Linquan Hou, Xiangjing Xie, Ye Li, Ting Song*, Xiayi Hu, Bei Long and Guo-Jun Deng*,
{"title":"疏水施主-(π-受体)共价有机框架增强光催化CO2还原制备多碳燃料","authors":"Linquan Hou, Xiangjing Xie, Ye Li, Ting Song*, Xiayi Hu, Bei Long and Guo-Jun Deng*, ","doi":"10.1021/acssuschemeng.5c04175","DOIUrl":null,"url":null,"abstract":"<p >Covalent organic frameworks (COFs) have emerged as promising candidates for photocatalytic CO<sub>2</sub> reduction, yet achieving high efficiency for C<sub>2+</sub> (C<sub>2</sub>H<sub>4</sub>, C<sub>3</sub>H<sub>6</sub>) products remains challenging due to inherent hydrophilicity and rapid charge recombination. We synthesized three isostructural COFs by polymerizing 2,4,6-triformylphloroglucinol with fluorine-tuned amine monomers. Strategic fluorination induces in-plane hydrogen bonding to lock π-conjugated acceptor (A) units, forming a donor-(π-acceptor) (D-(π-A)) architecture that suppresses electron–hole recombination postexcitation while enhancing charge carrier mobility through π-A coplanarity. Concurrently, fluorination creates a hydrophobic surface to mitigate CO<sub>2</sub> mass-transfer limitations, elevating local CO<sub>2</sub> concentration and optimizing proton availability at the three-phase interface. The multifluorinated COF demonstrates exceptional photocatalytic activity for CO<sub>2</sub>-to-propylene conversion, exhibiting 18.1-fold and 1.5-fold enhancements over its nonfluorinated and monofluorinated counterparts, respectively. This work establishes fluorination as a dual-functional strategy to simultaneously regulate electronic structures and surface properties in COFs, providing new pathways for solar-driven synthesis of multicarbon chemicals from sustainable C<sub>1</sub> feedstocks while contributing to ecological sustainability.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 33","pages":"13354–13364"},"PeriodicalIF":7.3000,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enhancing Photocatalytic CO2 Reduction to Multicarbon Fuels via Hydrophobic Donor-(π-Acceptor) Covalent Organic Frameworks\",\"authors\":\"Linquan Hou, Xiangjing Xie, Ye Li, Ting Song*, Xiayi Hu, Bei Long and Guo-Jun Deng*, \",\"doi\":\"10.1021/acssuschemeng.5c04175\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Covalent organic frameworks (COFs) have emerged as promising candidates for photocatalytic CO<sub>2</sub> reduction, yet achieving high efficiency for C<sub>2+</sub> (C<sub>2</sub>H<sub>4</sub>, C<sub>3</sub>H<sub>6</sub>) products remains challenging due to inherent hydrophilicity and rapid charge recombination. We synthesized three isostructural COFs by polymerizing 2,4,6-triformylphloroglucinol with fluorine-tuned amine monomers. Strategic fluorination induces in-plane hydrogen bonding to lock π-conjugated acceptor (A) units, forming a donor-(π-acceptor) (D-(π-A)) architecture that suppresses electron–hole recombination postexcitation while enhancing charge carrier mobility through π-A coplanarity. Concurrently, fluorination creates a hydrophobic surface to mitigate CO<sub>2</sub> mass-transfer limitations, elevating local CO<sub>2</sub> concentration and optimizing proton availability at the three-phase interface. The multifluorinated COF demonstrates exceptional photocatalytic activity for CO<sub>2</sub>-to-propylene conversion, exhibiting 18.1-fold and 1.5-fold enhancements over its nonfluorinated and monofluorinated counterparts, respectively. This work establishes fluorination as a dual-functional strategy to simultaneously regulate electronic structures and surface properties in COFs, providing new pathways for solar-driven synthesis of multicarbon chemicals from sustainable C<sub>1</sub> feedstocks while contributing to ecological sustainability.</p>\",\"PeriodicalId\":25,\"journal\":{\"name\":\"ACS Sustainable Chemistry & Engineering\",\"volume\":\"13 33\",\"pages\":\"13354–13364\"},\"PeriodicalIF\":7.3000,\"publicationDate\":\"2025-08-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Sustainable Chemistry & Engineering\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acssuschemeng.5c04175\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Sustainable Chemistry & Engineering","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acssuschemeng.5c04175","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Enhancing Photocatalytic CO2 Reduction to Multicarbon Fuels via Hydrophobic Donor-(π-Acceptor) Covalent Organic Frameworks
Covalent organic frameworks (COFs) have emerged as promising candidates for photocatalytic CO2 reduction, yet achieving high efficiency for C2+ (C2H4, C3H6) products remains challenging due to inherent hydrophilicity and rapid charge recombination. We synthesized three isostructural COFs by polymerizing 2,4,6-triformylphloroglucinol with fluorine-tuned amine monomers. Strategic fluorination induces in-plane hydrogen bonding to lock π-conjugated acceptor (A) units, forming a donor-(π-acceptor) (D-(π-A)) architecture that suppresses electron–hole recombination postexcitation while enhancing charge carrier mobility through π-A coplanarity. Concurrently, fluorination creates a hydrophobic surface to mitigate CO2 mass-transfer limitations, elevating local CO2 concentration and optimizing proton availability at the three-phase interface. The multifluorinated COF demonstrates exceptional photocatalytic activity for CO2-to-propylene conversion, exhibiting 18.1-fold and 1.5-fold enhancements over its nonfluorinated and monofluorinated counterparts, respectively. This work establishes fluorination as a dual-functional strategy to simultaneously regulate electronic structures and surface properties in COFs, providing new pathways for solar-driven synthesis of multicarbon chemicals from sustainable C1 feedstocks while contributing to ecological sustainability.
期刊介绍:
ACS Sustainable Chemistry & Engineering is a prestigious weekly peer-reviewed scientific journal published by the American Chemical Society. Dedicated to advancing the principles of green chemistry and green engineering, it covers a wide array of research topics including green chemistry, green engineering, biomass, alternative energy, and life cycle assessment.
The journal welcomes submissions in various formats, including Letters, Articles, Features, and Perspectives (Reviews), that address the challenges of sustainability in the chemical enterprise and contribute to the advancement of sustainable practices. Join us in shaping the future of sustainable chemistry and engineering.