The rational configuration of built-in electric field(IEF)in heterogeneous materials can significantly optimize the band structure to accelerate the separation of photogenerated charge carriers.However,the strength mo...The rational configuration of built-in electric field(IEF)in heterogeneous materials can significantly optimize the band structure to accelerate the separation of photogenerated charge carriers.However,the strength modulation of IEF formed by various materials has an uncertain enhancing effect on the separation of photogenerated carriers.Herein,a mesoporous MIL-125(Ti)@BiOCl S-scheme heterojunction with controllable IEF is prepared by green photoreduction reaction to investigate the relationship between IEF,microstructure,and photocatalytic activity.Moreover,the corresponding results demonstrate the MIL-125(Ti)@BiOCl effectively regulates the IEF strength through controlling the concentration of ligand defects,thereby optimizing the band structure and improving the efficiency of photogenerated charge separation.The optimized IEF significantly enhances the photocatalytic degradation performance of mesoporous MIL-125(Ti)-3@BiOCl towards tetracycline,with a k value of 0.07 min^(–1),which are approximately 5.5 and 4.7 times greater than that of BiOCl(0.0127 min^(–1))and MIL-125(Ti)-3(0.015 min^(–1)).These findings provide a new pathway for regulating IEF within MOF-based heterojunctions,and offer new insights into the intrinsic correlations between defect structure,IEF,and photocatalytic activity.展开更多
Photo-assisted Li–O_(2)batteries present a promising avenue for reducing overpotential and enhancing the capacity of next-generation energy storage devices.In this study,we introduce a novel photo-assisted Li–O_(2)s...Photo-assisted Li–O_(2)batteries present a promising avenue for reducing overpotential and enhancing the capacity of next-generation energy storage devices.In this study,we introduce a novel photo-assisted Li–O_(2)system featuring a Z-scheme In_(2)S_(3)/MnO_(2)/BiOCl heterojunction as a photocathode.This innovative design significantly boosts visible light absorption and facilitates the spatial separation of photogenerated electron-hole pairs.The Z-scheme charge transfer pathway establishes efficient channels for enhancing electron transfer and charge separation,thereby fostering high photocatalytic efficiency.During illumination,photo-generated electrons traverse within the band structure,participating in the Oxygen Reduction Reaction(ORR)during discharging,while photo-induced holes in the valence band facilitate the oxidation reaction of discharge products during the charging process.Under illumination,the surface electrons of In_(2)S_(3)/MnO_(2)/BiOCl modify the morphology of the discharge product(Li_(2)O_(2)),leading to accelerated decomposition kinetics of Li_(2)O_(2)during charging.Remarkably,the In_(2)S_(3)/MnO_(2)/BiOCl photoelectrode exhibits a high specific capacity of 19330 mAh/g under illumination,surpassing performance in the dark by a significant margin.This results in an ultranarrow discharge/charge overpotential of 0.19/0.16 V,coupled with excellent cyclic stability and a long cycle life of 1500 h at 200 mA/g.Further surface tests on the photoelectrode demonstrate that light energy application promotes the decomposition of Li_(2)O_(2),corroborated by density function theory(DFT)theoretical calculations.This study of Z-scheme heterostructured photocathodes sheds light on the mechanism of photo-generated charge carriers in Li–O_(2)batteries,providing valuable insights into their functionality and potential for future battery technologies.展开更多
文摘The rational configuration of built-in electric field(IEF)in heterogeneous materials can significantly optimize the band structure to accelerate the separation of photogenerated charge carriers.However,the strength modulation of IEF formed by various materials has an uncertain enhancing effect on the separation of photogenerated carriers.Herein,a mesoporous MIL-125(Ti)@BiOCl S-scheme heterojunction with controllable IEF is prepared by green photoreduction reaction to investigate the relationship between IEF,microstructure,and photocatalytic activity.Moreover,the corresponding results demonstrate the MIL-125(Ti)@BiOCl effectively regulates the IEF strength through controlling the concentration of ligand defects,thereby optimizing the band structure and improving the efficiency of photogenerated charge separation.The optimized IEF significantly enhances the photocatalytic degradation performance of mesoporous MIL-125(Ti)-3@BiOCl towards tetracycline,with a k value of 0.07 min^(–1),which are approximately 5.5 and 4.7 times greater than that of BiOCl(0.0127 min^(–1))and MIL-125(Ti)-3(0.015 min^(–1)).These findings provide a new pathway for regulating IEF within MOF-based heterojunctions,and offer new insights into the intrinsic correlations between defect structure,IEF,and photocatalytic activity.
基金funded by the Natural Science Project of the Zhengzhou Science and Technology Bureau(No.22ZZRDZX04).
文摘Photo-assisted Li–O_(2)batteries present a promising avenue for reducing overpotential and enhancing the capacity of next-generation energy storage devices.In this study,we introduce a novel photo-assisted Li–O_(2)system featuring a Z-scheme In_(2)S_(3)/MnO_(2)/BiOCl heterojunction as a photocathode.This innovative design significantly boosts visible light absorption and facilitates the spatial separation of photogenerated electron-hole pairs.The Z-scheme charge transfer pathway establishes efficient channels for enhancing electron transfer and charge separation,thereby fostering high photocatalytic efficiency.During illumination,photo-generated electrons traverse within the band structure,participating in the Oxygen Reduction Reaction(ORR)during discharging,while photo-induced holes in the valence band facilitate the oxidation reaction of discharge products during the charging process.Under illumination,the surface electrons of In_(2)S_(3)/MnO_(2)/BiOCl modify the morphology of the discharge product(Li_(2)O_(2)),leading to accelerated decomposition kinetics of Li_(2)O_(2)during charging.Remarkably,the In_(2)S_(3)/MnO_(2)/BiOCl photoelectrode exhibits a high specific capacity of 19330 mAh/g under illumination,surpassing performance in the dark by a significant margin.This results in an ultranarrow discharge/charge overpotential of 0.19/0.16 V,coupled with excellent cyclic stability and a long cycle life of 1500 h at 200 mA/g.Further surface tests on the photoelectrode demonstrate that light energy application promotes the decomposition of Li_(2)O_(2),corroborated by density function theory(DFT)theoretical calculations.This study of Z-scheme heterostructured photocathodes sheds light on the mechanism of photo-generated charge carriers in Li–O_(2)batteries,providing valuable insights into their functionality and potential for future battery technologies.
