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Nanoporous gold (NPG) is characterized by a bicontinuous network of nanometer-sized metallic struts and interconnected pores formed spontaneously by oxidative dissolution of the less noble element from gold alloys. The resulting material exhibits decent catalytic activity for low-temperature, aerobic total as well as partial oxidation reactions, the oxidative coupling of methanol to methyl formate being the prototypical example. This review not only provides a critical discussion of ways to tune the morphology and composition of this material and its implication for catalysis and electrocatalysis, but will also exemplarily review the current mechanistic understanding of the partial oxidation of methanol using information from quantum chemical studies, model studies on single-crystal surfaces, gas phase catalysis, aerobic liquid phase oxidation, and electrocatalysis. In this respect, a particular focus will be on mechanistic aspects not well understood, yet. Apart from the mechanistic aspects of catalysis, best practice examples with respect to material preparation and characterization will be discussed. These can improve the reproducibility of the materials property such as the catalytic activity and selectivity as well as the scope of reactions being identified as the main challenges for a broader application of NPG in target-oriented organic synthesis.

When using the unit cell average of first moment data from four-dimensional scanning transmission electron microscopy (4D-STEM) to characterize ferroelectric materials, a variety of sources of systematic errors needs to be taken into account. In particular, these are the magnitude of the acceleration voltage, STEM probe semi-convergence angle, sample thickness, and sample tilt out of zone axis. Simulations show that a systematic error of calculated electric fields using the unit cell averaged momentum transfer originates from violation of point symmetry within the unit cells. Thus, values can easily exceed those of potential polarization-induced electric fields in ferroelectrics. Importantly, this systematic error produces deflection gradients between different domains seemingly representing measured fields. However, it could be shown that for PbZr0.2Ti0.8O3, many adjacent domains exhibit a relative crystallographic mistilt and in-plane rotation. The experimental results show that the method gives qualitative domain contrast. Comparison of the calculated electric field with the systematic error showed that the domain contrast of the unit cell averaged electric fields is mainly caused by dynamical scattering effects and the electric field plays only a minor role, if present at all.

The luminescence of InxGa1−xN nanowires (NWs) is frequently reported with large red-shifts as compared to the theoretical value expected from the average In content. Both compositional fluctuations and radial built-in fields were considered accountable for this effect, depending on the size, structure, composition, and surrounding medium of the NWs. In the present work, the emission properties of InGaN/GaN NWs grown by plasma-assisted molecular beam epitaxy are investigated in a comprehensive study combining ultraviolet-Raman and photoluminescence spectroscopy (PL) on vertical arrays, polarization-dependent PL on bundles of a few NWs, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, and calculations of the band profiles. The roles of inhomogeneous In distribution and radial fields in the context of optical emission properties are addressed. The radial built-in fields are found to be modest, with a maximum surface band bending below 350 meV. On the other hand, variations in the local In content have been observed that give rise to potential fluctuations whose impact on the emission properties is shown to prevail over band-bending effects. Two luminescence bands with large positive and moderate negative polarization ratios of ≈+80% and ≤−60%, respectively, were observed. The red-shift in the luminescence is associated with In-rich inclusions in the NWs due to thermodynamic decomposition during growth. The negative polarization anisotropy is suggested to result from spontaneously formed superlattices in the In-rich regions of the NWs. The NWs show a preferred orthogonal absorption due to the dielectric boundary conditions and highlight the extreme sensitivity of these structures towards light polarization.

