Liquid Cell Transmission Electron Microscopy Research Articles

Multilayer Graphene—A Promising Electrode Material in Liquid Cell Electrochemistry

AbstractThe combination of imaging with electrochemical quantification in liquid cell transmission electron microscopy (TEM) provides opportunities for visualizing material processes in liquid with good spatial and temporal resolution in a way that is inaccessible in bench‐top electrochemical experiments. The electrode material used in liquid cell TEM determines the reliability and consistency of the electrochemical measurements and also influences the resolution when imaging processes on the electrode. Here, the opportunities arising from the use of 2D materials in liquid cell electrochemistry are explored. Through electrochemical imaging and modeling, it is demonstrated that the use of graphene electrodes enables quantitative study of electrochemical metal deposition and it is suggested that the minimal electron scattering and electric‐field enhanced wettability are advantageous in obtaining interpretable and higher resolution data. It is anticipated that incorporation of 2D materials into electrode design will present new opportunities for investigating problems in crystal growth, energy storage, and electrocatalysis.

Design of Highly Durable Core-Shell Catalysts by Controlling Shell Distribution Guided by In-Situ Corrosion Study.

Most degradations in electrocatalysis are caused by corrosion in operation, for example the corrosion of the core in a core-shell electrocatalyst during the oxygen reduction reaction (ORR). Herein, according to the in-situ study on nanoscale corrosion kinetics via liquid cell transmission electron microscopy (LC-TEM) in the authors' previous work, they sequentially designed an optimized nanocube with the protection of more layers on the corners by adjusting the Pt atom distribution on corners and terraces. This modified nanocube (MNC) is much more corrosion resistant in the in-situ observation. Furthermore, in the practical electrochemical stability testing, the MNC catalyst also showed the best stability performance with the 0.37% and 9.01% loss in specific and mass activity after 30 000 cycles accelerated durability test (ADT). This work also demonstrates that how an in-situ study can guide the design of desired materials with improved properties and build a bridge between in-situ study and practical application.

Quantitative In Situ Visualization of Thermal Effects on the Formation of Gold Nanocrystals in Solution.

Understanding temperature effects in nanochemistry requires real-time in situ measurements because this key parameter of wet-chemical synthesis simultaneously influences the kinetics of chemical reactions and the thermodynamic equilibrium of nanomaterials in solution. Here, temperature-controlled liquid cell transmission electron microscopy is exploited to directly image the radiolysis-driven formation of gold nanoparticles between 25 °C and 85 °C and provide a deeper understanding of the atomic-scale processes determining the size and shape of gold colloids. By quantitatively comparing the nucleation and growth rates of colloidal assemblies with classical models for nanocrystal formation, it is shown that the increase of the molecular diffusion and the solubility of gold governs the drastic changes in the formation dynamics of nanostructures in solution with temperature. In contraction with the common view of coarsening processes in solution, it is also demonstrated that the dissolution of nanoparticles and thus the Ostwald ripening is not only driven by size effects. Furthermore, visualizing thermal effects on faceting processes at the single nanoparticle level reveals how the competition between the growth speed and the surface diffusion dictates the final shape of nanocrystals.

Insights into the Defect Structure Resulting from the Hydrogen Absorption in Palladium Nanocubes Using Liquid Cell Transmission Electron Microscopy

Insights into the Defect Structure Resulting from the Hydrogen Absorption in Palladium Nanocubes Using Liquid Cell Transmission Electron Microscopy

Automated Crystal Orientation Mapping with a Liquid-Cell TEM

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Observation of Surface Ligands-Controlled Etching of Palladium Nanocrystals.

