Environmental Scanning Transmission Electron Microscopy Research Articles

Multimodal Insights of Regeneration Dynamics of Spent Bimetallic Catalysts by Full Field Hyperspectral Quick‐EXAFS Imaging and Environmental Transmission Electron Microscopy

Multimodal measurements involving time‐resolved Ni and Cu K edges Quick‐EXAFS, time‐resolved hyperspectral Full Field quick‐EXAFS imaging with micrometer spatial resolution and aberration‐corrected Environmental Scanning Transmission Electron Microscopy have been performed over a NiCu catalyst used for the ethanol steam reforming reaction to establish structure‐activity relationships after regeneration. Activated catalysts are composed of 5‐10 nm monometallic nickel nanoparticles and 20 nm or larger bimetallic randomly alloyed NiCu nanoparticles. After 3h time on reactive stream, the monitoring of the regeneration of the coked deactivated catalyst at 500°C by Full Field hyperspectral XAS imaging evidences that the oxidative propagation front affects faster metallic Ni species than metallic Cu ones. This is ascribed to the presence of both NPs populations and to a restructuration of the alloyed bimetallic particles from a homogeneous solid solution towards a Ni‐rich shell upon oxygen adsorption. Furthermore, ESTEM characterization of the deactivated catalyst when passing from H2 to O2 atmosphere at 500°C for burning coke deposits evidences the fragmentation of the Ni and NiCu‐NPs driven by the Kirkendall effect in the encapsulated coked catalyst. The resulting increase of specific surface of active species is assumed to be responsible for the activity boost observed after regeneration.

In Situ Scanning Transmission Electron Microscopy Calcination of Palladium Nitrate Supported on Zinc Oxide

Metallic nanoparticles are essential materials in various applications, such as nanomedicine, nanotechnology, and catalysis. While it is known that their catalytic performance is determined by their microstructure and thus by their preparation, the influence of an important but commonly used calcination treatment during nanoparticle preparation on their properties is often overlooked. Herein, structural and morphological changes during the calcination of Pd(NO3)2/ZnO are studied systematically by performing in situ heating experiments mimicking typical preparation conditions, by employing environmental scanning transmission electron microscopy. The effect of different calcination parameters on Pd(NO3)2/ZnO is explored and guidance to enhance control over the preparation of small supported nanoparticles is provided. It is shown that a calcination treatment of Pd(NO3)2/ZnO between 200 and 400 °C for 15–120 min is ideally suited to obtain particles smaller than 4 nm with a narrow size distribution.

Electron Beam Induced Enhancement and Suppression of Oxidation in Cu Nanoparticles in Environmental Scanning Transmission Electron Microscopy.

We have investigated the effects of high-energy electron irradiation on the oxidation of copper nanoparticles in environmental scanning transmission electron microscopy (ESTEM). The hemispherically shaped particles were oxidized in 3 mbar of O2 in a temperature range 100-200 °C. The evolution of the particles was recorded with sub-nanometer spatial resolution in situ in ESTEM. The oxidation encompasses the formation of outer and inner oxide shells on the nanoparticles, arising from the concurrent diffusion of copper and oxygen out of and into the nanoparticles, respectively. Our results reveal that the electron beam actively influences the reaction and overall accelerates the oxidation of the nanoparticles when compared to particles oxidized without exposure to the electron beam. However, the extent of this electron beam-assisted acceleration of oxidation diminishes at higher temperatures. Moreover, we observe that while oxidation through the outward diffusion of Cu+ cations is enhanced, the electron beam appears to hinder oxidation through the inward diffusion of O2- anions. Our results suggest that the impact of the high-energy electrons in ESTEM oxidation of Cu nanoparticles is mostly related to kinetic energy transfer, charging, and ionization of the gas environment, and the beam can both enhance and suppress reaction rates.

Environmental STEM Study of the Oxidation Mechanism for Iron and Iron Carbide Nanoparticles.

