An electrostatic model based on the effective-point-charge approach is proposed to predict the quantized axis of rare-earth ions,even in low symmetry.The effective charges of coordination atoms create an electrostatic...An electrostatic model based on the effective-point-charge approach is proposed to predict the quantized axis of rare-earth ions,even in low symmetry.The effective charges of coordination atoms create an electrostatic potential interacting with the aspherical 4f electron cloud of the rare-earth ion.The quantized axis can be determined by minimizing the electrostatic energy.The effective charge displacements must be considered according to the nature of the coordination bond,which can be calculated by the atomic orbital wavefunctions for theσ-andπ-bonds,respectively.Using our model,the experimentally determined magnetic easy axis of some complexes with Tb^(3+),Dy^(3+)and Er^(3+)can be very well reproduced.展开更多
The design and synthesis of functional materials with desired properties is the ultimate goal for chemical pursuers.Single-crystal to single-crystal(SCSC)transformations are an important component of solidstate reacti...The design and synthesis of functional materials with desired properties is the ultimate goal for chemical pursuers.Single-crystal to single-crystal(SCSC)transformations are an important component of solidstate reactions.These transformations not only create new materials but also provide an opportunity to explore the process of forming a chemical bond,which is conducive to making function-oriented crystal synthesis a reality.展开更多
Photocatalytic nitrogen reduction offers a carbon-neutral route to access ammonia by directly converting solar energy into chemical bonds,presenting a promising alternative to the energy-intensive Haber-Bosch process....Photocatalytic nitrogen reduction offers a carbon-neutral route to access ammonia by directly converting solar energy into chemical bonds,presenting a promising alternative to the energy-intensive Haber-Bosch process.However,current progress in pNRR is hindered by the formidable activation barrier of the NuN triple bond,which severely limits catalytic activity and NH_(3) yield.BiOBr-based semiconductors,distinguished by their layered lattice and tunable band structure,exhibit strong visible-light absorption and efficient charge separation,positioning them as compelling platforms for pNRR.This review provides the first comprehensive survey of BiOBr-based photocatalysts for photocatalytic nitrogen fixation.It begins by introducing the fundamental thermodynamics and reaction pathways of pNRR,followed by an analysis of four key modification strategies employed to enhance BiOBr performance.The review critically assesses the reliability of ammonia quantification protocols,highlighting concerns regarding contamination and artefactual sources.Additionally,three advanced in situ characterization techniques are discussed for their role in elucidating charge-transfer kinetics.By pinpointing current challenges and outlining future research priorities,this review aims to steer academic exploration,inspire innovative catalyst design,and accelerate the translation of BiOBr-based photocatalysis toward sustainable,modular ammonia production.展开更多
文摘An electrostatic model based on the effective-point-charge approach is proposed to predict the quantized axis of rare-earth ions,even in low symmetry.The effective charges of coordination atoms create an electrostatic potential interacting with the aspherical 4f electron cloud of the rare-earth ion.The quantized axis can be determined by minimizing the electrostatic energy.The effective charge displacements must be considered according to the nature of the coordination bond,which can be calculated by the atomic orbital wavefunctions for theσ-andπ-bonds,respectively.Using our model,the experimentally determined magnetic easy axis of some complexes with Tb^(3+),Dy^(3+)and Er^(3+)can be very well reproduced.
基金supported by the National Natural Science Foundation of China(No.21701016,21622104 and 21471080)Priority Academic Program Development of Jiangsu Higher Education Institutions and the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials.
文摘The design and synthesis of functional materials with desired properties is the ultimate goal for chemical pursuers.Single-crystal to single-crystal(SCSC)transformations are an important component of solidstate reactions.These transformations not only create new materials but also provide an opportunity to explore the process of forming a chemical bond,which is conducive to making function-oriented crystal synthesis a reality.
基金supported by the National Natural Science Foundation of China(No.22168040 and 22162025)the Yan’an University Graduate Student Scientific Research Innovation Program Project(No.YKY2025066)+2 种基金the Graduate Education Innovation Program of Yan’an University(YCX2024052)National Natural Science Foundation of China(No.22568049)Science and Technology Planning Project of Yan’an City(No.2024-CYL-030).
文摘Photocatalytic nitrogen reduction offers a carbon-neutral route to access ammonia by directly converting solar energy into chemical bonds,presenting a promising alternative to the energy-intensive Haber-Bosch process.However,current progress in pNRR is hindered by the formidable activation barrier of the NuN triple bond,which severely limits catalytic activity and NH_(3) yield.BiOBr-based semiconductors,distinguished by their layered lattice and tunable band structure,exhibit strong visible-light absorption and efficient charge separation,positioning them as compelling platforms for pNRR.This review provides the first comprehensive survey of BiOBr-based photocatalysts for photocatalytic nitrogen fixation.It begins by introducing the fundamental thermodynamics and reaction pathways of pNRR,followed by an analysis of four key modification strategies employed to enhance BiOBr performance.The review critically assesses the reliability of ammonia quantification protocols,highlighting concerns regarding contamination and artefactual sources.Additionally,three advanced in situ characterization techniques are discussed for their role in elucidating charge-transfer kinetics.By pinpointing current challenges and outlining future research priorities,this review aims to steer academic exploration,inspire innovative catalyst design,and accelerate the translation of BiOBr-based photocatalysis toward sustainable,modular ammonia production.
