Search

For first-order phase transitions, the second derivatives of Gibbs free energy (specific heat and compressibility) diverge at the transition point, resulting in an effect known as super-elasticity along the pressure axis, or super-thermicity along the temperature axis. Here we report a chemical analogy of these singularity effects along the atomic doping axis, where the second derivative of Gibbs free energy (chemical susceptibility) diverges at the transition point, leading to an anomalously high energy barrier for dopant diffusion in co-existing phases, an effect we coin as super-susceptibility. The effect is realized in hydrogen diffusion in vanadium dioxide (VO2) with a metal-insulator transition (MIT). We show that hydrogen faces three times higher energy barrier and over one order of magnitude lower diffusivity when it diffuses across a metal-insulator domain wall in VO2. The additional energy barrier is attributed to a volumetric energy penalty that the diffusers need to pay for the reduction of latent heat. The super-susceptibility and resultant retarded atomic diffusion are expected to exist universally in all phase transformations where the transformation temperature is coupled to chemical composition, and inspires new ways to engineer dopant diffusion in phase-coexisting material systems.

Phase transformations have been a prominent topic of study for both fundamental and applied science. Solid-liquid reaction-induced phase transformations can be hard to characterize, and the transformation mechanisms are often not fully understood. Here, we report reversible phase transformations between a metal (Pb) nanocrystal and a viscous liquid-like phase unveiled by in situ liquid cell transmission electron microscopy. The reversible phase transformations are obtained by modulating the electron current density (between 1000 and 3000 electrons Å-2 s-1). The metal-organic viscous liquid-like phase exhibits short-range ordering with a preferred Pb-Pb distance of 0.5 nm. Assisted by density functional theory and molecular dynamics calculations, we show that the viscous liquid-like phase results from the reactions of Pb with the CH3O fragments from the triethylene glycol solution under electron beam irradiation. Such reversible phase transformations may find broad implementations.

Electrified solid-liquid interfaces (ESLIs) play a key role in various electrochemical processes relevant to energy1-5, biology6 and geochemistry7. The electron and mass transport at the electrified interfaces may result in structural modifications that markedly influence the reaction pathways. For example, electrocatalyst surface restructuring during reactions can substantially affect the catalysis mechanisms and reaction products1-3. Despite its importance, direct probing the atomic dynamics of solid-liquid interfaces under electric biasing is challenging owing to the nature of being buried in liquid electrolytes and the limited spatial resolution of current techniques for in situ imaging through liquids. Here, with our development of advanced polymer electrochemical liquid cells for transmission electron microscopy (TEM), we are able to directly monitor the atomic dynamics of ESLIs during copper (Cu)-catalysed CO2 electroreduction reactions (CO2ERs). Our observation reveals a fluctuating liquid-like amorphous interphase. It undergoes reversible crystalline-amorphous structural transformations and flows along the electrified Cu surface, thus mediating the crystalline Cu surface restructuring and mass loss through the interphase layer. The combination of real-time observation and theoretical calculations unveils an amorphization-mediated restructuring mechanism resulting from charge-activated surface reactions with the electrolyte. Our results open many opportunities to explore the atomic dynamics and its impact in broad systems involving ESLIs by taking advantage of the in situ imaging capability.

Crystallographic defects play a crucial role in cement hydration, with initial dissolution being dominated by the formation of etch pits that rely on the intersection of defects on surfaces. However, the defects present in cement particles have remained a mystery due to the lack of detailed direct observation at the atomic scale. In this study, we used scanning transmission electron microscopy to unravel the defects in alite particles at the single-atom level. Our observations identified different types of defects, including vacancies, doping, dislocations, rough surfaces, and grain boundaries. Atomic ordering in the alite crystal was further examined based on our single-atom recognition method. Our findings indicate that defects in cement particles may serve as reactive sites during the early hydration stage, facilitating the initial dissolution and providing nucleation sites for hydration products. This work provides insights into cement defect formation at the single-atom level and offers new opportunities in tuning the hydration process through defect engineering of cement particles.

Unveiling materials corrosion pathways is significant for understanding the corrosion mechanisms and designing corrosion-resistant materials. Here, we investigate the corrosion behavior of Sn@Ni3Sn4 and Sn nanocrystals in an aqueous solution in real time by using high-resolution liquid cell transmission electron microscopy. Our direct observation reveals an unprecedented level of detail on the corrosion of Sn metal with/without a coating of Ni3Sn4 at the nanometric and atomic levels. The Sn@Ni3Sn4 nanocrystals exhibit pitting corrosion, which is initiated at the defect sites in the Ni3Sn4 protective layer. The early stage isotropic etching transforms into facet-dependent etching, resulting in a cavity terminated with low-index facets. The Sn nanocrystals under fast etching kinetics show uniform corrosion, and smooth surfaces are obtained. Sn nanocrystals show creeping-like etching behavior and rough surfaces. This study provides critical insights into the impacts of coating, defects, and ion diffusion on corrosion kinetics and the resulting morphologies.

