Environmental 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.

In situ Tracking the Constrained Reconstruction of Cu3Pd@SiO2 Nanoparticles Driven by Redox Atmospheres

AbstractEndowed with flexible surface coordination and synergetic electronic status, bimetallic particles serve as promising heterogeneous catalysts as their microstructures evolved sensitively to the treatment atmospheres, whereas knowledge of dynamic manners is less. Herein, utilizing environmental transmission electron microscopy (ETEM), the reconstructions of Cu3Pd particles in oxidization/reduction atmospheres were explored at atomic scale. Specifically, bare Cu3Pd particles went through a phase separation of CuOx and PdOx during in situ oxidation, and subsequent agglomeration after H2 reduction. While protected in a silica shell, the confined Cu3Pd particles were oxidized into Cu1.5Pd0.5O2 phase after air calcination and subsequently restructured into versatile configurations during H2 reduction. Specifically, hollow Cu3Pd alloy architecture with Pd enriched layer near surface as reduced at 200 °C. Further rising 400 to 600 °C, it yielded disordered Cu3Pd alloys with slightly Pd atoms enrichment at outmost surface. The dynamical behaviors of single Cu1.5Pd0.5O2 particle during in situ reduction have been visualized in ETEM, wherein a series of deformation, elongation and rotation is involved during the hollow architecture firstly formation, and then vanished into a Cu3Pd solid solution nanoparticle. The tunable microstructures of Cu3Pd@SiO2 driven by redox atmospheres demonstrate efficient approach for precisely regulating the chemical environments of constrained bimetallic nanocatalysts.

The mechanism of room‐temperature oxidation of a HF‐etched Ti3C2TxMXene determined via environmental transmission electron microscopy and molecular dynamics

AbstractThe oxidation chemistry of two‐dimensional transition metal carbide MXenes has brought new research significance to their protection and application. However, the oxidation behavior and degradation mechanism of MXenes, in particular with time under oxygen conditions at room temperature, remain largely unexplored. Here, several experimental and theoretical techniques are used to determine a very early stage of the oxidation mechanism of HF‐etched Ti3C2Tx (a major member of MXenes and Tx = surface functional groups) in an oxygen environment at room temperature. Aberration‐corrected environmental transmission electron microscopy coupled with reactive molecular dynamics simulations show that the crystal plane‐dependent oxidation rate of Ti3C2Tx and oxide expansion are attributed to differences in the coordination and charge of superficial Ti atoms, and the existence of the channels between neighboring MXene layers on the different crystal planes. The complementary x‐ray photoelectron spectroscopy and Raman spectroscopy analyses indicate that the anatase and a tiny fraction of brookite TiO2 successively precipitate from the amorphous region of oxidized Ti3C2Tx, grow irregularly and transform to rutile TiO2. Our study reveals the early‐stage structural evolution of MXenes in the presence of oxygen and facilitates further tailoring of the MXene performance employing oxidation strategy.

Field emission characterization of field-aligned carbon nanotubes synthesized in an environmental transmission electron microscope

Optimizing the synthesis of carbon nanotubes (CNTs) for applications like field emission (FE) sources requires a fundamental understanding of the growth kinetics of individual CNTs. In this article, we explore how applying electric fields during CNT synthesis influences the as-grown nanotubes and their FE performance. We observe growth and undertake FE measurements in real time using an environmental transmission electron microscope. This is achieved through a polarizable capacitor gap within a microchip sample heater specifically designed for this purpose. Individual nanotubes are easily resolved and are predominantly single-wall CNTs. At low-applied fields, the growing nanotubes can span the gap and link with the opposite electrode, albeit with some loss due to mechanical failure. With a high-applied field and positive bias for FE, we continue to observe the oriented growth of nanotubes. However, this growth is constrained within the gap due to the possibility of FE occurring during the growth process, which can result in either saturation or damage. At any given time, we have the flexibility to halt the growth process and conduct in situ FE experiments. This approach enables us to comprehensively track the complete development of the CNTs and gain insights into the various mechanisms responsible for limiting the performance of CNT cathodes. Interestingly, we report an original self-oscillation induced destruction mechanism that has not been reported before.

