Role of Interfacial Hydrogen in Ethylene Hydrogenation on Graphite-Supported Ag, Au, and Cu Catalysts.

A combined surface science/microreactor approach was applied to examine interface effects in ethylene hydrogenation on carbon-supported Ag, Au, and Cu nanoparticle catalysts. Turnover frequencies (TOFs) were substantially higher for supported catalysts than for (unsupported) polycrystalline metal foils, especially for Ag. Spark ablation of the corresponding metals on highly oriented pyrolytic graphite (HOPG) and carbon-coated grids yielded nanoparticles of around 3 nm size that were well-suited for characterization by X-ray photoelectron spectroscopy (XPS), high-resolution (scanning) transmission electron microscopy (HRTEM/STEM), and energy dispersive X-ray spectroscopy (EDX).

Biomimetic Cooling: Functionalizing Biodegradable Chitosan Films with Saharan Silver Ant Microstructures.

The increasing occurrence of hot summer days causes stress to both humans and animals, particularly in urban areas where temperatures can remain high, even at night. Living nature offers potential solutions that require minimal energy and material costs. For instance, the Saharan silver ant () can endure the desert heat by means of passive radiative cooling induced by its triangular hairs.

Electro-tuned catalysts: voltage-controlled activity selection of bimetallic exsolution particles.

In this work, we show how the activity states of bimetallic Ni-Fe catalysts exsolved from NdCaFeNiO (NCFNi) can be influenced electrochemically. The NCFNi parent oxide was employed in the form of thin film mixed conducting model electrodes, which were operated in a humid hydrogen atmosphere. By precisely controlling the oxygen chemical potential in the parent oxide electrode applying an electrochemical polarisation, we managed to selectively exsolve Ni nanoparticles from the perovskite lattice and study their catalytic activity switching characteristics.

Current opinion on the prospect of mapping electronic orbitals in the transmission electron microscope: State of the art, challenges and perspectives.

The concept of electronic orbitals has enabled the understanding of a wide range of physical and chemical properties of solids through the definition of, for example, chemical bonding between atoms. In the transmission electron microscope, which is one of the most used and powerful analytical tools for high-spatial-resolution analysis of solids, the accessible quantity is the local distribution of electronic states. However, the interpretation of electronic state maps at atomic resolution in terms of electronic orbitals is far from obvious, not always possible, and often remains a major hurdle preventing a better understanding of the properties of the system of interest.

Optimizing experimental parameters for orbital mapping.

A new material characterization technique is emerging for the transmission electron microscope (TEM). Using electron energy-loss spectroscopy, real space mappings of the underlying electronic transitions in the sample, so called orbital maps, can be produced. Thus, unprecedented insight into the electronic orbitals responsible for most of the electrical, magnetic and optical properties of bulk materials can be gained.

Urethane functions can reduce metal salts under hydrothermal conditions: synthesis of noble metal nanoparticles on flexible sponges applied in semi-automated organic reduction.

We report an additive-free one-pot hydrothermal synthesis of Au, Ag, Pd, and alloy AuPd nanoparticles (NPs) anchored on commercial polyurethane (PU) foams. While unable to reduce the precursor metal salts at room temperature, PU is able to serve as a reducing agent under hydrothermal conditions. The resulting NP@PU sponge materials perform comparably to reported state-of-the-art reduction catalysts, and are additionally very well suited for use in semi-automated synthesis: the NP anchoring is strong enough and the support flexible enough to be used as a 'catalytic sponge' that can be manipulated with a robotic arm, , be repeatedly dipped into and drawn out of solutions, wrung out, and re-soaked.

Se Nanopowder Conversion into Lubricious 2D Selenide Layers by Tribochemical Reactions.

Transition metal dichalcogenide (TMD) coatings have attracted enormous scientific and industrial interest due to their outstanding tribological behavior. The paradigmatic example is MoS , even though selenides and tellurides have demonstrated superior tribological properties. Here, an innovative in operando conversion of Se nanopowders into lubricious 2D selenides, by sprinkling them onto sliding metallic surfaces coated with Mo and W thin films, is described.

l-Ascorbic Acid Treatment of Electrochemical Graphene Nanosheets: Reduction Optimization and Application for De-Icing, Water Uptake Prevention, and Corrosion Resistance.