The oxidation of solution-synthesized iron (Fe) and iron carbide (Fe2C) nanoparticles was studied in an environmental scanning transmission electron microscope (ESTEM) at elevated temperatures under oxygen gas. The nanoparticles studied had a native oxide shell present, that formed after synthesis, an ~3 nm iron oxide (FexOy) shell for the Fe nanoparticles and ~2 nm for the Fe2C nanoparticles, with small void areas seen in several places between the core and shell for the Fe and an ~0.8 nm space between the core and shell for the Fe2C. The iron nanoparticles oxidized asymmetrically, with voids on the borders between the Fe core and FexOy shell increasing in size until the void coalesced, and finally the Fe core disappeared. In comparison, the oxidation of the Fe2C progressed symmetrically, with the core shrinking in the center and the outer oxide shell growing until the iron carbide had fully disappeared. Small bridges of iron oxide formed during oxidation, indicating that the Fe transitioned to the oxide shell surface across the channels, while leaving the carbon behind in the hollow core. The carbon in the carbide is hypothesized to suppress the formation of larger crystallites of iron oxide during oxidation, and alter the diffusion rates of the Fe and O during the reaction, which explains the lower sensitivity to oxidation of the Fe2C nanoparticles.

Tracking the redox reaction-induced reconstruction of NiAu nanoparticles via environmental scanning transmission electron microscopy.

Atmosphere-related atom migration and phase reconstruction are an easy way for optimizing the catalytic activity of a bimetallic catalyst. Herein, the structure evolutions of NiAu nanoparticles under oxidative and reductive environments are investigated via combining identical location and in situ environmental scanning transmission electron microscopy. During oxidation, a NiO layer first forms and the redispersion of Ni and Au atoms yields a Ni@Au@NiO multi-shell structure at 350 °C. Further, Ni and Au segregate into an Au-NiO hybrid structure at 600 °C. During reduction, Au atoms disperse over the particle surface forming a NiAu alloy shell with scattered Au atoms/clusters. In situ observation further discloses that the reduction changes the local structural ordering from Ni3Au to NiAu alloy. Very interestingly, the reduced NiAu exhibits promoted activity over oxidized ones for the CO-NO reaction. Density functional theory calculations further reveal the structure-property relationships of CO, NO, and O adsorbates on NiAu alloy surfaces. This study is beneficial for understanding the atmosphere-related evolution behaviors of bimetallic systems, thereby inspiring the catalytic surface optimization.

Competing oxidation mechanisms in Cu nanoparticles and their plasmonic signatures.

Chemical reactions involving nanoparticles often follow complex processes. In this respect, real-time probing of single nanoparticles under reactive conditions is crucial for uncovering the mechanisms driving the reaction pathway. Here, we have captured in situ the oxidation of single Cu nanoparticles to unravel a sequential competitive activation of different mechanisms at temperatures 50-200 °C. Using environmental scanning transmission electron microscopy, we monitor the evolution of oxide formation with sub-nanometre spatial resolution, and show how the prevalence of oxide island nucleation, Cabrera-Mott, Valensi-Carter and Kirkendall mechanisms under different conditions determines the morphology of the particles. Moreover, using in situ electron energy-loss spectroscopy, we probe the localised surface plasmons of individual particles during oxidation, and with the aid of finite-difference time-domain electrodynamic simulations investigate the signature of each mechanism in their plasmonic response. Our results shed light on the rich and intricate processes involved in the oxidation of nanoparticles, and provide in-depth insight into how these processes govern their morphology and optical response, beneficial for applications in catalysis, sensing, nanomedicine and plasmonics.

Heterogeneous oxidation of powder and individual carbon nanoparticles catalyzed by ceria nanoparticles

To comply with stricter regulations on particulate emissions, ceria based catalyst has been researched in developing diesel particulate filters. Here chemical reaction parameters are determined experimentally for CeO2-nanoparticle catalyzed soot oxidation for two representative environments: a bulk process with a catalyst/carbon mixture and individual carbon-nanoparticles attached to CeO2. The first task was carried out in simultaneous thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) experiments, while the second was performed with in-situ environmental scanning transmission electron microscopy (ESTEM). The TGA/DSC results suggested the role of gas diffusion through the porous sample was significant and slowed down the reaction rate. The ESTEM videos affirmed the catalyzed reaction resulted in a higher oxidation rate at the contact area between CeO2 and carbon, which caused the movement of carbon nanoparticles towards CeO2. Measured reaction kinetics data were compared to the Darcy’s model and their discrepancies were elaborated.

Antifungal Activity of Polyoxometalate-Ionic Liquids on Historical Brick.

