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

IF 7.3 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Linquan Hou, Xiangjing Xie, Ye Li, Ting Song*, Xiayi Hu, Bei Long and Guo-Jun Deng*, 
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引用次数: 0

摘要

共价有机框架(COFs)已成为光催化CO2还原的有希望的候选材料,但由于其固有的亲水性和快速电荷重组,实现C2+ (C2H4, C3H6)产物的高效还原仍然具有挑战性。通过将2,4,6-三甲酰间苯三酚与氟调胺单体聚合,合成了三个同结构COFs。策略氟化诱导平面内氢键锁定π共轭受体(A)单元,形成供体-(π-受体)(D-(π-A))结构,抑制激发后电子-空穴复合,同时通过π-A共平面性增强载流子迁移率。同时,氟化产生疏水表面以减轻CO2传质限制,提高局部CO2浓度并优化三相界面的质子可用性。多氟化COF对二氧化碳到丙烯的转化表现出优异的光催化活性,分别比非氟化和单氟化COF增强18.1倍和1.5倍。这项工作确立了氟化作为一种双重功能策略,可以同时调节COFs的电子结构和表面性质,为太阳能驱动合成多碳化学品提供新的途径,同时促进生态可持续性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Enhancing Photocatalytic CO2 Reduction to Multicarbon Fuels via Hydrophobic Donor-(π-Acceptor) Covalent Organic Frameworks

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.

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来源期刊
ACS Sustainable Chemistry & Engineering
ACS Sustainable Chemistry & Engineering CHEMISTRY, MULTIDISCIPLINARY-ENGINEERING, CHEMICAL
CiteScore
13.80
自引率
4.80%
发文量
1470
审稿时长
1.7 months
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.
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