The influence of self-assembled short-period superlattices (SPSLs) on the structural and optical properties of InGaN/GaN nanowires (NWs) grown by PAMBE on Si (111) was investigated by STEM, EDXS, µ-PL analysis and k·p simulations. STEM analysis on single NWs indicates that in most of the studied nanostructures, SPSLs self-assemble during growth. The SPSLs display short-range ordering of In-rich and In-poor InxGa1-xN regions with a period of 2–3 nm that are covered by a GaN shell and that transition to a more homogenous InxGa1-xN core. Polarization- and temperature-resolved PL analysis performed on the same NWs shows that they exhibit a strong parallel polarized red-yellow emission and a predominantly perpendicular polarized blue emission, which are ascribed to different In-rich regions in the nanostructures. The correlation between STEM, µ-PL and k·p simulations provides better understanding of the rich optical emission of complex III-N nanostructures and how they are impacted by structural properties, yielding the significant impact of strain on self-assembly and spectral emission. Graphical abstract

In this article we shed light on newly emerging perspectives to characterize and understand the interplay of diffusive mass transport and surface catalytic processes in pores of gas phase metal catalysts. As a case study, nanoporous gold, as an interesting example exhibiting a well-defined pore structure and a high activity for total and partial oxidation reactions is considered. PFG NMR (pulsed field gradient nuclear magnetic resonance) measurements allowed here for a quantitative evaluation of gas diffusivities within the material. STEM (scanning transmission electron microscopy) tomography furthermore provided additional insight into the structural details of the pore system, helping to judge which of its features are most decisive for slowing down mass transport. Based on the quantitative knowledge about the diffusion coefficients inside a porous catalyst, it becomes possible to disentangle mass transport contributions form the measured reaction kinetics and to determine the kinetic rate constant of the underlying catalytic surface reaction. In addition, predictions can be made for an improved effectiveness of the catalyst, i.e., optimized conversion rates. This approach will be discussed at the example of low-temperature CO oxidation, efficiently catalysed by npAu at 30 °C. The case study shall reveal that novel porous materials exhibiting well-defined micro- and mesoscopic features and sufficient catalytic activity, in combination with modern techniques to evaluate diffusive transport, offer interesting new opportunities for an integral understanding of catalytic processes. Graphical Abstract

Porous networks of Pt nanoparticles interlinked by bifunctional organic ligands have shown high potential as catalysts in micro‐machined hydrogen gas sensors. By varying the ligand among p‐phenylenediamine, benzidine, 4,4‘‘‐diamino‐p‐terphenyl, 1,5‐diaminonaphthalene, and trans‐1,4‐diaminocyclohexane, new variants of such networks were synthesized. Inter‐particle distances within the networks, determined via transmission electron microscopy tomography, varied from 0.8 to 1.4 nm in accordance with the nominal length of the respective ligand. While stable structures with intact and coordinatively bonded diamines were formed with all ligands, aromatic diamines showed superior thermal stability. The networks exhibited mesoporous structures depending on ligand and synthesis strategy and performed well as catalysts in hydrogen gas microsensors. They demonstrate the possibility of deliberately tuning micro‐ and mesoporosity and thereby transport properties and steric demands by choice of the right ligand also for other applications in heterogeneous catalysis., Pt nanocatalyst construction kit: variants of stable Pt nanoparticle networks were synthesized from the same Pt nanoparticle building block and 5 different aromatic and aliphatic diamines as joints. These ligand‐linked networks demonstrate the possibility of deliberately tuning their microporosity for applications in heterogeneous catalysis by choice of the right ligand.

The ISTEM mode for TEM has been demonstrated to have several advantages in regard to resolution and precision. While previous works primarily focussed on the advantages due to the reduced spatial coherence, the actual image contrast, i.e. how bright or dark certain atom columns are imaged, has mostly been of secondary concern. The present work sets out to achieve the contrast of annular bright field STEM in ISTEM, producing the high contrast of light elements, for which this method is popular. It is shown from theoretical considerations that using an annular condenser aperture this aim can be realised. The optimal size of this aperture is found by simulative studies. It is then manufactured from platinum foil and installed in an image-aberration corrected microscope. ABF-like ISTEM images of strontium titanate in [100] projection are acquired. The pure oxygen columns are clearly resolved with significant contrast. The image pattern is indeed identical to what is achieved by ABF STEM. A close look at the image formation also shows that the dose needed for a given signal-to-noise ratio is at least a quarter smaller for ABF-like ISTEM compared to ABF STEM, assuming detectors of similar detective quantum efficiency.