The aeronautical industry demands facile lightweight and low-cost solutions to address climate crisis challenges. Graphene can be a valid candidate to tackle these functionalities, although its upscalability remains difficult to achieve. Consequently, graphene-related materials (GRM) are gathering massive attention as top-down graphite exfoliation processes at the industrial scale are feasible and often employed.

Autolysis Affects the Iron Cargo of Ferritins in Neurons and Glial Cells at Different Rates in the Human Brain.

Iron is known to accumulate in neurological disorders, so a careful balance of the iron concentration is essential for healthy brain functioning. An imbalance in iron homeostasis could arise due to the dysfunction of proteins involved in iron homeostasis. Here, we focus on ferritin-the primary iron storage protein of the brain.

Discrimination of coherent and incoherent cathodoluminescence using temporal photon correlations.

We present a method to separate coherent and incoherent contributions of cathodoluminescence (CL) by using a time-resolved coincidence detection scheme. For a proof-of-concept experiment, we generate CL by irradiating an optical multimode fiber with relativistic electrons in a transmission electron microscope. A temporal analysis of the CL reveals a large peak in coincidence counts for small time delays, also known as photon bunching.

Who Does the Job? How Copper Can Replace Noble Metals in Sustainable Catalysis by the Formation of Copper-Mixed Oxide Interfaces.

Following the need for an innovative catalyst and material design in catalysis, we provide a comparative approach using pure and Pd-doped LaCu Mn O ( = 0.3 and 0.5) perovskite catalysts to elucidate the beneficial role of the Cu/perovskite and the promoting effect of Cu Pd /perovskite interfaces developing under model NO + CO reaction conditions.

Image difference metrics for high-resolution electron microscopy.

Digital image comparison and matching brings many advantages over the traditional subjective human comparison, including speed and reproducibility. Despite the existence of an abundance of image difference metrics, most of them are not suited for high-resolution transmission electron microscopy (HRTEM) images. In this work we adopt two image difference metrics not widely used for TEM images.

Surface Anchoring and Active Sites of [MoS] Clusters as Co-Catalysts for Photocatalytic Hydrogen Evolution.

Achieving light-driven splitting of water with high efficiency remains a challenging task on the way to solar fuel exploration. In this work, to combine the advantages of heterogeneous and homogeneous photosystems, we covalently anchor noble-metal- and carbon-free thiomolybdate [MoS] clusters onto photoactive metal oxide supports to act as molecular co-catalysts for photocatalytic water splitting. We demonstrate that strong and surface-limited binding of the [MoS] to the oxide surfaces takes place.

Imaging the Spatial Distribution of Electronic States in Graphene Using Electron Energy-Loss Spectroscopy: Prospect of Orbital Mapping.

The spatial distributions of antibonding π^{*} and σ^{*} states in epitaxial graphene multilayers are mapped using electron energy-loss spectroscopy in a scanning transmission electron microscope. Inelastic channeling simulations validate the interpretation of the spatially resolved signals in terms of electronic orbitals, and demonstrate the crucial effect of the material thickness on the experimental capability to resolve the distribution of unoccupied states. This work illustrates the current potential of core-level electron energy-loss spectroscopy towards the direct visualization of electronic orbitals in a wide range of materials, of huge interest to better understand chemical bonding among many other properties at interfaces and defects in solids.

A method for a column-by-column EELS quantification of barium lanthanum ferrate.

High-resolution STEM-EELS provides information about the composition of crystalline materials at the atomic scale, though a reliable quantitative chemical analysis is often hampered by zone axis conditions, where neighbouring atomic column intensities contribute to the signal at the probe position. In this work, we present a procedure to determine the concentration of two elements within equivalent atomic columns from EELS elemental maps - in our case barium and lanthanum within the A-sites of BaLaFeO, a second order Ruddlesden-Popper phase. We took advantage of the large changes in the elemental distribution from column to column and introduced a technique, which substitutes inelastic scattering cross sections during the quantification step by using parameters obtained from the actual experiment.

Unitary two-state quantum operators realized by quadrupole fields in the electron microscope.