Selective adsorption of ligands on nanocrystal surfaces can affect oxidative etching. Here, we report the etching of palladium nanocrystals imaged using liquid cell transmission electron microscopy. The adsorption of surface ligands (i.e., iron acetylacetonate and its derivatives) and their role as inhibitor molecules on the etching process were investigated. Our observations revealed that the etching was dominated by the interplay between palladium facets and ligands and that the etching exhibited different pathways at different concentrations of ligands. At a low concentration of iron acetylacetonate (0.1 mM), rapid etching primarily at {100} facets led to a concave structure. At a high concentration (1.0 mM), the etch rate was decreased owing to a protective film of iron acetylacetonate on the {100} facets and a round nanoparticle was achieved. Ab initio calculations showed that the differences in adsorption energy of inhibitor molecules on palladium facets were responsible for the etching behavior.

Elucidating the Role of Halides and Iron during Radiolysis-Driven Oxidative Etching of Gold Nanocrystals Using Liquid Cell Transmission Electron Microscopy and Pulse Radiolysis.

Graphene liquid cell transmission electron microscopy (TEM) has enabled the observation of a variety of nanoscale transformations. Yet understanding the chemistry of the liquid cell solution and its impact on the observed transformations remains an important step toward translating insights from liquid cell TEM to benchtop chemistry. Gold nanocrystal etching can be used as a model system to probe the reactivity of the solution. FeCl3 has been widely used to promote gold oxidation in bulk and liquid cell TEM studies, but the roles of the halide and iron species have not been fully elucidated. In this work, we observed the etching trajectories of gold nanocrystals in different iron halide solutions. We observed an increase in gold nanocrystal etch rate going from Cl-- to Br-- to I--containing solutions. This is consistent with a mechanism in which the dominant role of halides is as complexation agents for oxidized gold species. Additionally, the mechanism through which FeCl3 induces etching in liquid cell TEM remains unclear. Ground-state bleaching of the Fe(III) absorption band observed through pulse radiolysis indicates that iron may react with Cl2·- radicals to form an oxidized transient species under irradiation. Complete active space self-consistent field (CASSCF) calculations indicate that the FeCl3 complex is oxidized to an Fe species with an OH radical ligand. Together our data indicate that an oxidized Fe species may be the active oxidant, while halides modulate the etch rate by tuning the reduction potential of gold nanocrystals.

Revealing Au13 as Elementary Clusters During the Early Formation of Au Nanocrystals.

Understanding the formation mechanism of nanocrystals in solution is fundamental to the development of materials science. For a metal nanocrystal, the cluster-mediated formation mechanism is still poorly understood. In particular, identifying what types of clusters are dominant and how they evolve into a nanocrystal in the early nucleation stage remains a great challenge. Here, using liquid-cell transmission electron microscopy, we directly observe the formation of ultrasmall Au clusters (∼0.84 nm) in the presence of PAA-Na. These clusters, which correspond to the size of the Au13 cluster, coalesce to form nanocrystals. Our molecular dynamics simulations suggest that Au13 in an aqueous environment has greater stability when compared to other cluster sizes and provide atomistic details of growth by cluster coalescence. Collectively, our demonstration of Au13 as the dominant species with an elaboration of their coalescence kinetics sheds light on nonclassical nanocrystal formation mechanisms and offers useful guidelines for designing innovative pathways for the synthesis of nanomaterials.

Tunability of Interactions between the Core and Shell in Rattle-Type Particles Studied with Liquid-Cell Electron Microscopy.

Yolk–shell or rattle-type particles consist of a core particle that is free to move inside a thin shell. A stable core with a fully accessible surface is of interest in fields such as catalysis and sensing. However, the stability of a charged nanoparticle core within the cavity of a charged thin shell remains largely unexplored. Liquid-cell (scanning) transmission electron microscopy is an ideal technique to probe the core–shell interactions at nanometer spatial resolution. Here, we show by means of calculations and experiments that these interactions are highly tunable. We found that in dilute solutions adding a monovalent salt led to stronger confinement of the core to the middle of the geometry. In deionized water, the Debye length κ–1 becomes comparable to the shell radius Rshell, leading to a less steep electric potential gradient and a reduced core–shell interaction, which can be detrimental to the stability of nanorattles. For a salt concentration range of 0.5–250 mM, the repulsion was relatively long-ranged due to the concave geometry of the shell. At salt concentrations of 100 and 250 mM, the core was found to move almost exclusively near the shell wall, which can be due to hydrodynamics, a secondary minimum in the interaction potential, or a combination of both. The possibility of imaging nanoparticles inside shells at high spatial resolution with liquid-cell electron microscopy makes rattle particles a powerful experimental model system to learn about nanoparticle interactions. Additionally, our results highlight the possibilities for manipulating the interactions between core and shell that could be used in future applications.

