Chemical Interactions at the Interface of Au on BiSe Topological Insulator.

This study explores the intricate chemical processes at the interface between the topological insulator BiSe and deposited Au. The study mainly focused on room-temperature interactions that can cause the aging of, e.g.

Quasi-operando Transmission Electron Microscopy Diagnostics for Electrocatalytic Processes in Liquids.

The need to relate the mechano-physico-chemical phenomena in liquid-based electrocatalysts to the stages of start-up, operation, and shut-down phases is one of the major challenges that the energy community is facing. Understanding these phenomena will pave the way for the tailor-made design of efficient, commercially viable electrocatalytic systems. Transmission electron microscopy plays an important role in the investigation of local electrocatalytic effects, complementing other operando characterization techniques.

Graphene Electrode for Studying CO Electroreduction Nanocatalysts under Realistic Conditions in Microcells.

The ability to resolve the dynamic evolution of electrocatalytically induced processes with electrochemical liquid-phase electron microscopy (EM) is limited by the microcell configuration. Herein, a free-standing tri-layer graphene is integrated as a membrane and electrode material into the electrochemical chip and its suitability as a substrate electrode at the high cathodic potentials required for CO electroreduction (COER) is evaluated. The three-layer stacked graphene is transferred onto an in-house fabricated single-working electrode chip for use with bulk-like reference and counter electrodes to facilitate evaluation of its effectiveness.

Insights into Electrocatalyst Transformations Studied in Real Time with Electrochemical Liquid-Phase Transmission Electron Microscopy.

ConspectusThe value of operando and in situ characterization methodologies for understanding electrochemical systems under operation can be inferred from the upsurge of studies that have reported mechanistic insights into electrocatalytic processes based on such measurements. Despite the widespread availability of performing dynamic experiments nowadays, these techniques are in their infancy because the complexity of the experimental design and the collection and analysis of data remain challenging, effectively necessitating future developments. It is also due to their extensive use that a dedicated for acquiring dynamic electrocatalytic information is imperative.

Elucidating the Mechanism of Fe Incorporation in In Situ Synthesized Co-Fe Oxygen-Evolving Nanocatalysts.

Ni- and Co-based catalysts with added Fe demonstrate promising activity in the oxygen evolution reaction (OER) during alkaline water electrolysis, with the presence of Fe in a certain quantity being crucial for their enhanced performance. The mode of incorporation, local placement, and structure of Fe ions in the host catalyst, as well as their direct/indirect contribution to enhancing the OER activity, remain under active investigation. Herein, the mechanism of Fe incorporation into a Co-based host was investigated using an in situ synthesized Co-Fe catalyst in an alkaline electrolyte containing Co and Fe.

Three-dimensional nanoimaging of fuel cell catalyst layers.

Catalyst layers in proton exchange membrane fuel cells consist of platinum-group-metal nanocatalysts supported on carbon aggregates, forming a porous structure through which an ionomer network percolates. The local structural character of these heterogeneous assemblies is directly linked to the mass-transport resistances and subsequent cell performance losses; its three-dimensional visualization is therefore of interest. Herein we implement deep-learning-aided cryogenic transmission electron tomography for image restoration, and we quantitatively investigate the full morphology of various catalyst layers at the local-reaction-site scale.

Decoupling the Contributions of Different Instability Mechanisms to the PEMFC Performance Decay of Non-noble Metal O-Reduction Catalysts.

Non-noble metal catalysts (NNMCs) hold the potential to replace the expensive Pt-based materials currently used to speed up the oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC) cathodes, but they feature poor durability that inhibits their implementation in commercial PEMFCs. This performance decay is commonly ascribed to the operative demetallation of their ORR-active sites, the electro-oxidation of the carbonaceous matrix that hosts these active centers, and/or the chemical degradation of the ionomer, active sites, and/or carbon support by radicals derived from the HO produced as an ORR by-product. However, little is known regarding the relative contributions of these mechanisms to the overall PEMFC performance loss.

Decoding the Mechanisms of Phase Transitions from In Situ Microscopy Observations.

Analysis of the temperature- and stimulus-dependent imaging data toward elucidation of the physical transformations is an ubiquitous problem in multiple fields. Here, temperature-induced phase transition in BaTiO is explored using the machine learning analysis of domain morphologies visualized via variable-temperature scanning transmission electron microscopy (STEM) imaging data. This approach is based on the multivariate statistical analysis of the time or temperature dependence of the statistical descriptors of the system, derived in turn from the categorical classification of observed domain structures or projection on the continuous parameter space of the feature extraction-dimensionality reduction transform.