The ternary mixed metal oxides with high specific surface area are industrially important for sensors, catalysis, energy storage, and optoelectronics. However, synthesis of such metal oxides is alw...

Nano letters 21(5), 2018-2025 (2021). doi:10.1021/acs.nanolett.0c04544, Published by American Chemical Society, Washington, DC

In this paper we perform angular resolved annular-dark field (ADF) scanning-transmission electron microscopy (STEM) to study the scattered intensity in an InGaN layer buried in GaN as a function of the scattering angle. We achieved angular resolution with a motorized iris aperture in front of the ADF detector. Using this setup, we investigated how the intensities measured in various angular ranges agree with multislice simulations in the frozen-lattice approximation. We observed a strong influence of relaxation induced surface-strain fields on the ADF intensity, measured its angular characteristics and compared the result with simulations. To assess the agreement of the measured intensity with simulations, we evaluated the specimen thickness in GaN and the indium concentration in InGaN for each angular interval by comparing the measured intensities with simulations. The thickness was strongly overestimated for scattering angles below 40mrad and also the evaluated indium concentration varies with the considered angular range. Using simulations, we investigated which angular ranges show a high sensitivity to variations of the thickness and which intervals strongly depend on the indium concentration. By combining two angular intervals, the indium concentration and the specimen thickness were determined simultaneously, which has potential advantages over the usual quantification method. It is shown that inelastic scattering, surface contamination and mistilt can have an influence on the measured intensity, especially at lower scattering angles below 30-50mrad, which might explain the observed difference between the frozen lattice simulation and the experiment.

Quantitative structural characterization of nanomaterials is important to tailor their functional properties. Corrosion of AgAu-alloy nanoparticles (NPs) results in porous structures, making them interesting for applications especially in the fields of catalysis and surface-enhanced Raman spectroscopy. For the present report, structures of dealloyed NPs were reconstructed three-dimensionally using scanning transmission electron microscopy tomography. These reconstructions were evaluated quantitatively, revealing structural information such as pore size, porosity, specific surface area, and tortuosity. Results show significant differences compared to the structure of dealloyed bulk samples and can be used as input for simulations of diffusion or mass transport processes, for example, in catalytic applications.

Dealloyed nanoporous metals hold great promise in the field of heterogeneous catalysis; however their tendency to coarsen at elevated temperatures or under catalytic reaction conditions sometimes limit further applications. Here, we report on a highly stable nanoporous gold catalyst (npAu) functionalized with praseodymia-titania mixed oxides as synthesized by a sol-gel method. Specifically, we used aberration-corrected transmission electron microscopy to study the morphology and the interface between the oxide deposits and the npAu substrate at the atomic level. Based on electron energy loss spectroscopy (EELS), it is concluded that Pr-TiOx mixed oxides form a solid solution. Flow reactor tests reveal that the Pr-TiOx functionalized nanoporous gold is not only highly active but also very stable for the water gas shift reaction in a large temperature range (180-400 °C). Our results demonstrate the potential of engineering the compositions of oxides coatings on npAu for advanced functional systems.

The measurement of electric fields in scanning transmission electron microscopy (STEM) is a highly investigated field of research. The constant improvement of spatial resolution in STEM and the development of new hardware for the fast acquisition of diffraction patterns even paved the way for the measurement of atomic electric fields. Although the basic principle that an electric field leads to a tilt of the focussed electron probe that can be detected as a shift of the diffraction pattern in the back focal plane of the objective lens seems quite simple, many challenges arose in the measurement of fields in a quantitative way. In the present study we investigate whether a shift of the diffraction pattern that occurs at an interface between two materials can be related to the electric field which is caused by the difference of the mean inner potentials of the two materials. To this end, experiments and simulations are compared. It is demonstrated that the difference in mean inner potential has an influence on the observed effect, but a quantitative interpretation is difficult. The influence of image recording effects such as shot noise and the modulation transfer function are investigated as well as further effects such as e.g. sample tilt. In addition, the influence of the observed effect on a strain measurement is shown.