Developing atomically synergistic bifunctional catalysts relies on the creation of colocalized active atoms to facilitate distinct elementary steps in catalytic cycles. Herein, we show that the atomically-synergistic binuclear-site catalyst (ABC) consisting of [Formula: see text]-O-Cr6+ on zeolite SSZ-13 displays unique catalytic properties for iso-stoichiometric co-conversion of ethane and CO2. Ethylene selectivity and utilization of converted CO2 can reach 100 % and 99.0% under 500  °C at ethane conversion of 9.6%, respectively. In-situ/ex-situ spectroscopic studies and DFT calculations reveal atomic synergies between acidic Zn and redox Cr sites. [Formula: see text] ([Formula: see text]) sites facilitate β-C-H bond cleavage in ethane and the formation of Zn-Hδ- hydride, thereby the enhanced basicity promotes CO2 adsorption/activation and prevents ethane C-C bond scission. The redox Cr site accelerates CO2 dissociation by replenishing lattice oxygen and facilitates H2O formation/desorption. This study presents the advantages of the ABC concept, paving the way for the rational design of novel advanced catalysts.

When an ionic crystal dissolves in solvent, the positive and negative ions associated with solvent molecules release from the crystal. However, the existing form, interaction, and dynamics of ions in real solution are poorly understood because of the substantial experimental challenge. We observed the diffusion and aggregation of polyoxometalate (POM) ions in water by using liquid phase transmission electron microscopy. Real-time observation reveals an unexpected local reciprocating hopping motion of the ions in water, which may be caused by the short-range polymerized bridge of water molecules. We find that ion oligomers, existing as highly active clusters, undergo frequent splitting, aggregation, and rearrangement in dilute solution. The formation and dissociation of ion oligomers indicate a weak counterion-mediated interaction. Furthermore, POM ions with tetrahedral geometry show directional interaction compared with spherical ions, which presents structure-dependent dynamics.

Understanding nanodiamond structures is of great scientific and practical interest. It has been a long-standing challenge to unravel the complexity underlying nanodiamond structures and to resolve the controversies surrounding their polymorphic forms. Here, we use transmission electron microscopy with high-resolution imaging, electron diffraction, multislice simulations, and other supplementary techniques to study the impacts of small sizes and defects on cubic diamond nanostructures. The experimental results show that common cubic diamond nanoparticles display the (200) forbidden reflections in their electron diffraction patterns, which makes them indistinguishable from new diamond (n-diamond). The multislice simulations demonstrate that cubic nanodiamonds smaller than 5 nm can present the d-spacing at 1.78 Å corresponding to the (200) forbidden reflections, and the relative intensity of these reflections increases as the particle size decreases. Our simulation results also reveal that defects, such as surface distortions, internal dislocations, and grain boundaries can also make the (200) forbidden reflections visible. These findings provide valuable insights into the diamond structural complexity at nanoscale, the impact of defects on nanodiamond structures, and the discovery of novel diamond structures.

Determining the degree and the spatial extent of structural order in liquids is a grand challenge. Here, we are able to resolve the structural order in a model organic electrolyte of 1 M lithium hexafluorophosphate (LiPF6) dissolved in 1:1 (v/v) ethylene carbonate:diethylcarbonate by developing an integrated method of liquid-phase transmission electron microscopy (TEM), cryo-TEM operated at -30°C, four-dimensional scanning TEM, and data analysis based on deep learning. This study reveals the presence of short-range order (SRO) in the high-salt concentration domains of the liquid electrolyte from liquid phase separation at the low temperature. Molecular dynamics simulations suggest the SRO originates from the Li+-(PF6-)n (n > 2) local structural order induced by high LiPF6 salt concentration.

An understanding of lithium stripping is as important as that of lithium plating to achieve significant advances in using lithium metal anodes for high-energy rechargeable batteries. However, there have been limited studies on lithium stripping compared to lithium plating. Here we report the lithium stripping mechanisms revealed through in-situ electrochemical liquid cell transmission electron microscopy (TEM). We directly observe and compare the stripping behavior of the in-situ grown lithium dendrites and lithium nanograins covered by a lithium fluoride-rich solid-electrolyte interphase (SEI). We find the sporadic lithium stripping behavior and three important modes that can describe the stripping of individual lithium deposits, regardless of their morphology: (i) symmetric stripping, (ii) surface-preferred asymmetric stripping, and (iii) interface-preferred asymmetric stripping. In addition, SEI chemical mapping with high spatial resolution shows a remarkable SEI loss at the end of the lithium metal stripping, which illustrates the importance of SEI protection in the subsequent cycles.