On the role of pore constrictions in gas diffusion electrodes.

Water management by gas diffusion electrodes is a fundamental aspect of the performance of electrochemical cells. Herein, we introduce the characteristic constrictions size as a descriptor for microporous layers (MPL). This parameter is calculated by volumetric analysis of focused ion beam nanotomography and compared to mercury intrusion porosimetry measurements.

Induced giant piezoelectricity in centrosymmetric oxides.

Piezoelectrics are materials that linearly deform in response to an applied electric field. As a fundamental prerequisite, piezoelectric materials must have a noncentrosymmetric crystal structure. For more than a century, this has remained a major obstacle for finding piezoelectric materials.

Switchable wetting of oxygen-evolving oxide catalysts.

The surface wettability of catalysts is typically controlled via surface treatments that promote catalytic performance. Here we report on potential-regulated hydrophobicity/hydrophilicity at cobalt-based oxide interfaces with an alkaline solution. The switchable wetting of single particles, directly related to their activity and stability towards the oxygen evolution reaction, was revealed by electrochemical liquid-phase transmission electron microscopy.

Phosphorene Nanoribbon-Augmented Optoelectronics for Enhanced Hole Extraction.

Phosphorene nanoribbons (PNRs) have been widely predicted to exhibit a range of superlative functional properties; however, because they have only recently been isolated, these properties are yet to be shown to translate to improved performance in any application. PNRs show particular promise for optoelectronics, given their predicted high exciton binding energies, tunable bandgaps, and ultrahigh hole mobilities. Here, we verify the theorized enhanced hole mobility in both solar cells and space-charge-limited-current devices, demonstrating the potential for PNRs improving hole extraction in universal optoelectronic applications.

Individual Barkhausen Pulses of Ferroelastic Nanodomains.

Ferroelectric materials, upon electric field biasing, display polarization discontinuities known as Barkhausen jumps, a subclass of a more general phenomenon known as crackling noise. Herein, we follow and visualize in real time the motion of single 90° needle domains induced by an electric field applied in the polarization direction of the prototypical ferroelectric BaTiO_{3}, inside a transmission electron microscope. The nature of motion and periodicity of the Barkhausen pulses leads to distinctive interactions between domains forming a herringbone pattern.

Challenges and Applications to and TEM Imaging and Spectroscopic Capabilities in a Cryogenic Temperature Range.

ConspectusIn this Account, we describe the challenges and promising applications of transmission electron microscopy (TEM) imaging and spectroscopy at cryogenic temperatures. Our work focuses on two areas of application: the delay of electron-beam-induced degradation and following low-temperature phenomena in a continuous and variable temperature range. For the former, we present a study of LiMnNiO lithium ion battery cathode material that undergoes electron beam-induced degradation when studied at room temperature by TEM.

A Method for Spatial Quantification of Water in Microporous Layers of Polymer Electrolyte Fuel Cells by X-ray Tomographic Microscopy.

A microporous layer (MPL) is typically added to the gas diffusion layer of polymer electrolyte fuel cells (PEFCs) to promote cell performance and water management. The transport mechanism of the water through the MPL is, however, not well understood due to its small pores (20-500 nm). Here, we demonstrate that polychromatic X-ray tomographic microscopy (XTM) can be used to determine the porosity and the spatial distribution of water in nanoporous materials and can quantitatively map the liquid water saturation of MPLs.

Real-time Monitoring Reveals Dissolution/Redeposition Mechanism in Copper Nanocatalysts during the Initial Stages of the CO Reduction Reaction.

Size, morphology, and surface sites of electrocatalysts have a major impact on their performance. Understanding how, when, and why these parameters change under operating conditions is of importance for designing stable, active, and selective catalysts. Herein, we study the reconstruction of a Cu-based nanocatalysts during the startup phase of the electrochemical CO reduction reaction by combining results from electrochemical in situ transmission electron microscopy with operando X-ray absorption spectroscopy.

Oxygen Evolution Reaction in BaSrCoFeO Aided by Intrinsic Co/Fe Spinel-Like Surface.

Among the perovskites used to catalyze the oxygen evolution reaction (OER), BaSrCoFeO (BSCF) exhibits excellent activity which is thought to be related to dynamic reconstruction at the flexible perovskite surface due to accommodation of large amount of oxygen vacancies. By studying the local structure and chemistry of BSCF surfaces, in detail, via a range of transmission electron microscopy (TEM) methods, we show that the surfaces of the as-synthesized BSCF particles are Co/Fe rich, and remarkably, adopt a spinel-like structure with a reduced valence of Co ions. Post-mortem and identical location TEM analyses reveal that the Co/Fe spinel-like surface retains a stable chemical environment of the Co/Fe ions, although its structure weakens after electrochemical processing.

