Given their unique structure-dependent properties,strategically designing semiconductor-based photocatalysts,which expose highly reactive crystalline facets,is widely used to tune their performance.Herein,AgBr/Ag/TiO_...Given their unique structure-dependent properties,strategically designing semiconductor-based photocatalysts,which expose highly reactive crystalline facets,is widely used to tune their performance.Herein,AgBr/Ag/TiO_(2){100}nanorods Z-scheme heterojunction composites were prepared via hydrothermal and in situ facet-induced reduction.Transmission electron microscopy,X-ray diffraction,X-ray photoelectron spectroscopy,electron paramagnetic resonance spectroscopy,and density functional theory calculations reveal that the selective exposure of TiO_(2){100}facets with abundant oxygen vacancies(OV)promotes the formation of metallic silver on the interfaces between AgBr and TiO_(2){100}.Metallic silver can mediate interfacial charge transfer by facilitating the photogenerated carrier recombination of the conduction band of TiO_(2){100}and the valence band of AgBr.As a result,a Z-scheme heterojunction is formed in AgBr/Ag/TiO_(2){100}.The AgBr/Ag/TiO_(2){100}exhibits faster degradation of tetracycline in aqueous solution compared to pristine AgBr,TiO_(2){101},TiO_(2){100}and AgBr/TiO_(2){101}p-n heterojunctions.This is attributed to the effect of the Z-scheme heterojunction on prolonging the lifetime of photogenerated carriers,which is confirmed by femtosecond transient absorption spectroscopy.The photocatalytic mechanism and degradation pathways are discussed along with a toxicity assessment of the intermediates.Overall,this work develops a new approach for designing Z-scheme heterojunction photocatalysts via selective facet control of anatase TiO_(2).展开更多
Controllable anisotropic growth of perovskite nanocrystals(NCs)is challenging since it is difficult to separate the nucleation and growth processes.Here,a two-step nucleation strategy is proposed to control the bindin...Controllable anisotropic growth of perovskite nanocrystals(NCs)is challenging since it is difficult to separate the nucleation and growth processes.Here,a two-step nucleation strategy is proposed to control the binding interaction between surface ligands and NCs,resulting in facet-induced coordination competition.Oleic acid as surface activated ligand leads to the formation of defective lead bromine octahedron,and the binding interaction between 4-dodecylbenzenesulfonic acid and lead atoms promotes the formation of two kinds of binding interactions.Based on this strategy,the anisotropic growth of CsPbBr_(3) nanoplatelet(NPLs)with adjusted length from 11.4 to 24 nm,and the evolution of NPLs from stacked to tongue-shaped have been realized.Elemental line scan reveals the sulfur atoms mainly distribute at the edge of NPLs.Furthermore,binding energy calculation and experimental results illustrate the coordination competition of different binding interaction on specific facets induces the anisotropic growth of NPLs.Importantly,strong emission anisotropy of highly ordered NPLs with polarization ratio up to 0.58 is illustrated.This work not only deepens our understanding of the controllable synthesis of perovskite NCs,but also provides a reference for the regulation of light emitting diode and soler cells.展开更多
文摘Given their unique structure-dependent properties,strategically designing semiconductor-based photocatalysts,which expose highly reactive crystalline facets,is widely used to tune their performance.Herein,AgBr/Ag/TiO_(2){100}nanorods Z-scheme heterojunction composites were prepared via hydrothermal and in situ facet-induced reduction.Transmission electron microscopy,X-ray diffraction,X-ray photoelectron spectroscopy,electron paramagnetic resonance spectroscopy,and density functional theory calculations reveal that the selective exposure of TiO_(2){100}facets with abundant oxygen vacancies(OV)promotes the formation of metallic silver on the interfaces between AgBr and TiO_(2){100}.Metallic silver can mediate interfacial charge transfer by facilitating the photogenerated carrier recombination of the conduction band of TiO_(2){100}and the valence band of AgBr.As a result,a Z-scheme heterojunction is formed in AgBr/Ag/TiO_(2){100}.The AgBr/Ag/TiO_(2){100}exhibits faster degradation of tetracycline in aqueous solution compared to pristine AgBr,TiO_(2){101},TiO_(2){100}and AgBr/TiO_(2){101}p-n heterojunctions.This is attributed to the effect of the Z-scheme heterojunction on prolonging the lifetime of photogenerated carriers,which is confirmed by femtosecond transient absorption spectroscopy.The photocatalytic mechanism and degradation pathways are discussed along with a toxicity assessment of the intermediates.Overall,this work develops a new approach for designing Z-scheme heterojunction photocatalysts via selective facet control of anatase TiO_(2).
基金supported by the National Natural Science Foundation of China(Nos.61874054,51902160,61725402,and 51972058)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX20_0271)+2 种基金the Natural Science Foundation of Jiangsu Province(No.BK20180489)Young Elite Scientists Sponsorship Program by CAST(No.2018QNRC001)Fundamental Research Funds for the Central Universities(No.30918011208).
文摘Controllable anisotropic growth of perovskite nanocrystals(NCs)is challenging since it is difficult to separate the nucleation and growth processes.Here,a two-step nucleation strategy is proposed to control the binding interaction between surface ligands and NCs,resulting in facet-induced coordination competition.Oleic acid as surface activated ligand leads to the formation of defective lead bromine octahedron,and the binding interaction between 4-dodecylbenzenesulfonic acid and lead atoms promotes the formation of two kinds of binding interactions.Based on this strategy,the anisotropic growth of CsPbBr_(3) nanoplatelet(NPLs)with adjusted length from 11.4 to 24 nm,and the evolution of NPLs from stacked to tongue-shaped have been realized.Elemental line scan reveals the sulfur atoms mainly distribute at the edge of NPLs.Furthermore,binding energy calculation and experimental results illustrate the coordination competition of different binding interaction on specific facets induces the anisotropic growth of NPLs.Importantly,strong emission anisotropy of highly ordered NPLs with polarization ratio up to 0.58 is illustrated.This work not only deepens our understanding of the controllable synthesis of perovskite NCs,but also provides a reference for the regulation of light emitting diode and soler cells.