Achieving hierarchical nanomaterials from a bottom-up approach remains challenging. Here, we report a closed-cage, onion nanostructure of covalent organic framework (COF) obtained through a low-temperature solvothermal synthesis. Atomic resolution transmission electron microscopy revealed the atomic arrangement in this COF onion, in which rich nitrogen was uniformly embedded in the periodic porous graphitic framework. The COF onion structure displayed graphitic features at a 0.33 nm interlayer spacing with Van der Waals interactions predominated between the layers. The onion layers exhibited significant heterogeneity in layer stacking by adopting a combination of different stacking modes. Defects were also found, such as five- or seven-member rings deviating from the perfect hexagonal lattice. These geometrical defects resulted in curving the 2D layers, which may have promoted the formation of onion nanostructures through a layer-by-layer attachment. We constructed a corresponding model that predicts COF onion properties. This novel onion exhibited a bandgap value of 2.56 eV, resembling other carbon-based nanomaterials, suggesting potential applications in sensors, photocatalysts, and nanoelectronics.

Twinning frequently occurs in nanocrystals during various thermal, chemical, or mechanical processes. However, the nucleation and propagation mechanisms of twinning in nanocrystals remain poorly understood. Through in situ atomic resolution transmission electron microscopy observation at millisecond temporal resolution, we show the twinning in Pb individual nanocrystals via a double-layer swap motion where two adjacent atomic layers shift relative to one another. The swap motion results in twin nucleation, and it also serves as a basic unit of movement for twin propagation. Our calculations reveal that the swap motion is a phonon eigenmode of the face-centered cubic crystal structure of Pb, and it is enhanced by the quantum size effect of nanocrystals.

Nanocapsules are hollow nanoscale shells that have applications in drug delivery, batteries, self-healing materials, and as model systems for naturally occurring shell geometries. In many applications, nanocapsules are designed to release their cargo as they buckle and collapse, but the details of this transient buckling process have not been directly observed. Here, we use in situ liquid-phase transmission electron microscopy to record the electron-irradiation-induced buckling in spherical 60-187 nm polymer capsules with ∼3.5 nm walls. We observe in real time the release of aqueous cargo from these nanocapsules and their buckling into morphologies with single or multiple indentations. The in situ buckling of nanoscale capsules is compared to ex situ measurements of collapsed and micrometer-sized capsules and to Monte Carlo (MC) simulations. The shape and dynamics of the collapsing nanocapsules are consistent with MC simulations, which reveal that the excessive wrinkling of nanocapsules with ultrathin walls results from their large Föppl-von Kármán numbers around 105. Our experiments suggest design rules for nanocapsules with the desired buckling response based on parameters such as capsule radius, wall thickness, and collapse rate.

Understanding nanostructure ripening mechanisms is desirable for gaining insight on the growth and potential applications of nanoscale materials. However, the atomic pathways of nanostructure ripening in solution have rarely been observed directly. Here, we report defect-mediated ripening of Cd-CdCl2 core-shell nanoparticles (CSN) revealed by in-situ atomic resolution imaging with liquid cell transmission electron microscopy. We find that ripening is initiated by dissolution of the nanoparticle with an incomplete CdCl2 shell, and that the areas of the Cd core that are exposed to the solution are etched first. The growth of the other nanoparticles is achieved by generating crack defects in the shell, followed by ion diffusion through the cracks. Subsequent healing of crack defects leads to a highly crystalline CSN. The formation and annihilation of crack defects in the CdCl2 shell, accompanied by disordering and crystallization of the shell structure, mediate the ripening of Cd-CdCl2 CSN in the solution.

Metal-organic layers (MOLs) are highly attractive for application in catalysis, separation, sensing and biomedicine, owing to their tunable framework structure. However, it is challenging to obtain comprehensive information about the formation and local structures of MOLs using standard electron microscopy methods due to serious damage under electron beam irradiation. Here, we investigate the growth processes and local structures of MOLs utilizing a combination of liquid-phase transmission electron microscopy, cryogenic electron microscopy and electron ptychography. Our results show a multistep formation process, where precursor clusters first form in solution, then they are complexed with ligands to form non-crystalline solids, followed by the arrangement of the cluster-ligand complex into crystalline sheets, with additional possible growth by the addition of clusters to surface edges. Moreover, high-resolution imaging allows us to identify missing clusters, dislocations, loop and flat surface terminations and ligand connectors in the MOLs. Our observations provide insights into controllable MOL crystal morphology, defect engineering, and surface modification, thus assisting novel MOL design and synthesis.