Atomistic insights into the nucleation and growth of platinum on palladium nanocrystals

Despite the large number of reports on colloidal nanocrystals, very little is known about the mechanistic details in terms of nucleation and growth at the atomistic level. Taking bimetallic core-shell nanocrystals as an example, here we integrate in situ liquid-cell transmission electron microscopy with first-principles calculations to shed light on the atomistic details involved in the nucleation and growth of Pt on Pd cubic seeds. We elucidate the roles played by key synthesis parameters, including capping agent and precursor concentration, in controlling the nucleation site, diffusion path, and growth pattern of the Pt atoms. When the faces of a cubic seed are capped by Br−, Pt atoms preferentially nucleate from corners and then diffuse to edges and faces for the creation of a uniform shell. The diffusion does not occur until the Pt deposited at the corner has reached a threshold thickness. At a high concentration of the precursor, self-nucleation takes place and the Pt clusters then randomly attach to the surface of a seed for the formation of a non-uniform shell. These atomistic insights offer a general guideline for the rational synthesis of nanocrystals with diverse compositions, structures, shapes, and related properties.

The studies on wet chemical etching via in situ liquid cell TEM

Wet chemical etching is a widely used process to fabricate fascinating nanomaterials, such as nanoparticles with precisely controlled size and shape. Understanding the etching mechanism and kinetic evolution process is crucial for controlling wet chemical etching. The development of in situ liquid cell transmission electron microscopy (LCTEM) enables the study on wet chemical etching with high temporal and spatial resolutions. However, there still lack a detailed literature review on the wet chemical etching studies by in situ LCTEM. In this review, we summarize the studies on wet etching nanoparticles, one-dimensional nanomaterials and nanoribbons by in situ LCTEM, including etching rate, anisotropic etching, morphology evolution process, and etching mechanism. The challenges and opportunities of in situ LCTEM are also discussed.

Microscopic Kinetics Pathway of Salt Crystallization in Graphene Nanocapillaries.

The fundamental understanding of crystallization, in terms of microscopic kinetic and thermodynamic details, remains a key challenge in the physical sciences. Here, by using insitu graphene liquid cell transmission electron microscopy, we reveal the atomistic mechanism of NaCl crystallization from solutions confined within graphene cells. We find that rock salt NaCl forms with a peculiar hexagonal morphology. We also see the emergence of a transitory graphitelike phase, which may act as an intermediate in a two-step pathway. With the aid of density functional theory calculations, we propose that these observations result from a delicate balance between the substrate-solute interaction and thermodynamics under confinement. Our results highlight the impact of confinement on both the kinetics and thermodynamics of crystallization, offering new insights into heterogeneous crystallization theory and a potential avenue for materials design.

Radiolysis-Induced Crystallization of Sodium Chloride in Acetone by Electron Beam Irradiation.

In situ liquid cell transmission electron microscopy (LC-TEM) is an innovative method for studying the processes involved in the formation of crystals in liquids. However, it is difficult to capture early stages of crystallization because of the small field of view and the unfavorable changes in sample composition resulting from electron-beam radiolysis. Nevertheless, if the radiolysis required to induce the crystallization of a sample could be controlled in LC-TEM, this would be advantageous for observing the crystallization process. Here, we examined this possibility by using a mixture of sodium chlorate (NaClO3) and acetone in the LC-TEM. The electron beam induced the formation of dendritic crystals in a saturated acetone solution of NaClO3; moreover, these crystals consisted of sodium chloride (NaCl), rather than NaClO3, suggesting that chloride ions (Cl−), which were not present in the initial solution, were generated by radiolysis of chlorate ions ${\rm \lpar ClO}_3^- \rpar$. As a result, the solution then supersaturated with NaCl because its solubility in acetone is much lower than that of NaClO3. The combination of radiolysis and a solvent in which a solute is much less soluble is potentially useful for establishing crystallization conditions for materials that are difficult to crystallize directly in LC-TEM experiments.

