Hsin-Lung Chen, Tien-Lin Wu, Chia-Chih Chang, Bo-Han Chen, Shang-Da Yang, Kun-Han Lin, Ho-Hsiu Chou","doi":"10.1126/sciadv.adx1629","DOIUrl":null,"url":null,"abstract":"<div >The fused sulfone unit has been a key building block for hydrogen evolution photocatalysts for 9 years but still faces the challenge of a poor water/polymer interface due to its rigid structure. This work introduces nonfused, flexible sulfur segments (SSs) into the polymer’s backbone to enhance hydrophilicity and active site access. Unlike rigid, fused sulfone moieties, our flexible SS improves interfacial water contact and charge transport. P-2SO<sub>2</sub>, with sulfone-functionalized SS, represents a 237% improvement over the control polymer, PBDTTSO. In addition, P-2SO<sub>2</sub> demonstrated an outstanding hydrogen evolution rate of 1060.1 micromoles per hour and an apparent quantum yield of 32.4% (460 nanometers). Molecular dynamics simulations indicate SS improves hydrophilicity and water/polymer interface while promoting a hairpin-like conformation that increases intrachain π-π stacking for better charge hopping. Transient absorption spectroscopy shows sulfone-functionalized SS enhances electron transfer to platinum cocatalysts, increases active site density, and reduces exciton migration lengths through stronger polymer/platinum interactions.</div>","PeriodicalId":21609,"journal":{"name":"Science Advances","volume":"11 30","pages":""},"PeriodicalIF":12.5000,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.science.org/doi/reader/10.1126/sciadv.adx1629","citationCount":"0","resultStr":"{\"title\":\"Flexible, nonfused sulfone functionalized polymer with enhanced active site access for photocatalytic sacrificial hydrogen evolution\",\"authors\":\"Tse-Fu Huang, Kuei-Jhong Lin, Ying-Rang Zhuang, Yu-En Sun, Wei-Cheng Lin, Chun-Hao Li, Chien-Cheng Lin, En-Chi Chang, Chih-Li Chang, Yung-Ching Liu, Ling-Yu Hsu, Bing-Heng Li, Wan-Ling Chang, Pimjai Pimbaotham, Cheng-Yun Bai, Wei-Hsiang Huang, Dung Chau Kim Hoang, Khanh Do Gia Huynh, Yi-Chan Huang, Chao-Yan Chung, Mohamed M. Elsenety, Chia-An Chang, Hsin-Ni Huang, Siriporn Jungsuttiwong, Chih-Wen Pao, Hsin-Lung Chen, Tien-Lin Wu, Chia-Chih Chang, Bo-Han Chen, Shang-Da Yang, Kun-Han Lin, Ho-Hsiu Chou\",\"doi\":\"10.1126/sciadv.adx1629\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div >The fused sulfone unit has been a key building block for hydrogen evolution photocatalysts for 9 years but still faces the challenge of a poor water/polymer interface due to its rigid structure. This work introduces nonfused, flexible sulfur segments (SSs) into the polymer’s backbone to enhance hydrophilicity and active site access. Unlike rigid, fused sulfone moieties, our flexible SS improves interfacial water contact and charge transport. P-2SO<sub>2</sub>, with sulfone-functionalized SS, represents a 237% improvement over the control polymer, PBDTTSO. In addition, P-2SO<sub>2</sub> demonstrated an outstanding hydrogen evolution rate of 1060.1 micromoles per hour and an apparent quantum yield of 32.4% (460 nanometers). Molecular dynamics simulations indicate SS improves hydrophilicity and water/polymer interface while promoting a hairpin-like conformation that increases intrachain π-π stacking for better charge hopping. Transient absorption spectroscopy shows sulfone-functionalized SS enhances electron transfer to platinum cocatalysts, increases active site density, and reduces exciton migration lengths through stronger polymer/platinum interactions.</div>\",\"PeriodicalId\":21609,\"journal\":{\"name\":\"Science Advances\",\"volume\":\"11 30\",\"pages\":\"\"},\"PeriodicalIF\":12.5000,\"publicationDate\":\"2025-07-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.science.org/doi/reader/10.1126/sciadv.adx1629\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Science Advances\",\"FirstCategoryId\":\"103\",\"ListUrlMain\":\"https://www.science.org/doi/10.1126/sciadv.adx1629\",\"RegionNum\":1,\"RegionCategory\":\"综合性期刊\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MULTIDISCIPLINARY SCIENCES\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Science Advances","FirstCategoryId":"103","ListUrlMain":"https://www.science.org/doi/10.1126/sciadv.adx1629","RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MULTIDISCIPLINARY SCIENCES","Score":null,"Total":0}
Flexible, nonfused sulfone functionalized polymer with enhanced active site access for photocatalytic sacrificial hydrogen evolution
The fused sulfone unit has been a key building block for hydrogen evolution photocatalysts for 9 years but still faces the challenge of a poor water/polymer interface due to its rigid structure. This work introduces nonfused, flexible sulfur segments (SSs) into the polymer’s backbone to enhance hydrophilicity and active site access. Unlike rigid, fused sulfone moieties, our flexible SS improves interfacial water contact and charge transport. P-2SO2, with sulfone-functionalized SS, represents a 237% improvement over the control polymer, PBDTTSO. In addition, P-2SO2 demonstrated an outstanding hydrogen evolution rate of 1060.1 micromoles per hour and an apparent quantum yield of 32.4% (460 nanometers). Molecular dynamics simulations indicate SS improves hydrophilicity and water/polymer interface while promoting a hairpin-like conformation that increases intrachain π-π stacking for better charge hopping. Transient absorption spectroscopy shows sulfone-functionalized SS enhances electron transfer to platinum cocatalysts, increases active site density, and reduces exciton migration lengths through stronger polymer/platinum interactions.
期刊介绍:
Science Advances, an open-access journal by AAAS, publishes impactful research in diverse scientific areas. It aims for fair, fast, and expert peer review, providing freely accessible research to readers. Led by distinguished scientists, the journal supports AAAS's mission by extending Science magazine's capacity to identify and promote significant advances. Evolving digital publishing technologies play a crucial role in advancing AAAS's global mission for science communication and benefitting humankind.