An understanding of solid-liquid interfaces is of great importance for fundamental research as well as industrial applications. However, it has been very challenging to directly image solid-liquid interfaces with high resolution, thus their structure and properties are often unknown. Here, we report a quasi-liquid phase between metal (In, Sn) nanoparticle surfaces and an aqueous solution observed using liquid cell transmission electron microscopy. Our real-time high-resolution imaging reveals a thin layer of liquid-like materials at the interfaces with the frequent appearance of small In nanoclusters. Such a quasi-liquid phase serves as an intermediate for the mass transport from the metal nanoparticle to the liquid. Density functional theory-molecular dynamics simulations demonstrate that the positive charges of In ions greatly contribute to the stabilization of the quasi-liquid phase on the metal surface.

Fire poses a substantial threat to concrete structures because calcium silicate hydrate (C-S-H) is not thermally stable at high temperatures. Herein, in situ TEM at temperatures from 20 to 800 °C was conducted to study the thermal-induced structural changes in C-S-H. We captured C-S-H shrinks at an average rate of 0.02 μm2/oC upon heating with three stages observed, including induction, constant, and rapid periods. Our observation revealed that an 800 nm pore could be healed during pore structure evolution owing to the reconstruction and deformation among C-S-H blocks. The Ca/Si ratio was dropped at higher temperatures because of the leakage of calcium ions from the C-S-H structure to form CaO precipitates. The temperature-driven phase transformation and degradation were also detected using electron diffraction that C-S-H was transformed into metastable calcium silicate minerals above 800 °C. This work provides insights into the nanoscale transformation of C-S-H at high temperatures.

Cu metal nanostructures have attracted wide interest of study as catalysts for CO2 reduction reaction and other applications. Controlling the structure and morphology of Cu nanostructures during synthesis is crucial for achieving desired properties. Here, we studied temperature effects on electrochemical deposition of Cu nanoparticles. We found the size, nucleation density, and crystallinity of Cu nanoparticles are strongly influenced by low temperature processing. The electrodeposition at low temperature (-20°C) results in clusters of assembled small Cu nanoparticles, which is distinctly different from the large individual highly crystalline Cu nanoparticles obtained from the room temperature process. The differences in Cu nanoparticle morphology and crystallinity are attributed to the variations in reduction reaction rate and surface diffusion. The limitation of the reaction rate promotes multiple nuclei, and low surface diffusion induces poor crystallinity. This study deepens our understanding of low-temperature effects on electrochemical processes assisting the design of diverse hierarchical catalytic materials.

Covalent organic frameworks (COFs) with efficient charge transport and exceptional chemical stability are emerging as an import class of semiconducting materials for opto-/electronic devices and energy-related applications. However, the limited synthetic chemistry to access such materials and the lack of mechanistic understanding of carrier mobility greatly hinder their practical applications. Herein, we report the synthesis of three chemically stable polyarylether-based metallophthalocyanine COFs (PAE-PcM, M = Cu, Ni, and Co) and facile in situ growth of their thin films on various substrates (i.e., SiO2/Si, ITO, quartz) under solvothermal conditions. We show that PAE-PcM COFs thin films with van der Waals layered structures exhibit p-type semiconducting properties with the intrinsic mobility up to ∼19.4 cm2 V-1 s-1 and 4 orders of magnitude of increase in conductivity for PAE-PcCu film (0.2 S m-1) after iodine doping. Density functional theory calculations reveal that the carrier transport in the framework is anisotropic, with the out-of-plane hole transport along columnar stacked phthalocyanine more favorable. Furthermore, PAE-PcCo shows the redox behavior maximumly contributes ∼88.5% of its capacitance performance, giving rise to a high surface area normalized capacitance of ∼19 μF cm-2. Overall, this work not only offers fundamental understandings of electronic properties of polyarylether-based 2D COFs but also paves the way for their energy-related applications.

The development of liquid cells for transmission electron microscopy has enabled breakthroughs in our ability to follow nanoscale structural, morphological, or chemical changes during materials growth and applications. Time-resolved high-resolution imaging and chemical analysis through liquids opened the opportunity to capture nanoscale dynamic processes of materials, including reaction intermediates and the transformation pathways. In this article, a series of work is highlighted with topics ranging from liquid cell developments to in situ studies of nanocrystal growth and transformations, dendrite formation, and suppression of lithium dendrites through in situ characterization of the solid–electrolyte interphase chemistry. The understanding garnered is expected to accelerate the discovery of novel materials for applications in energy storage, catalysis, sensors, and other functional devices.