Anomalous nanoparticle surface diffusion in LCTEM is revealed by deep learning-assisted analysis

The motion of nanoparticles near surfaces is of fundamental importance in physics, biology, and chemistry. Liquid cell transmission electron microscopy (LCTEM) is a promising technique for studying motion of nanoparticles with high spatial resolution. Yet, the lack of understanding of how the electron beam of the microscope affects the particle motion has held back advancement in using LCTEM for in situ single nanoparticle and macromolecule tracking at interfaces. Here, we experimentally studied the motion of a model system of gold nanoparticles dispersed in water and moving adjacent to the silicon nitride membrane of a commercial LC in a broad range of electron beam dose rates. We find that the nanoparticles exhibit anomalous diffusive behavior modulated by the electron beam dose rate. We characterized the anomalous diffusion of nanoparticles in LCTEM using a convolutional deep neural-network model and canonical statistical tests. The results demonstrate that the nanoparticle motion is governed by fractional Brownian motion at low dose rates, resembling diffusion in a viscoelastic medium, and continuous-time random walk at high dose rates, resembling diffusion on an energy landscape with pinning sites. Both behaviors can be explained by the presence of silanol molecular species on the surface of the silicon nitride membrane and the ionic species in solution formed by radiolysis of water in presence of the electron beam.

Studying the Effects of Temperature on the Nucleation and Growth of Nanoparticles by Liquid-Cell Transmission Electron Microscopy.

Temperature control is a recent development that provides an additional degree of freedom to study nanochemistry by liquid cell transmission electron microscopy. In this paper, we describe how to prepare an in situ heating experiment for studying the effect of temperature on the formation of gold nanoparticles driven by radiolysis in water. The protocol of the experiment is fairly simple involving a special liquid cell with uniform heating capabilities up to 100 °C, a liquid-cell TEM holder with flow capabilities and an integrated interface for controlling the temperature. We show that the nucleation and growth mechanisms of gold nanoparticles are drastically impacted by the temperature in liquid cell. Using STEM imaging and nanodiffraction, the evolution of the density, size, shape and atomic structure of the growing nanoparticles are revealed in real time. Automated image processing algorithms are exploited to extract useful quantitative data from video sequences, such as the nucleation and growth rates of nanoparticles. This approach provides new inputs for understanding the complex physico-chemical processes at play during the liquid-phase synthesis of nanomaterials.

Studying the Effects of Temperature on the Nucleation and Growth of Nanoparticles by Liquid-Cell Transmission Electron Microscopy

Studying the Effects of Temperature on the Nucleation and Growth of Nanoparticles by Liquid-Cell Transmission Electron Microscopy

Accelerated decomposition of Bi2S3 nanorods in water under an electron beam: a liquid phase transmission electron microscopy study

Evaluating the stability of semiconductor photocatalysts is critical in the development of efficient catalysts. The morphological and microstructural behaviors of nanorod-shaped Bi2S3 semiconductors in aqueous solution were studied using a liquid cell transmission electron microscopy (TEM) technique. The rapid decomposition of Bi2S3 in water was observed under electron beam irradiation during TEM. Rounded bright spots due to a reduction in thickness were observed on the Bi2S3 nanorods at the initial stage of the decomposition, and rounded dark particles appeared outside of the nanorods in the solution, continuing the decomposition. This was confirmed by analyzing the atomic structure of the newly formed small particles, which consisted of an orthorhombic Bi2S3 phase. The stability-related decomposition of the Bi2S3 nanorods was demonstrated by considering the reduction and oxidation potentials of Bi2S3 in an aqueous solution. The effect of water radiolysis by the incident electron during TEM observations on the decomposition process was also determined by considering the time-dependent concentration behavior of the chemical species. Our study therefore reflects a novel route to evaluate the stabilities of semiconductor photocatalysts, which could ultimately solve a range of energy and environmental pollution problems.