Development of an integrated high-voltage electron microscope-gas chromatograph-quadrupole mass spectrometer system for the operando analysis of catalytic gas reactions.

This paper describes the development of a gas chromatography-quadrupole mass spectrometry system attached to a differential-pumping-type environmental cell of the reaction science high-voltage electron microscopy instrument at Nagoya University to distinguish unambiguously between different gas species with the same mass-to-charge ratio. Several model experiments were used to verify the efficacy of the newly proposed system, confirming its ability to analye the atomic-level structural changes during heterogeneous catalysts and the associated gas-reaction kinetics simultaneously, providing new insights into operando measurements in the field of environmental transmission electron microscopy.

Effect of CaCl2 on the micromorphology of a self-thickening agent (TZXJ) for acidizing diversion

The effect of CaCl2 on the micromorphology of a self-thickening agent (TZXJ) was investigated. This study involved analyzing the compositional changes in acid solutions during acid–rock reactions. It combined dynamic light scattering and viscosity testing to confirm that the presence of CaCl2 enhances the aggregation strength of the TZXJ network structure in acid solutions. This enhancement is macroscopically evident as an increase in viscosity. Incorporating 10 % CaCl2 as a promoter into a fresh acid solution, the hydrodynamic radius (Rh) distribution of TZXJ in varying reaction stages was analyzed using dynamic light scattering experiments. The results indicated that the promoter CaCl2 further strengthens the network association of the TZXJ acid solution, thereby improving its thickening capability. Investigating the viscosity of TZXJ aqueous solutions with varying concentrations of CaCl2 revealed that TZXJ exhibits notable salt-thickening effects and can withstand saturated CaCl2 solutions. The microstructural aggregation state and morphology of TZXJ in aqueous solutions were characterized at different CaCl2 concentrations. Dynamic light scattering results demonstrated an increase in the Rh of TZXJ solutions with CaCl2 concentrations. In particular, the mean Rh of a 0.8 % TZXJ solution increased from 150.8 nm to 3078.93 nm. Ultraviolet spectral analysis confirmed that the absorption intensity of the TZXJ solutions increased with CaCl2 concentration, indicating a strengthened network aggregate structure in the TZXJ solutions. Microscopic observations using environmental scanning electron microscopy and transmission electron microscopy revealed that under the influence of calcium chloride, the microstructure of TZXJ transitions from a non-associated, linear carbon chain skeleton to a dense, aggregated network structure. The findings of this study offer theoretical insights for researching polymers resistant to extreme concentrations of CaCl2.

In Situ Monitoring of Non-Thermal Plasma Cleaning of Surfactant Encapsulated Nanoparticles

Surfactants are widely used in the synthesis of nanoparticles, as they have a remarkable ability to direct their growth to obtain well-defined shapes and sizes. However, their post-synthesis removal is a challenge, and the methods used often result in morphological changes that defeat the purpose of the initial controlled growth. Moreover, after the removal of surfactants, the highly active surfaces of nanomaterials may undergo structural reconstruction by exposure to a different environment. Thus, ex situ characterization after air exposure may not reflect the effect of the cleaning methods. Here, combining X-ray photoelectron spectroscopy, in situ infrared reflection absorption spectroscopy, and environmental transmission electron microscopy measurements with CO probe experiments, we investigated different surfactant-removal methods to produce clean metallic Pt nanoparticles from surfactant-encapsulated ones. It was demonstrated that both ultraviolet-ozone (UV-ozone) treatment and room temperature O2 plasma treatment led to the formation of Pt oxides on the surface after the removal of the surfactant. On the other hand, when H2 was used for plasma treatment, both the Pt0 oxidation state and nanoparticle size distribution were preserved. In addition, H2 plasma treatment can reduce Pt oxides after O2-based treatments, resulting in metallic nanoparticles with clean surfaces. These findings provide a better understanding of the various options for surfactant removal from metal nanoparticles and point toward non-thermal plasmas as the best route if the integrity of the nanoparticle needs to be preserved.