In this work, a novel method for using a set of electromagnetic quadrupole fields is presented to implement arbitrary unitary operators on a two-state quantum system of electrons. In addition to analytical derivations of the required quadrupole and beam settings which allow an easy direct implementation, numerical simulations of realistic scenarios show the feasibility of the proposed setup. This is expected to pave the way not only for new measurement schemes in electron microscopy and related fields but even one day for the implementation of quantum computing in the electron microscope.

Steering the methanol steam reforming reactivity of intermetallic Cu-In compounds by redox activation: stability formation of an intermetallic compound-oxide interface.

To compare the inherent methanol steam reforming properties of intermetallic compounds and a corresponding intermetallic compound-oxide interface, we selected the Cu-In system as a model to correlate the stability limits, self-activation and redox activation properties with the catalytic performance. Three distinct intermetallic Cu-In compounds - CuIn, CuIn and CuIn - were studied both in an untreated and redox-activated state resulting from alternating oxidation-reduction cycles. The stability of all studied intermetallic compounds during methanol steam reforming (MSR) operation is essentially independent of the initial stoichiometry and all accordingly resist substantial structural changes.

Experimental realization of a π/2 vortex mode converter for electrons using a spherical aberration corrector.

In light optics, beams with orbital angular momentum (OAM) can be produced by employing a properly-tuned two-cylinder-lens arrangement, also called π/2 mode converter. It is not possible to convey this concept directly to the beam in an electron microscope due to the non-existence of cylinder lenses in commercial transmission electron microscopes (TEMs). A viable work-around are readily-available electron optical elements in the form of quadrupole lenses.

Exploiting the Acceleration Voltage Dependence of EMCD.

Energy-loss magnetic chiral dichroism (EMCD) is a versatile method for measuring magnetism down to the atomic scale in transmission electron microscopy (TEM). As the magnetic signal is encoded in the phase of the electron wave, any process distorting this characteristic phase is detrimental for EMCD. For example, elastic scattering gives rise to a complex thickness dependence of the signal.

Coherent light emission in cathodoluminescence when using GaAs in a scanning (transmission) electron microscope.

For most materials science oriented applications incoherent cathodoluminescence (CL) is of main interest, for which the recombination of electron-hole pairs yields the emission of light. However, the incoherent signal is superimposed by coherently excited photons, similar to the situation for X-rays in Energy-Dispersive X-ray spectra (EDX). In EDX two very different processes superimpose in each spectrum: Bremsstrahlung and characteristic X-ray radiation.

Fundamental Limit of Plasmonic Cathodoluminescence.

We use cathodoluminescence (CL) spectroscopy in a transmission electron microscope to probe the radial breathing mode of plasmonic silver nanodisks. A two-mirror detection system sandwiching the sample collects the CL emission in both directions, that is, backward and forward with respect to the electron beam trajectory. We unambiguously identify a spectral shift of about 8 nm in the CL spectra acquired from both sides and show that this asymmetry is induced by the electron beam itself.

Understanding electrochemical switchability of perovskite-type exsolution catalysts.

Exsolution of metal nanoparticles from perovskite-type oxides is a very promising approach to obtain catalysts with superior properties. One particularly interesting property of exsolution catalysts is the possibility of electrochemical switching between different activity states. In this work, synchrotron-based in-situ X-ray diffraction experiments on electrochemically polarized LaSrFeO thin film electrodes are performed, in order to simultaneously obtain insights into the phase composition and the catalytic activity of the electrode surface.

Thermoelectric performance of a metastable thin-film Heusler alloy.

Thermoelectric materials transform a thermal gradient into electricity. The efficiency of this process relies on three material-dependent parameters: the Seebeck coefficient, the electrical resistivity and the thermal conductivity, summarized in the thermoelectric figure of merit. A large figure of merit is beneficial for potential applications such as thermoelectric generators.

Elastic propagation of fast electron vortices through amorphous materials.

This work studies the elastic scattering behavior of electron vortices when propagating through amorphous samples. A formulation of the multislice approach in cylindrical coordinates is used to theoretically investigate the redistribution of intensity between different angular momentum components due to scattering. To corroborate and elaborate on our theoretical results, extensive numerical simulations are performed on three model systems (SiN, FeB, Pt) for a wide variety of experimental parameters to quantify the purity of the vortices, the net angular momentum transfer, and the variability of the results with respect to the random relative position between the electron beam and the scattering atoms.