In this paper we study the effect of lens aberrations (spherical aberration and astigmatism), beam tilt, contamination and shot noise on the accuracy and precision of position determination in imaging scanning transmission electron microscopy (ISTEM) on the example of BaTiO

The spinel LiMn

Nanoporous gold (npAu) fabricated from a AuCu alloy is a complex procedure mostly because of the passivated outer surface and the inhibited corrosion phenomena observed in those materials as a consequence of the formation of a Pm¯3m (AuCu3). To further deepen our understanding of the leaching of Cu in these materials, a series of experiments were performed to study the corrosion process and finally start giving an answer to this problem. Here we compare different corrosion methods, beginning with free corrosion (as the standard synthetic route for npAu) and finishing with an optimized potentiostatic dealloying (four-step method) procedure. In order to distinguish between the structural and chemical effects affecting the catalytic activity, a series of experiments employing scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) coupled with Energy-dispersive X-ray spectroscopy (EDXS), and X-ray photoelectron spectroscopy (XPS) were performed before and after catalytic CO oxidation. The data reveals a clear influence in key synthetic steps in the master alloy synthesis (thermal treatment), as well as in the dealloying procedure.

The angle-resolved electron scattering is investigated in scanning-transmission electron microscopy (STEM) using a motorised iris aperture placed above a conventional annular detector. The electron intensity scattered into various angle ranges is compared with simulations that were carried out in the frozen-lattice approximation. As figure of merit for the agreement of experiment and simulation we evaluate the specimen thickness which is compared with the thickness obtained from position-averaged convergent beam electron diffraction (PACBED). We find deviations whose strengths depend on the angular range of the detected electrons. As possible sources of error we investigate, for example, the influences of amorphous surface layers, inelastic scattering (plasmon excitation), phonon-correlation within the frozen-lattice approach, and distortions in the diffraction plane of the microscope. The evaluation is performed for four experimental thicknesses and two angle-resolved STEM series under different camera lengths. The results clearly show that especially for scattering angles below 50 mrad, it is mandatory that the simulations take scattering effects into account which are usually neglected for simulating high-angle scattering. Most influences predominantly affect the low-angle range, but also high scattering angles can be affected (e.g. by amorphous surface covering).

The spinel LiMn2O4 (LMO) is a promising cathode material for rechargeable Li-ion batteries due to its excellent properties, including cost effectiveness, eco-friendliness, high energy density, and rate capability. The commercial application of LiMn2O4 is limited by its fast capacity fading during cycling, which lowers the electrochemical performance. In the present work, phase-pure and crystalline LiMn2O4 spinel in the nanoscale were synthesized using single flame spray pyrolysis via screening 16 different precursor-solvent combinations. To overcome the drawback of capacity fading, LiMn2O4 was homogeneously mixed with different percentages of AlPO4 using versatile multiple flame sprays. The mixing was realized by producing AlPO4 and LiMn2O4 aerosol streams in two independent flames placed at 20° to the vertical axis. The structural and morphological analyses by X-ray diffraction indicated the formation of a pure LMO phase and/or AlPO4-mixed LiMn2O4. Electrochemical analysis indicated that LMO nanoparticles of 17.8 nm (dBET) had the best electrochemical performance among the pure LMOs with an initial capacity and a capacity retention of 111.4 mA h g-1 and 88% after 100 cycles, respectively. A further increase in the capacity retention to 93% and an outstanding initial capacity of 116.1 mA h g-1 were acquired for 1% AlPO4.