Moulds inhabiting mineral-based materials may cause their biodeterioration, contributing to inestimable losses, especially in the case of cultural heritage objects and architectures. Fungi in mouldy buildings may also pose a threat to human health and constitute the main etiological factor in building related illnesses. In this context, research into novel compounds with antifungal activity is of high importance. The aim of this study was to evaluate the antifungal activity of polyoxometalate-ionic liquids (POM-ILs) and their use in the eradication of moulds from historical brick. In the disc diffusion assay, all the tested POM-ILs inhibited growth of a mixed culture of moulds including Engyodontium album, Cladosporium cladosporioides, Alternaria alternata and Aspergillus fumigatus. These were isolated from the surfaces of historical brick barracks at the Auschwitz II-Birkenau State Museum in Oświęcim, Poland. POM-IL coatings on historical brick samples, under model conditions, showed that two compounds demonstrated very high antifungal activity, completely limiting mould growth and development. The antifungal activity of the POM-ILs appeared to stem from their toxic effects on conidia, as evidenced by environmental scanning transmission electron microscopy observations. The results herein indicated that POM-ILs are promising disinfectant materials for use not only on historical objects, but probably also on other mineral-based materials.

Visualizing single atom dynamics in heterogeneous catalysis using analytical in situ environmental scanning transmission electron microscopy.

Progress is reported in analytical in situ environmental scanning transmission electron microscopy (ESTEM) for visualizing and analysing in real-time dynamic gas-solid catalyst reactions at the single-atom level under controlled reaction conditions of gas environment and temperature. The recent development of the ESTEM advances the capability of the established ETEM with the detection of fundamental single atoms, and the associated atomic structure of selected solid-state heterogeneous catalysts, in catalytic reactions in their working state. The new data provide improved understanding of dynamic atomic processes and reaction mechanisms, in activity and deactivation, at the fundamental level; and in the chemistry underpinning important technological processes. The benefits of atomic resolution-E(S)TEM to science and technology include new knowledge leading to improved technological processes, reductions in energy requirements and better management of environmental waste. This article is part of a discussion meeting issue 'Dynamic in situ microscopy relating structure and function'.

Atom-by-atom analysis of sintering dynamics and stability of Pt nanoparticle catalysts in chemical reactions.

Supported Pt nanoparticles are used extensively in chemical processes, including for fuel cells, fuels, pollution control and hydrogenation reactions. Atomic-level deactivation mechanisms play a critical role in the loss of performance. In this original research paper, we introduce real-time in-situ visualization and quantitative analysis of dynamic atom-by-atom sintering and stability of model Pt nanoparticles on a carbon support, under controlled chemical reaction conditions of temperature and continuously flowing gas. We use a novel environmental scanning transmission electron microscope with single-atom resolution, to understand the mechanisms. Our results track the areal density of dynamic single atoms on the support between nanoparticles and attached to them; both as migrating species in performance degradation and as potential new independent active species. We demonstrate that the decay of smaller nanoparticles is initiated by a local lack of single atoms; while a post decay increase in single-atom density suggests anchoring sites on the substrate before aggregation to larger particles. The analyses reveal a relationship between the density and mobility of single atoms, particle sizes and their nature in the immediate neighbourhood. The results are combined with practical catalysts important in technological processes. The findings illustrate the complex nature of sintering and deactivation. They are used to generate new fundamental insights into nanoparticle sintering dynamics at the single-atom level, important in the development of efficient supported nanoparticle systems for improved chemical processes and novel single-atom catalysis.This article is part of a discussion meeting issue ‘Dynamic in situ microscopy relating structure and function’.

In Situ Tracking of Colloidally Stable and Ordered Assemblies of Gold Nanorods

Solution-phase self-assembly of anisotropic nanoparticles into complex 2D and 3D assemblies is one of the most promising strategies toward obtaining nanoparticle-based materials and devices with unique optical properties at the macroscale. However, controlling this process with single-particle precision is highly demanding, mostly due to insufficient understanding of the self-assembly process at the nanoscale. We report the use of in situ environmental scanning transmission electron microscopy (WetSTEM), combined with UV/vis spectroscopy, small-angle X-ray diffraction (SAXRD) and multiscale modeling, to draw a detailed picture of the dynamics of vertically aligned assemblies of gold nanorods. Detailed understanding of the self-assembly/disassembly mechanisms is obtained from real-time observations, which provide direct evidence of the colloidal stability of side-to-side nanorod clusters. Structural details and the forces governing the disassembly process are revealed with single particle resolution as well as in bulk samples, by combined experimental and theoretical modeling. In particular, this study provides unique information on the evolution of the orientational order of nanorods within side-to-side 2D assemblies and shows that both electrostatic (at the nanoscale) and thermal (in bulk) stimuli can be used to drive the process. These results not only give insight into the interactions between nanorods and the stability of their assemblies, thereby assisting the design of ordered, anisotropic nanomaterials but also broaden the available toolbox for in situ tracking of nanoparticle behavior at the single-particle level.