Enhancing and Mitigating Radiolytic Damage to Soft Matter in Aqueous Phase Liquid-Cell Transmission Electron Microscopy in the Presence of Gold Nanoparticle Sensitizers or Isopropanol Scavengers.

In this work, we describe the radiolytic environment experienced by a polymer in water during liquid-cell transmission electron microscopy (LCTEM). We examined the radiolytic environment of aqueous solutions of poly(ethylene glycol) (PEG, 2400 g/mol) in the presence of sensitizing gold nanoparticles (GNPs, 100 nm) or radical scavenging isopropanol (IPA). To quantify polymer damage, we employed post-mortem analysis via matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS). This approach confirms IPA (1-10% w/v) can significantly mitigate radiolysis-induced damage to polymers in water, while GNPs significantly enhance damage. We couple LCTEM experiments with simulations to provide a generalizable strategy for assessing radiolysis mitigation or enhancement. This study highlights the caution required for LCTEM experiments on inorganic nanoparticles where solution phase properties of surrounding organic materials or the solvent itself are under investigation. Furthermore, we anticipate an increased use of scavengers for LCTEM studies of all kinds.

In Situ Study of the Wet Chemical Etching of SiO2 and Nanoparticle@SiO2 Core-Shell Nanospheres.

The recent development of liquid cell (scanning) transmission electron microscopy (LC-(S)TEM) has opened the unique possibility of studying the chemical behavior of nanomaterials down to the nanoscale in a liquid environment. Here, we show that the chemically induced etching of three different types of silica-based silica nanoparticles can be reliably studied at the single particle level using LC-(S)TEM with a negligible effect of the electron beam, and we demonstrate this method by successfully monitoring the formation of silica-based heterogeneous yolk–shell nanostructures. By scrutinizing the influence of electron beam irradiation, we show that the cumulative electron dose on the imaging area plays a crucial role in the observed damage and needs to be considered during experimental design. Monte-Carlo simulations of the electron trajectories during LC-(S)TEM experiments allowed us to relate the cumulative electron dose to the deposited energy on the particles, which was found to significantly alter the silica network under imaging conditions of nanoparticles. We used these optimized LC-(S)TEM imaging conditions to systematically characterize the wet etching of silica and metal(oxide)–silica core–shell nanoparticles with cores of gold and iron oxide, which are representative of many other core–silica–shell systems. The LC-(S)TEM method reliably reproduced the etching patterns of Stöber, water-in-oil reverse microemulsion (WORM), and amino acid-catalyzed silica particles that were reported before in the literature. Furthermore, we directly visualized the formation of yolk–shell structures from the wet etching of Au@Stöber silica and Fe3O4@WORM silica core–shell nanospheres.

Liquid Cell Transmission Electron Microscopy Reveals C-S-H Growth Mechanism During Portland Cement Hydration

We report the first application of in-situ liquid cell transmission electron microscopy (LC-TEM) to research hydration reactions of nano OPC, providing nanoscale insight into early reaction mechanisms. We demonstrate that the formation and growth of C-S-H precipitates starts through lateral growth of planar silicate sheets, but soon continues in all directions resulting in a 3D microstructure. Furthermore, nanocrystalline C-S-H structures with sizes between 5 nm to 10 nm were observed inside the amorphous or highly disordered C-S-H matrix, denoting that C-S-H growth is conformed to layered structure model. Crack formation and propagation inside C-S-H precipitates confirms the presence of increasing lattice strain due to growing defects that limits the growth of a fully crystalline structure by buckling and separating the sheets. The rolling up and crumbling of C-S-H sheets promotes the formation of new embryos, leading to the growth of precipitates in all direction and finally their coalescence.