光响应有机模块自组装导致的氧自由基转化及其光催化应用
Transformation of reactive oxygen species caused by assembly of excitation modules into supramolecular organic frameworks for photocatalysis
姚娴雅 1于胜胜 1张荣震 1王发栋 1刘辉 1牛凯凯 1邢令宝 1李培洲2
作者信息
- 1. School of Chemistry and Chemical Engineering,Shandong University of Technology,Zibo 255000,China
- 2. School of Chemistry and Chemical Engineering,Shandong Provincial Key Laboratory for Science of Material Creation and Energy Conversion,Science Center for Material Creation and Energy Conversion,Institute of Frontier and Interdisciplinary Science,Shandong University,Jinan 250100,China
- 折叠
摘要
在光催化反应中实现对活性氧物种的单线态氧和超氧阴离子自由基的有效控制仍然是一个巨大挑战.本工作报道了一个从光敏模块构筑主客体超分子有机框架(SOF)策略,有效地实现了单线态氧到超氧阴离子自由基的转化.该TPA-BP-SOF结构中的光敏模块由四个4,4'-联吡啶盐(BP)单元修饰的苯基桥接双(三苯胺)衍生物(TPA-BP)构成.来自于不同的TPA-BP中的两个BP单元通过与葫芦[8]脲(CB[8])发生首尾相连的强络合作用,形成了具有周期性孔结构和均匀溶解度的二维超分子有机框架纳米片结构.与单体TPA-BP中检测到的生成单线态氧的能量转移机制不同,通过主客体相互作用形成的TPA-BP-SOF能够有效促进电子转移高效产生超氧阴离子自由基.同时,该TPA-BP-SOF生成的超氧阴离子自由基能有效地用于水相芳基硼酸的氧化羟基化和N-苯基四氢异唑啉的氧化,收率分别高达88％和83％.本研究提出了一种利用SOF实现Ⅱ型光敏剂向Ⅰ型光敏剂有效转化的新方法,成功展示了其在光催化有机转化中的实际应用.
Abstract
The efficient control of singlet oxygen(1O2)and superoxide radical(O2·-)of reactive oxygen species in photo-catalytic reactions is synthetically captivating but practically challenging.Herein,we report a new strategy that efficiently realizes the conversion of 1O2 to O2·-by the assembly of the excitation modules into a host-guest supramolecular organic framework(SOF).A photoactive organic module of a phenyl-bridged bis(triphenylamine)derivative modified by four 4,4'-bipyridin-1-ium(BP)units,named as triphenylamine(TPA)-BP,was pre-synthezied.After the assembly of TPA-BP with curcurbit[8]uril(CB[8])through the strong complexation of CB[8]with two BP units in a head-to-tail manner,a TPA-BP-SOF was sucessfully constructed,which is a two-dimensional nanosheet structure with a periodic pore structure and homogeneous solubility.It is noteworthy that the formation of TPA-BP-SOF through host-guest interactions might facilitate efficient electron transfer,leading to the production of O2·-.In contrast,its monomer TPA-BP dominantly generates 1O2 in the photocatalytic process.This study presents a novel ap-proach to effectively convert the type Ⅱ photosensitizer to the type Ⅰ photosensitizer by implementing TPA-BP-SOF.More-over,the O2·-species produced by TPA-BP-SOF under light irradiation can effectively catalyze the oxidative hydroxylation of arylboronic acids and the aerobic oxidation of N-phe-nyltetrahydroisoquinoline in water with the yields of up to 88％and 83％,respectively.
关键词
photocatalysis/reactive oxygen species/singlet oxy-gen/supramolecular organic frameworks/superoxide radicalKey words
photocatalysis/reactive oxygen species/singlet oxy-gen/supramolecular organic frameworks/superoxide radical引用本文复制引用
基金项目
国家自然科学基金(52205210)
山东省自然科学基金(ZR2020MB018)
山东省自然科学基金(ZR2022QE033)
山东省自然科学基金(ZR2021QB049)
出版年
2024
NETL
NSTL
万方数据