Electron energy dissipation is an important energy dissipation pathway that cannot be ignored in friction process.Two-dimensional zeolite imidazole frameworks(2D ZIFs)and fluorine doping strategies give 2D Zn-ZIF and ...Electron energy dissipation is an important energy dissipation pathway that cannot be ignored in friction process.Two-dimensional zeolite imidazole frameworks(2D ZIFs)and fluorine doping strategies give 2D Zn-ZIF and 2D Co-ZIF unique electrical properties,making them ideal materials for studying electron energy dissipation mechanism.In this paper,based on the superlubricity modulation of 2D fluoridated ZIFs,the optimal tribological properties are obtained on the 2D F-Co-ZIF surface,with the friction coefficient as low as 0.0010.Electrical experiments,density functional theory(DFT)simulation,and fluorescence detection are used to explain the mechanism of fluorine doping regulation of tribological properties from the two stages,namely energy transfer and energy release.Specifically,the energy will transfer into the friction system through the generation of electron–hole pairs under an external excitation,and release by radiation and non-radiation energy dissipation channels.Fluorination reduces energy transfer by altering the electronic properties and band structures of ZIFs,and slows down the charge transfer by enhancing the shielding efficiency,thus slowing the non-radiative energy dissipation rate during the energy release stage.Our insights not only help us better understand the role of fluorine doping in improving tribological properties,but also provide a new way to further explore the electron energy dissipation pathway during friction.展开更多
The merits of intrinsic electrical conductivity, high specific surface area, tunable chemical composition and tailor-made properties enable two-dimensional conductive metal-organic frameworks (2D c-MOFs) as promising ...The merits of intrinsic electrical conductivity, high specific surface area, tunable chemical composition and tailor-made properties enable two-dimensional conductive metal-organic frameworks (2D c-MOFs) as promising next-generation electrode materials in the field of energy storage and conversion. Herein, we have designed and synthesized a novel pyrazine-based 2D c-MOF (TPQG-Cu-MOF) bearing extended π-conjugated structure and abundant redox active sites. Thanks to the excellent redox reversibility of pyrazine units and CuO2 units, as well as the insolubility of the rigid framework skeleton, TPQG-Cu-MOF as the cathode material of lithium-ion battery exhibits a reversible specific capacity (150.2 mAh·g–1 at 20 mAh·g–1), good cycling stability (capacity retention of 82.6% after 500 cycles at 1 A·g–1) and excellent rate performance. Comprehensive ex-situ spectroscopic studies revealed the reversible redox activity of pyrazine units and CuO2 units of TPQG-Cu-MOF during the Li+ insertion/extraction process. The deepening fundamental understanding of the structure-property relationship was proposed, which might pave the way for further development of efficient MOF-based energy storage devices.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52350323 and 52105194)the National Postdoctoral Fellowship Program of China(No.GZB20230340)the Project was funded by the China Postdoctoral Science Foundation(Nos.2023TQ0184 and 2023M731941).
文摘Electron energy dissipation is an important energy dissipation pathway that cannot be ignored in friction process.Two-dimensional zeolite imidazole frameworks(2D ZIFs)and fluorine doping strategies give 2D Zn-ZIF and 2D Co-ZIF unique electrical properties,making them ideal materials for studying electron energy dissipation mechanism.In this paper,based on the superlubricity modulation of 2D fluoridated ZIFs,the optimal tribological properties are obtained on the 2D F-Co-ZIF surface,with the friction coefficient as low as 0.0010.Electrical experiments,density functional theory(DFT)simulation,and fluorescence detection are used to explain the mechanism of fluorine doping regulation of tribological properties from the two stages,namely energy transfer and energy release.Specifically,the energy will transfer into the friction system through the generation of electron–hole pairs under an external excitation,and release by radiation and non-radiation energy dissipation channels.Fluorination reduces energy transfer by altering the electronic properties and band structures of ZIFs,and slows down the charge transfer by enhancing the shielding efficiency,thus slowing the non-radiative energy dissipation rate during the energy release stage.Our insights not only help us better understand the role of fluorine doping in improving tribological properties,but also provide a new way to further explore the electron energy dissipation pathway during friction.
基金financially supported by the National Natural Science Foundation of China(Nos.51973153,22105144).
文摘The merits of intrinsic electrical conductivity, high specific surface area, tunable chemical composition and tailor-made properties enable two-dimensional conductive metal-organic frameworks (2D c-MOFs) as promising next-generation electrode materials in the field of energy storage and conversion. Herein, we have designed and synthesized a novel pyrazine-based 2D c-MOF (TPQG-Cu-MOF) bearing extended π-conjugated structure and abundant redox active sites. Thanks to the excellent redox reversibility of pyrazine units and CuO2 units, as well as the insolubility of the rigid framework skeleton, TPQG-Cu-MOF as the cathode material of lithium-ion battery exhibits a reversible specific capacity (150.2 mAh·g–1 at 20 mAh·g–1), good cycling stability (capacity retention of 82.6% after 500 cycles at 1 A·g–1) and excellent rate performance. Comprehensive ex-situ spectroscopic studies revealed the reversible redox activity of pyrazine units and CuO2 units of TPQG-Cu-MOF during the Li+ insertion/extraction process. The deepening fundamental understanding of the structure-property relationship was proposed, which might pave the way for further development of efficient MOF-based energy storage devices.