Electron microscopy touches on nearly every aspect of modern life, underpinning materials development for quantum computing, energy and medicine. We discuss the open, highly integrated and data-driven microscopy architecture needed to realize transformative discoveries in the coming decade.

Liquid cell transmission electron microscopy (TEM) enables the direct observation of dynamic physical and chemical processes in liquids at the nanoscale. Quantitative investigations into reactions with fast kinetics and/or multiple reagents will benefit from further advances in liquid cell design that facilitate rapid in situ mixing and precise control over reagent volumes and concentrations. This work reports the development of inorganic-organic nanocapsules for high-resolution TEM imaging of nanoscale reactions in liquids with well-defined zeptoliter volumes. These hybrid nanocapsules, with 48 nm average diameter, consist of a thin layer of gold coating a lipid vesicle. As a model reaction, the nucleation, growth, and diffusion of nanobubbles generated by the radiolysis of water is investigated inside the nanocapsules. When the nanobubbles are sufficiently small (10-25 nm diameter), they are mobile in the nanocapsules, but their movement deviates from Brownian motion, which may result from geometric confinement by the nanocapsules. Gases and fluids can be transported between two nanocapsules when they fuse, demonstrating in situ mixing without using complex microfluidic schemes. The ability to synthesize nanocapsules with controlled sizes and to monitor dynamics simultaneously inside multiple nanocapsules provides opportunities to investigate nanoscale processes such as single nanoparticle synthesis in confined volumes and biological processes such as biomineralization and membrane dynamics.

The practical application of high-capacity Li-rich cathode materials is hindered by capacity fading and voltage decay. The capacity fading and voltage decay could be effectively overcome by using water-soluble guar gum (GG) binder instead of traditional polyvinylidene fluoride (PVDF). However, the specific role of the GG binder is not clear yet, though the GG binder can significantly improve the electrochemical performance of Li-rich cathode. To understand the effect of GG binder on the morphology, microstructure of electrode and electrode/electrolyte interfaces, ex-situ scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray adsorption near edge spectroscopy (XANES), in-situ electrochemical impedance spectroscopy (EIS) were applied to comparatively study the charge-discharge processes of Li-rich Li1.2Ni0.2Mn0.6O2 cathode when using GG and PVDF as binders. The results indicate that the GG binder can prevent electrode crack and active material loss, ascribing to the strong mechanical adhesion of GG binder with active material particles and current collector. It has found that the GG binder can also induce the formation of a uniform layer on Li1.2Ni0.2Mn0.6O2 particles’ surface. As a consequence, both the electrolyte decomposition and the electrode corrosion were significantly inhibited. The strong chelation between Mn2+ and polar OH group restrain Mn ion dissolution, which contributes to surface structural transformation mitigation. The present study reveals the role of water-soluble GG binder in reducing capacity fading and voltage decay of Li-rich material and is of great importance in design functional binders for high-performance Li-rich electrodes.

The crystal phase-based heterostructures of noble metal nanomaterials are of great research interest for various applications, such as plasmonics and catalysis. However, the synthesis of unusual crystal phases of noble metals still remains a great challenge, making the construction of heterophase noble metal nanostructures difficult. Here, we report a one-pot wet-chemical synthesis of well-defined heterophase fcc-2H-fcc gold nanorods (fcc: face-centred cubic; 2H: hexagonal close-packed with stacking sequence of "AB") at mild conditions. Single particle-level experiments and theoretical investigations reveal that the heterophase gold nanorods demonstrate a distinct optical property compared to that of the conventional fcc gold nanorods. Moreover, the heterophase gold nanorods possess superior electrocatalytic activity for the carbon dioxide reduction reaction over their fcc counterparts under ambient conditions. First-principles calculations suggest that the boosted catalytic performance stems from the energetically favourable adsorption of reaction intermediates, endowed by the unique heterophase characteristic of gold nanorods.