Structured nanoscale metallic glass fibres with extreme aspect ratios.

Micro- and nanoscale metallic glasses offer exciting opportunities for both fundamental research and applications in healthcare, micro-engineering, optics and electronics. The scientific and technological challenges associated with the fabrication and utilization of nanoscale metallic glasses, however, remain unresolved. Here, we present a simple and scalable approach for the fabrication of metallic glass fibres with nanoscale architectures based on their thermal co-drawing within a polymer matrix with matched rheological properties.

The emergence of magnetic ordering at complex oxide interfaces tuned by defects.

Complex oxides show extreme sensitivity to structural distortions and defects, and the intricate balance of competing interactions which emerge at atomically defined interfaces may give rise to unexpected physics. In the interfaces of non-magnetic complex oxides, one of the most intriguing properties is the emergence of magnetism which is sensitive to chemical defects. Particularly, it is unclear which defects are responsible for the emergent magnetic interfaces.

Multi-modal and multi-scale non-local means method to analyze spectroscopic datasets.

A multi-modal and multi-scale non-local means (M3S-NLM) method is proposed to extract atomically resolved spectroscopic maps from low signal-to-noise (SNR) datasets recorded with a transmission electron microscope. This method improves upon previously tested denoising techniques as it takes into account the correlation between the dark-field signal recorded simultaneously with the spectroscopic dataset without compromising on the spatial resolution. The M3S-NLM method was applied to electron energy dispersive X-ray and electron-energy-loss spectroscopy (EELS) datasets.

Electrochemical Behavior of Carbon Electrodes for Redox Studies in a Transmission Electron Microscope.

Electrochemical liquid cell transmission electron microscopy (TEM) is a unique technique for probing nanocatalyst behavior during operation for a range of different electrocatalytic processes, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), or electrochemical CO2 reduction (eCO2R). A major challenge to the technique's applicability to these systems has to do with the choice of substrate, which requires a wide inert potential range for quantitative electrochemistry, and is also responsible for minimizing background gas generation in the confined microscale environment. Here, we report on the feasibility of electrochemical experiments using the standard redox couple Fe(CN)63-/4- and microchips featuring carbon-coated electrodes.

Production of phosphorene nanoribbons.

Phosphorene is a mono-elemental, two-dimensional (2D) substance with outstanding, highly directional properties and a bandgap that depends on the number of layers of the material. Nanoribbons, meanwhile, combine the flexibility and unidirectional properties of one-dimensional nanomaterials, the high surface area of 2D nanomaterials and the electron-confinement and edge effects of both. The structures of nanoribbons can thus lead to exceptional control over electronic band structure, the emergence of novel phenomena and unique architectures for applications.

Single Crystal, Luminescent Carbon Nitride Nanosheets Formed by Spontaneous Dissolution.

A primary method for the production of 2D nanosheets is liquid-phase delamination from their 3D layered bulk analogues. Most strategies currently achieve this objective by significant mechanical energy input or chemical modification but these processes are detrimental to the structure and properties of the resulting 2D nanomaterials. Bulk poly(triazine imide) (PTI)-based carbon nitrides are layered materials with a high degree of crystalline order.

Geometrical Effect in 2D Nanopores.

A long-standing problem in the application of solid-state nanopores is the lack of the precise control over the geometry of artificially formed pores compared to the well-defined geometry in their biological counterpart, that is, protein nanopores. To date, experimentally investigated solid-state nanopores have been shown to adopt an approximately circular shape. In this Letter, we investigate the geometrical effect of the nanopore shape on ionic blockage induced by DNA translocation using triangular h-BN nanopores and approximately circular molybdenum disulfide (MoS) nanopores.

Ionic solutions of two-dimensional materials.

Strategies for forming liquid dispersions of nanomaterials typically focus on retarding reaggregation, for example via surface modification, as opposed to promoting the thermodynamically driven dissolution common for molecule-sized species. Here we demonstrate the true dissolution of a wide range of important 2D nanomaterials by forming layered material salts that spontaneously dissolve in polar solvents yielding ionic solutions. The benign dissolution advantageously maintains the morphology of the starting material, is stable against reaggregation and can achieve solutions containing exclusively individualized monolayers.