Site Dependent Oxidation and Reduction Mechanisms in Nanoparticles Investigated via Environmental Scanning Transmission Electron Microscopy

Site Dependent Oxidation and Reduction Mechanisms in Nanoparticles Investigated via Environmental Scanning Transmission Electron Microscopy

Site-selective CO disproportionation mediated by localized surface plasmon resonance excited by electron beam.

Recent reports of hot-electron-induced dissociation of small molecules, such as hydrogen, demonstrate the potential application of plasmonic nanostructures for harvesting light to initiate catalytic reactions. Theories have assumed that plasmonic catalysis is mediated by the energy transfer from nanoparticles to adsorbed molecules during the dephasing of localized surface plasmon (LSP) modes optically excited on plasmonic nanoparticles. However, LSP-induced chemical processes have not been resolved at a sub-nanoparticle scale to identify the active sites responsible for the energy transfer. Here, we exploit the LSP resonance excited by electron beam on gold nanoparticles to drive CO disproportionation at room temperature in an environmental scanning transmission electron microscope. Using in situ electron energy-loss spectroscopy with a combination of density functional theory and electromagnetic boundary element method calculations, we show at the subparticle level that the active sites on gold nanoparticles are where preferred gas adsorption sites and the locations of maximum LSP electric field amplitude (resonance antinodes) superimpose. Our findings provide insight into plasmonic catalysis and will be valuable in designing plasmonic antennas for low-temperature catalytic processes.

Catalytic Etching of Multi‐Walled Carbon Nanotubes Controlled by Oxygen Gas Pressure

AbstractWe examined the catalytic behavior of platinum nanoparticles supported directly on a multi‐walled carbon nanotube with environmental scanning transmission electron microscopy. The catalytic etching behavior of the platinum nanoparticles toward the carbon nanotube was found to depend on the oxygen gas pressure. We supposed that direction of catalytic etching could be involved with amount of adsorbed oxygen onto catalytic nanoparticles. In situ observations give new insight of morphological control of carbon nanotube etched by catalytic nanoparticles.

In Situ Scanning Transmission Electron Microscopy of Ni Nanoparticle Redispersion via the Reduction of Hollow NiO

Oxidation and reduction cycles are used in the regeneration of nanoparticle catalysts that have deactivated due to sintering or poisoning. Nickel oxidation and reduction cycles for the redispersion of nickel nanoparticles were studied via in situ high angle annular dark field environmental scanning transmission electron microscopy. Cycling the Ni/NiO system through successive redox cycles shows that the particles retain the same general size distributions even though Ostwald ripening and particle migration and coalescence is occurring. The regeneration of the smallest nanoparticle sizes, which disappear due to sintering processes, occur by the ejection of small (2–3 nm) nickel particles during the reduction of the hollow nickel oxide nanostructures. The nickel nanoparticles above ∼3.5 nm in size form hollow polycrystalline nickel oxide nanostructures upon oxidation. Upon reduction, the grains making up the shell of the hollow nickel oxide reduce separately at the grains surface and at the grain boundaries...

Direct visualization of hydrogen absorption dynamics in individual palladium nanoparticles

Many energy storage materials undergo large volume changes during charging and discharging. The resulting stresses often lead to defect formation in the bulk, but less so in nanosized systems. Here, we capture in real time the mechanism of one such transformation—the hydrogenation of single-crystalline palladium nanocubes from 15 to 80 nm—to better understand the reason for this durability. First, using environmental scanning transmission electron microscopy, we monitor the hydrogen absorption process in real time with 3 nm resolution. Then, using dark-field imaging, we structurally examine the reaction intermediates with 1 nm resolution. The reaction proceeds through nucleation and growth of the new phase in corners of the nanocubes. As the hydrogenated phase propagates across the particles, portions of the lattice misorient by 1.5%, diminishing crystal quality. Once transformed, all the particles explored return to a pristine state. The nanoparticles’ ability to remove crystallographic imperfections renders them more durable than their bulk counterparts.