Effect of the Ni/Co ratio on the structural and initial oxidation properties of NiCo-based superalloys revealed by in situ microscopy

Oxidation is one of the main failure modes of superalloys, and the initial oxidation of a superalloy provides clues for its failure analysis. NiCo-based superalloys exhibit superior mechanical properties, but their oxidation behaviour is still debatable, especially in terms of the ratio of Ni/Co. Here, we show the effect of the Ni/Co ratio on the initial oxidation behaviour at the nanoscale by in situ environmental transmission electron microscopy (ETEM), which provides the initial microstructural changes in the γ/γ′ structure-based alloy. The results indicate that Ni-rich alloys exhibit better structural stability at high temperatures than Ni-deficient alloys. A high content of Ni promotes the formation of a dense oxide layer, inhibits the oxidation rate, and improves the oxidation resistance. This result will help to elucidate the basic process of oxide formation in NiCo-based single-crystal superalloys and provide ideas for improving their oxidation resistance for alloy design.

Visualization of the structural transformation of NiO/YSZ/BZY nanocomposite particles using in situ gas environmental transmission electron microscopy.

This study focused on investigating the dynamic structural transformations of spherical NiO/YSZ/BZY triple-phase nanocomposite particles, commonly employed for cermet anodes, during the hydrogen reduction reaction. We utilized both spherical aberration (Cs) corrected transmission electron microscopy (TEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observation modes under a controlled gaseous environment. The environmental gas pressure was set to 1 atm (760 Torr), mirroring real-world conditions. To elucidate pre- and post-hydrogen reduction compositional alterations, we conducted elemental mapping using energy-dispersive X-ray spectroscopy (EDS). Our findings indicated that NiO nanoparticles underwent reduction to Ni particles upon heat treatments in an environment containing H2 gas. Significantly, this reduction of NiO led to the migration of Ni along the external surface of each composite particle, ultimately resulting in the agglomeration at the interparticle spaces among the three NiO/YSZ/BZY nanocomposite particles.

Atomic origin of CO2-promoted oxidation dynamics of chromia-forming alloys

The development of atomic imperfections within oxide films from high-temperature oxidation of heat-resistant alloys significantly limits the self-protectiveness of the surface oxide, contributing to the failure of energy generating system components such as turbines, engines, and heat exchanges. Directly probing the dynamics of such atomic defects is challenging because of the extreme thermochemical conditions of high-temperature oxidation. Using environmental transmission electron microscopy observations, here we directly capture atomic-scale dynamics of vacancies in growing Cr2O3 film during high-temperature oxidation of NiCr alloy in CO2. Coordinated with theory modeling, we delineate the atomistic mechanisms associated with the effect of interstitial carbon derived from CO2 on promoting the formation, migration and clustering of atomic vacancies to result in the enhanced alloy oxidation. The identified oxidation mechanism can find broader applicability in utilizing the atmosphere to tune the formation and evolution of atomic-scale defects, thereby affecting the mass transport properties of the growing oxide film.

Operando analysis of a solid oxide fuel cell by environmental transmission electron microscopy

Correlating the microstructure of an energy conversion device to its performance is often a complex exercise, notably in solid oxide fuel cell research. Solid oxide fuel cells combine multiple materials and interfaces that evolve in time due to high operating temperatures and reactive atmospheres. We demonstrate here that operando environmental transmission electron microscopy can identify structure-property links in such devices. By contacting a cathode-electrolyte-anode cell to a heating and biasing microelectromechanical system in a single-chamber configuration, a direct correlation is found between the environmental conditions (oxygen and hydrogen partial pressures, temperature), the cell open circuit voltage, and the microstructural evolution of the fuel cell, down to the atomic scale. The results shed important insights into the impact of the anode oxidation state and its morphology on the cell electrical properties.