It is crucial to suppress lithium dendrite formation in lithium metal batteries. Formation of a good solid-electrolyte interphase (SEI) has been considered to be effective in limiting lithium dendrite growth. However, how the SEI may be modified during lithium deposition is hard to resolve due to challenges in in situ investigation of the SEI with fine details. We report an in situ study that uncovers the lithium dendrite suppression mechanism arising from SEI modification by a poly(diallyldimethylammonium chloride) (PDDA) cationic polymer film, using electrochemical liquid cell transmission electron microscopy (TEM). Lithium nanogranules are obtained in the presence of the polymer film. Chemical mapping of the deposits provides remarkable details of the SEI on individual nanogranules. It shows that lithium fluorides are uniformly distributed within the inner SEI layer of individual lithium nanogranules, arising from the instantaneous reaction of the deposited lithium with PF6- ions accumulated by the cationic polymer film, and thus the dendritic growth of lithium is prohibited. The ability to directly measure SEI chemistry at the nanoscale down to the individual nanograins in situ and unveil its correlation with the lithium deposition behavior opens future opportunities to explore unsolved mechanisms in batteries.

Na metal is an attractive anode material for rechargeable Na ion batteries, however, the dendritic growth of Na can cause serious safety issues. Along with modifications of solid-electrolyte interphase (SEI), engineering the electrode has been reported to be effective in suppressing Na dendritic growth, likely by reducing localized current density accumulation. However, fundamental understanding of Na growth at the nanoscale is still limited. Here, we report an in-situ study of Na electrodeposition in electrochemical liquid cells with the electrodes in different surface roughness, e.g., flat or sharp curvature. Real time observation using transmission electron microscopy (TEM) reveals the Na electrodeposition with remarkable details. Relatively large Na grains (in the micrometer scale) are achieved on the flat electrode surface. The local SEI thickness variations impact the growth rate, thus the morphology of individual grains. In contrast, small Na grains (in tens of nanometers) grow explosively on the electrode at the point with sharp curvature. The newly formed Na grains preferentially deposit at the base of existing grains close to the electrode. Further studies using continuum-based computational modeling suggest that the growth mode of an alkali metal (e.g. Na) is strongly influenced by the transport properties of SEI. Our direct observation of Na deposition in combination with the theoretical modeling provides insights for comprehensive understanding of electrode roughness and SEI effects on Na electrochemical deposition.

Porous graphitic framework (PGF) is a two-dimensional (2D) material that has emerging energy applications. An archetype contains stacked 2D layers, the structure of which features a fully annulated aromatic skeleton with embedded heteroatoms and periodic pores. Due to the lack of a rational approach in establishing in-plane order under mild synthetic conditions, the structural integrity of PGF has remained elusive and ultimately limited its material performance. Here, we report the discovery of the unusual dynamic character of the C=N bonds in the aromatic pyrazine ring system under basic aqueous conditions, which enables the successful synthesis of a crystalline porous nitrogenous graphitic framework with remarkable in-plane order, as evidenced by powder X-ray diffraction studies and direct visualization using high-resolution transmission electron microscopy. The crystalline framework displays superior performance as a cathode material for lithium-ion batteries, outperforming the amorphous counterparts in terms of capacity and cycle stability. Insertion of well-defined, evenly spaced nanoscale pores into the two-dimensional (2D) layers of graphene invokes exciting properties due to the modulation of its electronic band gaps and surface functionalities. A bottom-up synthesis approach to such porous graphitic frameworks (PGFs) is appealing but also remains a great challenge. The current methods of building covalent organic frameworks rely on a small collection of thermodynamically reversible reactions. Such reactions are, however, inadequate in generating a fully annulated aromatic skeleton in PGFs. With the discovery of dynamic pyrazine formation, we succeeded in applying this linking chemistry to obtain a crystalline PGF material, which has displayed high electrical conductivity and remarkable performance as a cathode material for lithium-ion batteries. We envision that the demonstrated success will open the door to a wide array of fully annulated 2D porous frameworks, which hold immense potential for clean energy applications. We report the unusual dynamic characteristics of the C=N bonds in the pyrazine ring promoted under basic aqueous conditions, which enables the successful synthesis of two-dimensional porous graphitic frameworks (PGFs) featuring fully annulated aromatic skeletons and periodic pores. The PGF displayed high electrical conductivity and remarkable performance as a cathode material for lithium-ion batteries, far outperforming the amorphous counterparts in terms of capacity and cycle stability.

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. [Figure not available: see fulltext.].

