Metal halide perovskite heterostructures that combine twodimensional(2D)and three-dimensional(3D)perovskites with desirable charge and exciton behaviors at heterointerfaces have attracted much attention recently[1].Th...Metal halide perovskite heterostructures that combine twodimensional(2D)and three-dimensional(3D)perovskites with desirable charge and exciton behaviors at heterointerfaces have attracted much attention recently[1].The integration of 2D and3D perovskites combines the commendable efficiency with the exceptional stability[2].Unfortunately,the electrically insulating nature of bulky organic cations in 2D perovskites impedes the charge transport between the heterointerface[3].展开更多
Systematic and in-depth explorations of the effects of side-chain modulation on the molecular assembly,optoelectronic properties,and photocatalytic properties of supramolecular systems,as well as the kinetics of charg...Systematic and in-depth explorations of the effects of side-chain modulation on the molecular assembly,optoelectronic properties,and photocatalytic properties of supramolecular systems,as well as the kinetics of charge separation and migration in these systems,are rare.In this study,a novel supramolecular photocatalyst with an alkoxy side chain(S-EPDI)was successfully developed through subtle design of the short and linear alkoxyl side chains,affording a phenol degradation efficiency approximately four times that of the counterpart with an alkyl side chain(S-APDI).Notably,combined density functional theory(DFT)calculations,absorption spectroscopy,and other characterizations revealed that the perylene diimide(PDI)molecular units,throughπ-πstacking,formed a unique rotationally offset stacked supramolecular structure,exhibiting a significant dipole moment.This gave rise to the formation of a larger inherent electric field within S-EPDI compared to S-APDI.Moreover,the study quantitatively demonstrated that a stronger inherent electric field and lower rate of surface charge recombination facilitate efficient separation of the photogenerated carriers.Therefore,the side-chain molecular engineering method employed in this study offers an effective approach for modulating the kinetics of charge migration.展开更多
基金supported by the National Natural Science Foundation of China(52325309,21971172,52071225,52302298,and 62005027)the Key Lab of Advanced Optical Manufacturing Technologies of Jiangsu Province&Key Lab of Modern Optical Technologies of Ministry of Education,Soochow University+2 种基金Soochow Municipal Laboratory for low carbon technologies and industries,Key Laboratory of Core Technology of High Specific Energy Battery and Key Materials for Petroleum and Chemical Industry,Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering in Changzhou Universitythe European Union’s Horizon Europe research and innovation programme(101087143)(Electron Beam Emergent Additive Manufacturing(EBEAM))REFRESH-Research Excellence For REgion Sustainability and High-tech Industries(CZ.10.03.01/00/22_003/0000048)via the Operational Programme Just Transition。
文摘Metal halide perovskite heterostructures that combine twodimensional(2D)and three-dimensional(3D)perovskites with desirable charge and exciton behaviors at heterointerfaces have attracted much attention recently[1].The integration of 2D and3D perovskites combines the commendable efficiency with the exceptional stability[2].Unfortunately,the electrically insulating nature of bulky organic cations in 2D perovskites impedes the charge transport between the heterointerface[3].
基金supported by the Chinese National Science Foundation(21806181)Fundamental Research Funds for the Central Universities(2023ZKPYHH05,2024ZKPYHH01).
文摘Systematic and in-depth explorations of the effects of side-chain modulation on the molecular assembly,optoelectronic properties,and photocatalytic properties of supramolecular systems,as well as the kinetics of charge separation and migration in these systems,are rare.In this study,a novel supramolecular photocatalyst with an alkoxy side chain(S-EPDI)was successfully developed through subtle design of the short and linear alkoxyl side chains,affording a phenol degradation efficiency approximately four times that of the counterpart with an alkyl side chain(S-APDI).Notably,combined density functional theory(DFT)calculations,absorption spectroscopy,and other characterizations revealed that the perylene diimide(PDI)molecular units,throughπ-πstacking,formed a unique rotationally offset stacked supramolecular structure,exhibiting a significant dipole moment.This gave rise to the formation of a larger inherent electric field within S-EPDI compared to S-APDI.Moreover,the study quantitatively demonstrated that a stronger inherent electric field and lower rate of surface charge recombination facilitate efficient separation of the photogenerated carriers.Therefore,the side-chain molecular engineering method employed in this study offers an effective approach for modulating the kinetics of charge migration.