Nanocarbon oxidation in the environmental transmission electron microscope - Disentangling the role of the electron beam

Environmental transmission electron microscopy (ETEM) can provide unique insights into nanocarbon oxidation processes through atomic resolution and real time imaging of materials at high temperatures in reactive atmospheres. However, the electron beam can also influence the reaction rates, and even alter the processes entirely, complicating the interpretation of the in situ observations. Many mechanisms have been proposed to account for the impact of the electron beam, predominantly involving ionization of the oxidative gases to form more reactive species. However, these mechanisms have not been critically evaluated and compared to predictions from theory. Here, we evaluate the impact of the electron beam both qualitatively (oxidation mode and spatial extent) and quantitatively (oxidation rates), using high resolution imaging and electron energy loss spectroscopy, at different electron energies and dose rates. We demonstrate that transient defects generated by elastic scattering, forming highly active sites for carbon abstraction by oxygen, is the main mechanism for the enhanced oxidation rates observed in situ. This is evident from an insensitivity to electron energy and saturation of the effects at high electron dose rates. To avoid undue influence of the electron beam in future ETEM studies, we therefore recommend conditions where the intrinsic oxidation dominates over the beam-enhanced oxidation (note that no conditions are completely “safe”) and extensive comparisons with other methods.

Controlled Growth of Pd Nanocrystals by Interface Interaction on Monolayer MoS2: An Atom-Resolved in Situ Study.

The crystal growth kinetics is crucial for the controllable preparation and performance modulation of metal nanocrystals (NCs). However, the study of growth mechanisms is significantly limited by characterization techniques, and it is still challenging to in situ capture the growth process. Real-time and real-space imaging techniques at the atomic scale can promote the understanding of microdynamics for NC growth. Herein, the growth of Pd NCs on monolayer MoS2 under different atmospheres was in situ studied by environmental transmission electron microscopy. Introducing carbon monoxide can modulate the diffusion of Pd monomers, resulting in the epitaxial growth of Pd NCs with a uniform orientation. The electron energy loss spectroscopy and theoretical calculations showed that the CO adsorption assured the specific exposed facets and good uniformity of Pd NCs. The insight into the gas-solid interface interaction and the microscopic growth mechanism of NCs may shed light on the precise synthesis of NCs on two-dimensional (2D) materials.

Environmental TEM Study of the Dispersion of Au/α-MoC: From Nanoparticles to Two-Dimensional Clusters.

The synthesis of highly dispersed Au nanoclusters that are stable under elevated temperatures in heterogeneous catalysis is challenging. Here, we directly observe a strong metal-support interaction (SMSI)-induced dispersion of Au nanoparticles (NPs) on α-MoC using an environmentally atomically resolved secondary imaging technique. Under a realistic environment, Au NPs flatten and spread out on the α-MoC to form two-dimensional atomic layered clusters. The formed highly dispersed Au/α-MoC catalyst shows excellent stability at 600 °C for 160 h in the reverse water-gas shift reaction. The X-ray photoelectron spectrum and extended X-ray absorption fine structure results show that Au NPs gradually become low-coordination-number cluster species and lose electrons to become Auδ+; these form chemical bonds with the α-MoC support and are responsible for the dispersion behavior. This work provides an insightful understanding of dispersion behavior and promotes the rational design and synthesis of reverse sintering catalysts.

Breaking the Axis-Symmetry of a Single-Wall Carbon Nanotube During Its Growth.

The asymmetrical growth of a single-wall carbon nanotube (SWCNT) by introducing a change of a local atomic structure, is usually inevitable and supposed to have a profound effect on the chirality control and property tailor. However, the breaking of the symmetry during SWCNT growth remains unexplored and its origins at the atomic-scale are elusive. Here, environmental transmission electron microscopy is used to capture the process of breaking the symmetry of a growing SWCNT from a sub-2-nm platinum catalyst nanoparticle in real-time, demonstrating that topological defects formed on the side of a SWCNT can serve as a buffer for stress release and inherently break its axis-symmetrical growth. Atomic-level details reveal the importance of the tube-catalyst interface and how the atom rearrangement of the solid-state platinum catalyst around the interface influences the final tubular structure. The active sites responsible for trapping carbon dimers and providing enough driving force for carbon incorporation and asymmetric growth are shown to be low-coordination step edges, as confirmed by theoretical simulations.