Oriented attachment of nanocrystals is an important route to constructing epitaxially-connected nanocrystal superlattices for various applications. During oriented attachment of semiconductor nanocrystals, neck can be formed between nanocrystals and it strongly influences the properties of the resulting superlattice. However, the neck formation mechanism is poorly understood. Here, we use in situ liquid cell transmission electron microscopy to directly observe the initiation and growth of homoepitaxial necks between PbSe nanocrystals with atomic details. We find that neck initiation occurs slowly (~ 10 s) when two nanocrystals approach to each other within an edge-to-edge distance of 0.6 nm. During neck initiation, Pb and Se atoms defuse from other facets into the gap, forming “dynamic reversible” filaments. Once the filament (neck) width is larger than a critical size of 0.9 nm, it gradually (15 s) widens into a 3-nm-wide neck. The atomic structure of the neck is further obtained using ex situ aberration-corrected scanning TEM imaging. Neck initiation and growth mechanisms are elucidated with density functional theory calculations. Our direct unveiling of the atomic pathways of neck formation during oriented attachment shed light into the fabrication of nanocrystal superlattices with improved structural order and electronic properties. [Figure not available: see fulltext.].

Surface oxidation, as one of fundamental chemical reactions in metals, greatly affects their properties. Herein, we develop a new quaternary GaInSnZn liquid metal with the melting temperature of 9.7 °C, which is the lowest among all reported Ga-based liquid metals. With high-resolution transmission electron microscopy, we directly observed the oxide layer formed on the surface of the liquid metal. The initially formed oxide layer is revealed to be amorphous and very sensitive to electron beam. Prolonged irradiation results in its structural change from amorphous to crystalline phases. The present finding refreshes the basic understanding of surface oxidization of liquid metals and opens up the possibility of tuning surface structures and morphologies by using electron beam irradiation.

We report an investigation of the pseudo-photocatalytic behavior of rutile TiO2 nanorods for water splitting observed with liquid cell transmission electron microscopy (TEM). The electron beam serves as a “light” source to initiate the catalytic reaction and a “water-in-salt” aqueous solution is employed as the electrolyte. The observation reveals that bubbles are generated preferentially residing near the {110} facet of a rutile TiO2 nanorod under a low electron dose rate (9.3–18.6 e-/Å2·s). These bubbles are ascribed to hydrogen gas generated from the pseudo-photocatalytic water splitting. As the electron beam current density increases to 93 e-/Å2 ·s, bubbles are also found at the {001} and {111} facets as well as in the bulk liquid solution, demonstrating the dominant effects of water electrolysis by electron beam under higher dose rates. The facet-dependent pseudo-photocatalytic behavior of rutile TiO2 nanorods is further validated using density functional theory (DFT)calculation. Our work establishes a facile liquid cell TEM setup for the study of pseudo-photocatalytic water splitting and it may also be applied to investigation of other photo-activated phenomena occurring at the solid-liquid interfaces.

Rational design and synthesis of transition metal sulfide complex nanostructures are significant for achieving desired materials properties for a variety of applications. Herein, we synthesized nickel sulfide (NiS) nanostructures using laser irradiation in an aqueous solution and under the ambient condition. Crystalline nanostructures with high phase-purity were achieved without further calcination. Other transition metal sulfides, such as CuS and ZnS, were also successfully synthesized using the laser irradiation approach, suggesting the practical application of this method. The hydrogen evolution reaction (HER) measurements show the NiS nanostructures synthesized for 4h (NiS-4h) not only exhibited competitive overpotential (−159 mV vs. RHE at 10 A/g), lower Tafel slope (218 mV/dec) but also delivered long-term stability (14 A/g at −250 mV vs. RHE for 12h). Moreover, the NiS-4h functioned as the electrode for supercapacitor with excellent specific capacitance (3761 F/g at 10 mV/s), reversibility and rate capability (1152 F/g at 100 mV/s). These superb electrochemical performances are attributed to the remarkable value of electrochemically active surface area (ECSA) and synergistic effect of Ni3+OOH for HER electrocatalytic activities, while the co-existence of Ni2+ and Ni3+ facilitates the rich redox reactions of NiS for supercapacitor.

The behavior of individual nanocrystals during superlattice phase transitions can profoundly affect the structural perfection and electronic properties of the resulting superlattices. However, details of nanocrystal morphological changes during superlattice phase transitions are largely unknown due to the lack of direct observation. Here, we report the dynamic deformability of PbSe semiconductor nanocrystals during superlattice phase transitions that are driven by ligand displacement. Real-time high-resolution imaging with liquid-phase transmission electron microscopy reveals that following ligand removal, the individual PbSe nanocrystals experience drastic directional shape deformation when the spacing between nanocrystals reaches 2 to 4 nm. The deformation can be completely recovered when two nanocrystals move apart or it can be retained when they attach. The large deformation, which is responsible for the structural defects in the epitaxially fused nanocrystal superlattice, may arise from internanocrystal dipole-dipole interactions.