Visualizing the Cu/Cu2(O) Interface Transition in Nanoparticles with Environmental Scanning Transmission Electron Microscopy.

Understanding the oxidation and reduction mechanisms of catalytically active transition metal nanoparticles is important to improve their application in a variety of chemical processes. In nanocatalysis the nanoparticles can undergo oxidation or reduction in situ, and thus the redox species are not what are observed before and after reactions. We have used the novel environmental scanning transmission electron microscope (ESTEM) with 0.1 nm resolution in systematic studies of complex dynamic oxidation and reduction mechanisms of copper nanoparticles. The oxidation of copper has previously been reported to be dependent on its crystallography and its interaction with the substrate. By following the dynamic oxidation process in situ in real time with high-angle annular dark-field imaging in the ESTEM, we use conditions ideal to track the oxidation front as it progresses across a copper nanoparticle by following the changes in the atomic number (Z) contrast with time. The oxidation occurs via the nucleation of the oxide phase (Cu2O) from one area of the nanoparticle which then progresses unidirectionally across the particle, with the Cu-to-Cu2O interface having a relationship of Cu{111}//Cu2O{111}. The oxidation kinetics are related to the temperature and oxygen pressure. When the process is reversed in hydrogen, the reduction process is observed to be similar to the oxidation, with the same crystallographic relationship between the two phases. The dynamic observations provide unique insights into redox mechanisms which are important to understanding and controlling the oxidation and reduction of copper-based nanoparticles.

Magnetic nanoparticle containing thiol‐ene crosslinked hydrogels for controlled and targeted release of hydrophobic drugs

This study reports a straightforward but very effective method to produce nanocomposite hydrogels for targeted drug delivery system. An organic network containing both hydrophilic and hydrophobic components was obtained using thiol‐ene cross‐linking. Magnetite nanoparticles (MNPs) were synthesized by chemical co‐precipitation. The surface of the MNPs was modified with allyl groups to avoid agglomeration. Composite hydrogels were prepared by addition of surface modified MNPs to hydrogel formulation at different ratios. The prepared composite hydrogels were investigated for their ability to loading and release hydrophobic drugs tamoxifen and clarithromycin. The morphological and structural characterizations of MNPs were performed by Fourier transform infrared spectroscopy (FT‐IR) and Environmental scanning electron microscopy (SEM) and Environmental scanning transmission electron microscopy (STEM). Moreover the superparamagnetic behavior of the hydrogels was studied by a vibrating sample magnetometer (VSM). The saturation magnetization values increased with the magnetite content. Swelling, gel content and degradation of the hydrogels were examined. According to the loading of drugs, the maximum loading efficiency was 91% for tamoxifen and 70% for clarithromycin due to the stronger hydrophobic interactions. In vitro release studies showed that controlled release of the drugs occurred over a prolonged period of time. Therefore, drug loaded hydrogels can be considered as potential long‐term sustained drug release systems. POLYM. COMPOS., 39:E200–E209, 2018. © 2016 Society of Plastics Engineers

The Effect of Electron Beam Irradiation in Environmental Scanning Transmission Electron Microscopy of Whole Cells in Liquid

Whole cells can be studied in their native liquid environment using electron microscopy, and unique information about the locations and stoichiometry of individual membrane proteins can be obtained from many cells thus taking cell heterogeneity into account. Of key importance for the further development of this microscopy technology is knowledge about the effect of electron beam radiation on the samples under investigation. We used environmental scanning electron microscopy (ESEM) with scanning transmission electron microscopy (STEM) detection to examine the effect of radiation for whole fixed COS7 fibroblasts in liquid. The main observation was the localization of nanoparticle labels attached to epidermal growth factor receptors (EGFRs). It was found that the relative distances between the labels remained mostly unchanged (<1.5%) for electron doses ranging from the undamaged native state at 10 e-/Å2 toward 103 e-/Å2. This dose range was sufficient to determine the EGFR locations with nanometer resolution and to distinguish between monomers and dimers. Various different forms of radiation damage became visible at higher doses, including severe dislocation, and the dissolution of labels.

Back Cover: Dynamic Imaging of Ostwald Ripening by Environmental Scanning Transmission Electron Microscopy (ChemCatChem 22/2015)

Back Cover: Dynamic Imaging of Ostwald Ripening by Environmental Scanning Transmission Electron Microscopy (ChemCatChem 22/2015)