Modern quantitative TEM methods such as the ζ -factor technique require precise knowledge of the electron beam current. To this end, a macroscopic Faraday cup was designed and constructed. It can replace the viewing screen in the projection chamber of a TEM and guarantees highly accurate measurement of the electron beam with precision only limited by the used amperemeter. The easy to install, affordable device is shown to be highly apt for precision measurement of currents > 5 pA . The Faraday cup results are used for an assessment and a comparison of various other beam current measurement methods. It is found that the built-in screen amperemeter of the used TEM is quite inaccurate and that measurements using the screen in general tend to underestimate the current. If present, the drift tube of a spectrometer can also be used as a Faraday cup, but certain described peculiarities have to be taken into account. Direct ultrafast electron detection cameras allow precise measurement at very small currents. For the electron counting technique, which exploits single electron detection capabilities of STEM detectors, a systematic current underestimation was observed and investigated. This results in a reformulated routine for the method and with these improvements it is demonstrated to be capable of accurate high-precision measurements for currents 5 pA .

A reformulated implementation of single-sideband ptychography enables analysis and display of live detector data streams in 4D scanning transmission electron microscopy (STEM) using the LiberTEM open-source platform. This is combined with live first moment and further virtual STEM detector analysis. Processing of both real experimental and simulated data shows the characteristics of this method when data is processed progressively, as opposed to the usual offline processing of a complete dataset. In particular, the single side band method is compared to other techniques such as the enhanced ptychographic engine in order to ascertain its capability for structural imaging at increased specimen thickness. Qualitatively interpretable live results are obtained also if the sample is moved, or magnification is changed during the analysis. This allows live optimization of instrument as well as specimen parameters during the analysis. The methodology is especially expected to improve contrast- and dose-efficient in-situ imaging of weakly scattering specimens, where fast live feedback during the experiment is required., 14 pages, 11 figures. Achim Strauch and Dieter Weber contributed equally to this work and share first-authorship. Corresponding Author: Achim Strauch

4D-scanning transmission electron microscopy (4D-STEM) can be used to measure electric fields such as atomic fields or polarization-induced electric fields in crystal heterostructures. The paper focuses on effects occurring in 4D-STEM at interfaces, where two model systems are used: an AlN/GaN nanowire superlattice as well as a GaN/vacuum interface. Two different methods are applied: First, we employ the centre-of mass (COM) technique which uses the average momentum transfer evaluated from the intensity distribution in the diffraction pattern. Second, we measure the shift of the undiffracted disc (disc-detection method) in nano-beam electron diffraction (NBED). Both methods are applied to experimental and simulated 4D-STEM data sets. We find for both techniques distinct variations in the momentum transfer at interfaces between materials: In both model systems, peaks occur at the interfaces and we investigate possible sources and routes of interpretation. In case of the AlN/GaN superlattice, the COM and disc-detection methods are used to measure internal polarization-induced electric fields and we observed a reduction of the measured fields with increasing specimen thickness.

Tin dioxide (SnO2) nanoparticles synthesized via flame spray pyrolysis (FSP) have promising applications for gas sensors. The formation of SnO2 nanoparticles in the gas-phase has been investigated using single droplet combustion and FSP. Precursor solutions of Tin (II) 2-ethylhexanoate dissolved in Xylene with varying Sn concentrations were selected as the precursor-solvent system. The selected precursor-solvent system has its stability and ability to synthesize homogeneous nanoparticles, compared to metal nitrate based precursor solutions. The precursor-solvent system was studied using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and thermogravimetric analysis (TGA). The SnO2 nanoparticles were characterized using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), and transmission electron microscopy (TEM). Droplet surface micro-explosions were observed during the single droplet combustion of the precursor solutions. It is because of the heterogeneous vapor-phase nucleation, which is beneath the liquid droplet surface and caused by precursor thermal decomposition. The results show that the size of nanoparticles obtained both from FSP and single droplet combustion increases with increasing metal-precursor concentration. The TEM images of the particles from such droplet combustion reveal two types of nanoparticles with different sizes and morphologies. The current work provides fundamental understanding of precursor decomposition and particle formation during single droplet combustion, which help in-depth understanding of the flame spray pyrolysis.