The first-cycle behavior of layered Li-rich oxides, including Li2MnO3 activation and cathode electrolyte interphase (CEI) formation, significantly influences their electrochemical performance. However, the Li2MnO3 activation pathway and the CEI formation process are still controversial. Here, the first-cycle properties of xLi2MnO3·(1- x) LiNi0.3Co0.3Mn0.4O2 ( x = 0, 0.5, 1) cathode materials were studied with an in situ electrochemical quartz crystal microbalance (EQCM). The results demonstrate that a synergistic effect between the layered Li2MnO3 and LiNi0.3Co0.3Mn0.4O2 structures can significantly affect the activation pathway of Li1.2Ni0.12Co0.12Mn0.56O2, leading to an extra-high capacity. It is demonstrated that Li2MnO3 activation in Li-rich materials is dominated by electrochemical decomposition (oxygen redox), which is different from the activation process of pure Li2MnO3 governed by chemical decomposition (Li2O evolution). CEI evolution is closely related to Li+ extraction/insertion. The valence state variation of the metal ions (Ni, Co, Mn) in Li-rich materials can promote CEI formation. This study is of significance for understanding and designing Li-rich cathode-based batteries.

Two dimensional (2D) materials have found various applications because of their unique physical properties. For example, graphene has been used as the electron transparent membrane for liquid cell transmission electron microscopy (TEM) due to its high mechanical strength and flexibility, single-atom thickness, chemical inertness, etc. Here, we report using 2D MoS2 as a functional substrate as well as the membrane window for liquid cell TEM, which is enabled by our facile and polymer-free MoS2 transfer process. This provides the opportunity to investigate the growth of Pt nanocrystals on MoS2 substrates, which elucidates the formation mechanisms of such heterostructured 2D materials. We find that Pt nanocrystals formed in MoS2 liquid cells have a strong tendency to align their crystal lattice with that of MoS2, suggesting a van der Waals epitaxial relationship. Importantly, we can study its impact on the kinetics of the nanocrystal formation. The development of MoS2 liquid cells will allow further study of various liquid phenomena on MoS2, and the polymer-free MoS2 transfer process will be implemented in a wide range of applications.

An understanding of nanocrystal shape evolution is significant for the design, synthesis, and applications of nanocrystals with surface-enhanced properties such as catalysis or plasmonics. Surface adsorbates that are selectively attached to certain facets may strongly affect the atomic pathways of nanocrystal shape development. However, it is a great challenge to directly observe such dynamic processes in situ with a high spatial resolution. Here, we report the anomalous shape evolution of Ag2O2 nanocrystals modulated by the surface adsorbates of Ag clusters during electron beam etching, which is revealed through in situ transmission electron microscopy (TEM). In contrast to the Ag2O2 nanocrystals without adsorbates, which display the near-equilibrium shape throughout the etching process, Ag2O2 nanocrystals with Ag surface adsorbates show distinct facet development during etching by electron beam irradiation. Three stages of shape changes are observed: a sphere-to-a cube transformation, side etching of a cuboid, and bottom etching underneath the surface adsorbates. We find that the Ag adsorbates modify the Ag2O2 nanocrystal surface configuration by selectively capping the junction between two neighboring facets. They prevent the edge atoms from being etched away and block the diffusion path of surface atoms. Our findings provide critical insights into the modulatory function of surface adsorbates on the shape control of nanocrystals.

Recent advances in graphene liquid cells for in situ transmission electron microscopy (TEM) have opened many opportunities for the study of materials transformations and chemical reactions in liquids with high spatial resolution. However, the behavior of thin liquids encapsulated in a graphene liquid cell has not been fully understood. Here, we report real time TEM imaging of the nanoscale dynamic behavior of liquids in graphene nanocapillaries. Our observations reveal that the interfaces between liquid and gas bubble can fluctuate, leading to the generation of liquid nanodroplets near the interfaces. Liquid nanodroplets often show irregular shape with dynamic changes of their configuration under the electron beam. We consider that the dynamic motion of liquid-gas interfaces might be introduced by the electrostatic energy from transiently charged interfaces. We find that improving the wettability of graphene liquid cells by ultraviolet-ozone treatment can significantly modify the dynamic motion of the encapsulated liquids. Our study provides valuable information of the interactions between liquid and graphene under the electron beam, and it also offers key insights on the nanoscale fluid dynamics in confined spaces.

Selective nitrogen-doping of graphene oxide with a high pyridinic N ratio (51%; L-GO) was achieved by laser irradiation of graphene oxide with ammonia. The resulting L-GO exhibited enhanced electrocatalytic properties; specifically, the overpotential of the hydrogen evolution reaction (HER) was improved by over 400 mV at 10 mA cm-2 compared to the pristine graphene oxide.