Correlating the fluctuated growth of carbon nanotubes with catalyst evolution by atmospheric-pressure environmental transmission electron microscopy

Correlating the fluctuated growth of carbon nanotubes with catalyst evolution by atmospheric-pressure environmental transmission electron microscopy

Reconstruction of Angstrom resolution exit-waves by the application of drift-corrected phase-shifting off-axis electron holography

Phase-shifting electron holography is an excellent method to reveal electron wave phase information with very high phase sensitivity over a large range of spatial frequencies. It circumvents the limiting trade-off between fringe spacing and visibility of standard off-axis holography. Previous implementations have been limited by the independent drift of biprism and sample. We demonstrate here an advanced drift correction scheme for the hologram series that exploits the presence of an interface of the TEM specimen to the vacuum area in the hologram. It allows to obtain reliable phase information up to 2π/452 at the 1 Å information limit of the Titan 80–300 kV environmental transmission electron microscope used, by applying a moderate voltage of 250 V to a single biprism for a fringe spacing of 1 Å. The obtained phase and amplitude information is validated at a thin Pt sample by use of multislice image simulation with the frozen lattice approximation and shows excellent agreement. The presented method is applicable in any TEM equipped with at least one electron biprism and thus enables achieving high resolution off-axis holography in various instruments including those for in-situ applications. A software implementation for the acquisition, calibration and reconstruction is provided.

In-situ investigation of the interaction between hydrogen and stacking faults in a bulk austenitic steel

The interaction between hydrogen (H) atoms and various microstructural defects remains a key to understand the H-induced damage and the subsequent premature failure of high-strength metallic materials. Previous studies on this subject are mainly focused on the in-situ probing of dislocations in a thin foil placed in an environmental transmission electron microscopy (TEM) cell. Here, a three-point bending test coupled with electron channeling contrast imaging (ECCI) has been applied to investigate the interaction of H with stacking faults (SFs) in a bulk high Mn austenitic steel. The expansion of some SFs, in terms of one partial dislocation movement within a partial dislocation pair, was observed on the H pre-charged sample when kept at a constant loading (i.e., a continuous H migration and likely build-up close to the pre-prepared notch tip). A temporal-resolved cross-correlation EBSD (CC-EBSD) measurement shows that the migration of H towards the notch tip region has a minor effect on the internal stress evolution. However, the local shear modulus (μ) and stacking fault energy (γSF) can be reduced by a local H segregation. Further theoretical calculation of SF ribbon width indicates that the reduction of μ by H results in the shrinkage of SF, while the H-induced reduction of γSF results in SF expansion at a lower resolved shear stress. The observed expansion of SF ribbons can be interrupted by a combined reduction of both μ and γSF due to H.

Understanding the Formation Mechanisms of Silicon Particles from the Thermal Disproportionation of Hydrogen Silsesquioxane.

Crystalline silicon particles sustaining Mie resonances are readily obtained from the thermal processing of hydrogen silsesquioxane (HSQ). Here, the mechanisms involved in silicon particle formation and growth from HSQ are investigated through real-time in situ analysis using an environmental transmission electron microscope and X-ray diffractometer. The nucleation of Si nanodomains is observed starting around 1000 °C. For the first time, a highly mobile intermediate phase is experimentally observed, thus demonstrating a previously unknown growth mechanism. At least two growth processes occur simultaneously: the coalescence of small particles into larger particles and growth mode by particle displacement through the matrix toward the HSQ grain surface. Postsynthetic characterization by scanning electron microscopy further supports the latter growth mechanism. The gaseous environment employed during synthesis impacts particle formation and growth under both in situ and ex situ conditions, impacting the particle yield and structural homogeneity. Understanding the formation mechanisms of particles provides promising pathways for reducing the energy cost of this synthetic route.