质子耦合电子转移(Proton-Coupled Electron Transfer,PCET)反应是生物和化学的重要过程,它与光合作用、呼吸过程、能量转化和存储,以及制备清洁能源材料等过程紧密相关。界面上的质子耦合电子转移反应是近年来的研究热点之一,本文对该...质子耦合电子转移(Proton-Coupled Electron Transfer,PCET)反应是生物和化学的重要过程,它与光合作用、呼吸过程、能量转化和存储,以及制备清洁能源材料等过程紧密相关。界面上的质子耦合电子转移反应是近年来的研究热点之一,本文对该领域进行了简要综述,主要介绍了发生在液/液界面和固/液界面上的质子耦合电子转移反应的研究进展。展开更多
Selective functionalization of C(sp^(3))–H bonds is a straightforward and practical method to construct complex molecule skeletons. In this field, direct transformation of unactivated C(sp^(3))–H bonds into C(sp^(3)...Selective functionalization of C(sp^(3))–H bonds is a straightforward and practical method to construct complex molecule skeletons. In this field, direct transformation of unactivated C(sp^(3))–H bonds into C(sp^(3))–SCF_(3) architectures is still a great challenge.We report a highly selective trifluoromethylthiolation of unactivated aliphatic C(sp^(3))–H bonds by combination of proton-coupled electron transfer(PCET) and hydrogen atom transfer(HAT) strategy. A wide range of structurally diverse alkyl trifluoromethyl sulfides are obtained. Furthermore, the use of two different photocatalysts can realize an unprecedented trifluoromethylthiolation and amidation cascade of different C(sp^(3))–H bonds. It can afford a good access to bifunctionalized molecules in synthetically useful yields.展开更多
Tuning electrolyte properties is a widely recognized strategy to enhance activity and selectivity in electrocatalysis,drawing increasing attention in this domain.Despite extensive experimental and theoretical studies,...Tuning electrolyte properties is a widely recognized strategy to enhance activity and selectivity in electrocatalysis,drawing increasing attention in this domain.Despite extensive experimental and theoretical studies,debates persist about how various electrolyte components influence electrocatalytic reactions.We offer a concise review focusing on current discussions,especially the contentious roles of cations.This article further examines how different factors affect the interfacial solvent structure,particularly the hydrogen-bonding network,and delves into the microscopic kinetics of electron and proton-coupled electron transfer.We also discuss the overarching influence of solvents from a kinetic modeling perspective,aiming to develop a robust correlation between electrolyte structure and reactivity.Lastly,we summarize ongoing research challenges and suggest potential directions for future studies on electrolyte effects in electrocatalysis.展开更多
文摘质子耦合电子转移(Proton-Coupled Electron Transfer,PCET)反应是生物和化学的重要过程,它与光合作用、呼吸过程、能量转化和存储,以及制备清洁能源材料等过程紧密相关。界面上的质子耦合电子转移反应是近年来的研究热点之一,本文对该领域进行了简要综述,主要介绍了发生在液/液界面和固/液界面上的质子耦合电子转移反应的研究进展。
基金National Key Research and Development Program of China (2021YFC2101900)the National Natural Science Foundation of China (22122103, 22101130, 22001117 and 22271144)+1 种基金Fundamental Research Funds for the Central Universities (020514380327)the Open Project of State Key Laboratory of Natural Medicines (SKLNMKF202401) for financial support。
文摘Selective functionalization of C(sp^(3))–H bonds is a straightforward and practical method to construct complex molecule skeletons. In this field, direct transformation of unactivated C(sp^(3))–H bonds into C(sp^(3))–SCF_(3) architectures is still a great challenge.We report a highly selective trifluoromethylthiolation of unactivated aliphatic C(sp^(3))–H bonds by combination of proton-coupled electron transfer(PCET) and hydrogen atom transfer(HAT) strategy. A wide range of structurally diverse alkyl trifluoromethyl sulfides are obtained. Furthermore, the use of two different photocatalysts can realize an unprecedented trifluoromethylthiolation and amidation cascade of different C(sp^(3))–H bonds. It can afford a good access to bifunctionalized molecules in synthetically useful yields.
基金supported by the National Key Research and Development Program of China(2023YFA1508300)the National Natural Science Foundation of China(22322202)supported by Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(HRTP-[2022]-47).
文摘Tuning electrolyte properties is a widely recognized strategy to enhance activity and selectivity in electrocatalysis,drawing increasing attention in this domain.Despite extensive experimental and theoretical studies,debates persist about how various electrolyte components influence electrocatalytic reactions.We offer a concise review focusing on current discussions,especially the contentious roles of cations.This article further examines how different factors affect the interfacial solvent structure,particularly the hydrogen-bonding network,and delves into the microscopic kinetics of electron and proton-coupled electron transfer.We also discuss the overarching influence of solvents from a kinetic modeling perspective,aiming to develop a robust correlation between electrolyte structure and reactivity.Lastly,we summarize ongoing research challenges and suggest potential directions for future studies on electrolyte effects in electrocatalysis.
