The fundamental understanding of the mechanism underlying the early stages of crystallization of hexagonal-close-packed(hcp)nanocrystals is crucial for their synthesis with desired properties,but it remains a signific...The fundamental understanding of the mechanism underlying the early stages of crystallization of hexagonal-close-packed(hcp)nanocrystals is crucial for their synthesis with desired properties,but it remains a significant challenge.Here,we report using in situ liquid cell transmission electron microscopy(TEM)to directly capture the dynamic nucleation process and track the real-time growth pathway of hcp Ni nanocrystals at the atomic scale.It is demonstrated that the growth of amorphous-phase-mediated hcp Ni nanocrystals is from the metal-rich liquid phases.In addition,the reshaped preatomic facet development of a single nanocrystal is also imaged.Theoretical calculations further identify the non-classical features of hcp Ni crystallization.These discoveries could enrich the nucleation and growth model theory and provide useful information for the rational design of synthesis pathways of hcp nanocrystals.展开更多
Crystallization in supersaturated solution plays a fundamental role in a variety of natural and industrial processes.However,a thorough understanding of crystallization phenomena in supersaturated solution is still di...Crystallization in supersaturated solution plays a fundamental role in a variety of natural and industrial processes.However,a thorough understanding of crystallization phenomena in supersaturated solution is still difficult because the real-time visualization of crystallization processes under supersaturated condition is a great challenge.Herein,an electron beam-induced crystallization method was carried out in in situ liquid cell transmission electron microscopy(TEM)to visualize the crystallization of NaCl under supersaturated condition in real time.Crucial steps and behaviors in the crystallization of NaCl were captured and clarified,including the growth of NaCl nanocrystals with different morphologies,the formation of initial crystalline seeds from amorphous ion clusters,and the non-equilibrium growth behaviors caused by uneven distribution of precursor ions.This study provides the real-time visualization of detailed nucleation and growth behaviors in NaCl crystallization and brings an ideal strategy for investigating crystallization phenomena under supersaturated condition.展开更多
The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view.Spherulite structures with radial fibrillar branches hav...The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view.Spherulite structures with radial fibrillar branches have been found in various solids;however,their growth mechanisms remain poorly understood.Here,we report real time imaging of the formation of two-dimensional(2D)iron oxide spherulite nanostructures in a liquid cell using transmission electron microscopy(TEM).By tracking the growth trajectories,we show the characteristics of the reaction front and growth kinetics.Our observations reveal that the tip of a growing branch splits as the width exceeds certain sizes(5.5–8.5 nm).The radius of a spherulite nanostructure increases linearly with time at the early stage,transitioning to nonlinear growth at the later stage.Furthermore,a thin layer of solid is accumulated at the tip and nanoparticles from secondary nucleation also appear at the growing front which later develop into fibrillar branches.The spherulite nanostructure is polycrystalline with the co-existence of ferrihydrite and Fe3O4 through-out the growth.A growth model is further established,which provides rational explanations on the linear growth at the early stage and the nonlinearity at the later stage of growth.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22001083,52072323,and 52122211)the“Double-First Class”Foundation of Materials and Intelligent Manufacturing Discipline of Xiamen University.J.Y.L.thanks the Research Startup Fund from Harbin Institute of Technology(Shenzhen)with the project number University(No.20210028)the Shenzhen Steady Support Plan(No.GXWD20201230155427003-20200824103000001).
文摘The fundamental understanding of the mechanism underlying the early stages of crystallization of hexagonal-close-packed(hcp)nanocrystals is crucial for their synthesis with desired properties,but it remains a significant challenge.Here,we report using in situ liquid cell transmission electron microscopy(TEM)to directly capture the dynamic nucleation process and track the real-time growth pathway of hcp Ni nanocrystals at the atomic scale.It is demonstrated that the growth of amorphous-phase-mediated hcp Ni nanocrystals is from the metal-rich liquid phases.In addition,the reshaped preatomic facet development of a single nanocrystal is also imaged.Theoretical calculations further identify the non-classical features of hcp Ni crystallization.These discoveries could enrich the nucleation and growth model theory and provide useful information for the rational design of synthesis pathways of hcp nanocrystals.
基金supported by the National Natural Science Foundation of China(Nos.61974021 and 12234005)New Cornerstone Science Foundation and XPLORER PRIZE,and the Fundamental Research Funds for the Central Universities.
文摘Crystallization in supersaturated solution plays a fundamental role in a variety of natural and industrial processes.However,a thorough understanding of crystallization phenomena in supersaturated solution is still difficult because the real-time visualization of crystallization processes under supersaturated condition is a great challenge.Herein,an electron beam-induced crystallization method was carried out in in situ liquid cell transmission electron microscopy(TEM)to visualize the crystallization of NaCl under supersaturated condition in real time.Crucial steps and behaviors in the crystallization of NaCl were captured and clarified,including the growth of NaCl nanocrystals with different morphologies,the formation of initial crystalline seeds from amorphous ion clusters,and the non-equilibrium growth behaviors caused by uneven distribution of precursor ions.This study provides the real-time visualization of detailed nucleation and growth behaviors in NaCl crystallization and brings an ideal strategy for investigating crystallization phenomena under supersaturated condition.
基金This project was supported by the U.S.Department of Energy(DOE),Office of Science,Office of Basic Energy Sciences(BES),Materials Sciences and Engineering Division under Contract No.DE-AC02-05-CH11231 within the in-situ TEM(KC22ZH)program.Work at the Molecular Foundry was supported by the Office of Science,Office of Basic Energy Sciences,of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231.We acknowledge Gatan Inc.for the advanced K2 IS camera and Dr.Ming Pan and Dr.Cory Czarnik for their help with part of experimental set up in this work.W.J.Z.acknowledges the support from Tianjin University Graduate School International Academic Exchange Fund.M.R.H.was funded by KAUST project under H.M.Z.at UC Berkeley.
文摘The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view.Spherulite structures with radial fibrillar branches have been found in various solids;however,their growth mechanisms remain poorly understood.Here,we report real time imaging of the formation of two-dimensional(2D)iron oxide spherulite nanostructures in a liquid cell using transmission electron microscopy(TEM).By tracking the growth trajectories,we show the characteristics of the reaction front and growth kinetics.Our observations reveal that the tip of a growing branch splits as the width exceeds certain sizes(5.5–8.5 nm).The radius of a spherulite nanostructure increases linearly with time at the early stage,transitioning to nonlinear growth at the later stage.Furthermore,a thin layer of solid is accumulated at the tip and nanoparticles from secondary nucleation also appear at the growing front which later develop into fibrillar branches.The spherulite nanostructure is polycrystalline with the co-existence of ferrihydrite and Fe3O4 through-out the growth.A growth model is further established,which provides rational explanations on the linear growth at the early stage and the nonlinearity at the later stage of growth.