Properties of dealloyed nanoporous gold (npAu) in catalysis, sensing or actuation applications depend on its structure and chemical composition. NpAu is obtained by corrosion of alloys of gold and a less noble metal such as silver or copper. Structural parameters can be tuned by variations in the preparation process. Due to the large number of parameters that can be varied a direct comparison of results obtained with various samples is often difficult. In this report we compare structure and chemical composition of npAu dealloyed from AuAg and AuCu alloys keeping the number of different sample preparation parameters at a minimum.

Strain analyses from experimental series of nano-beam electron diffraction (NBED) patterns in scanning transmission electron microscopy are performed for different specimen tilts. Simulations of NBED series are presented for which strain analysis gives results that are in accordance with experiment. This consequently allows to study the relation between measured strain and actual underlying strain. A two-tilt method which can be seen as lowest-order electron beam precession is suggested and experimentally implemented. Strain determination from NBED series with increasing beam convergence is performed in combination with the experimental realization of a probe-forming aperture with a cross inside. It is shown that using standard evaluation techniques, the influence of beam convergence on spatial resolution is lower than the influence of sharp rings around the diffraction disc which occur at interfaces and which are caused by the tails of the intensity distribution of the electron probe. (C) 2018 Elsevier B.V. All rights reserved.

Ultrathin bimetallic nanowires are of importance and interest for applications in electronic devices such as sensors and heterogeneous catalysts. In this work, we have designed a new, highly reproducible and generalized wet chemical method to synthesize uniform and monodispersed Au-based alloy (AuCu, AuPd, and AuPt) nanowires with tunable composition using microwave-assisted reduction at the liquid-liquid interface. These ultrathin alloy nanowires are below 4 nm in diameter and about 2 μm long. Detailed microstructural characterization shows that the wires have an face centred cubic (FCC) crystal structure, and they have low-energy twin-boundary and stacking-fault defects along the growth direction. The wires exhibit remarkable thermal and mechanical stability that is critical for important applications. The alloy wires exhibit excellent electrocatalytic activity for methanol oxidation in an alkaline medium.

Reversible macroscopic length changes in nanoporous structures can be achieved by applying electric potentials or by exposing them to different gases or liquids. Thus, these materials are interesting candidates for applications as sensors or actuators. Macroscopic length changes originate from microscopic changes of crystal lattice parameters. In this report, we show spatially resolved measurements of crystal lattice strain in dealloyed nanoporous gold. The results confirm theory by indicating a compression of the lattice along the axis of cylindrically shaped ligaments and an expansion in radial direction. Furthermore, we show that curved npAu surfaces show inward relaxation of the surface layer. (Figure presented) IMPACT STATEMENT We show spatially resolved measurements of strain in nanoporous gold confirming theory: Crystal lattice is compressed along the axis of cylindrical ligaments and expanded in radial direction, surfaces relax inward.

Reduction of lithium-ion battery (LIB) production costs is inevitable to make the use of LIB technology more viable for applications such as electric vehicles or stationary storage. To meet the requirements in today's LIB cost efficiency, our current research focuses on an alternative electrode fabrication method, characterized by a combination of double flame spray pyrolysis and lamination technique (DFSP/lamination). In-situ carbon coated nano-Li4Ti5O12 (LTO/C) was synthesized using versatile DFSP. The as-prepared composite powder was then directly laminated onto a conductive substrate avoiding the use of any solvent or binder for electrode preparation. The influence of lamination pressures on the microstructure and electrochemical performance of the electrodes was also investigated. Enhancements in intrinsic electrical conductivity were found for higher lamination pressures. Capacity retention of highest pressurized DFSP/lamination-prepared electrode was 87.4% after 200 dis-/charge cycles at 1C (vs. Li). In addition, LTO/C material prepared from the double flame spray pyrolysis was also used for fabricating electrodes via doctor blading technique. Laminated electrodes obtained higher specific discharge capacities compared to calendered and non-calendered blade-casted electrodes due to superior microstructural properties. Such a fast and industrially compelling integrative DFSP/lamination tool could be a prosperous, next generation technology for low-cost LIB electrode fabrication.