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Over the past decade, advances in the colloidal syntheses of octahedral-shaped Pt–Ni alloy nanocatalysts for use in fuel cell cathodes have raised our atomic-scale control of particle morphology and surface composition, which, in turn, helped raise their catalytic activity far above that of benchmark Pt catalysts. Future fuel cell deployment in heavy-duty vehicles caused the scientific priorities to shift from alloy particle activity to stability. Larger particles generally offer enhanced thermodynamic stability, yet synthetic approaches toward larger octahedral Pt–Ni alloy nanoparticles have remained elusive. In this study, we show how a simple manipulation of solvothermal synthesis reaction kinetics involving depressurization of the gas phase at different stages of the reaction allows tuning the size of the resulting octahedral nanocatalysts to previously unachieved scales. We then link the underlying mechanism of our approach to the classical “LaMer” model of nucleation and growth. We focus on large, annealed Mo-doped Pt–Ni octahedra and investigate their synthesis, post-synthesis treatments, and elemental distribution using advanced electron microscopy. We evaluate the electrocatalytic ORR performance and stability and succeed to obtain a deeper understanding of the enhanced stability of a new class of relatively large, active, and long-lived Mo-doped Pt–Ni octahedral catalysts for the cathode of PEMFCs.

A recently developed emulsion-templated assembly method promises the scalable, low-cost, and reproducible fabrication of hierarchical nanocrystal (NC) superstructures. These superstructures derive properties from the unique combination of choices of NC building blocks and superstructure morphology and therefore realize the concept of "artificial solids". To control the final properties of these superstructures, it is essential to control the assembly conditions that yield distinct architectural morphologies. Here, we explore the phase-space of experimental parameters describing the emulsion-templated assembly including temperature, interfacial tension, and NC polydispersity and demonstrate which conditions lead to the growth of the most crystalline NC superstructures or supercrystals. By using a combination of electron microscopy and small-angle X-ray scattering, we show that slower assembly kinetics, softer interfaces, and lower NC polydispersity contribute to the formation of supercrystals with grain sizes up to 600 nm, while reversing these trends yields glassy solids. These results provide a clear path to the realization of higher-quality supercrystals, necessary to many applications.

Recently proposed bimetallic octahedral Pt–Ni electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC) cathodes suffer from particle instabilities in the form of Ni corrosion and shape degradation. Advanced trimetallic Pt-based electrocatalysts have contributed to their catalytic performance and stability. In this work, we propose and analyse a novel quaternary octahedral (oh-)Pt nanoalloy concept with two distinct metals serving as stabilizing surface dopants. An efficient solvothermal one-pot strategy was developed for the preparation of shape-controlled oh-PtNi catalysts doped with Rh and Mo in its surface. The as-prepared quaternary octahedral PtNi(RhMo) catalysts showed exceptionally high ORR performance accompanied by improved activity and shape integrity after stability tests compared to previously reported bi- and tri-metallic systems. Synthesis, performance characteristics and degradation behaviour are investigated targeting deeper understanding for catalyst system improvement strategies. A number of different operando and on-line analysis techniques were employed to monitor the structural and elemental evolution, including identical location scanning transmission electron microscopy and energy dispersive X-ray analysis (IL-STEM-EDX), operando wide angle X-ray spectroscopy (WAXS), and on-line scanning flow cell inductively coupled plasma mass spectrometry (SFC-ICP-MS). Our studies show that doping PtNi octahedral catalysts with small amounts of Rh and Mo suppresses detrimental Pt diffusion and thus offers an attractive new family of shaped Pt alloy catalysts for deployment in PEMFC cathode layers.

The invention of silicon drift detectors has resulted in an unprecedented improvement in detection efficiency for energy-dispersive X-ray (EDX) spectroscopy in the scanning transmission electron microscope. The result is numerous beautiful atomic-scale maps, which provide insights into the internal structure of a variety of materials. However, the task still remains to understand exactly where the X-ray signal comes from and how accurately it can be quantified. Unfortunately, when crystals are aligned with a low-order zone axis parallel to the incident beam direction, as is necessary for atomic-resolution imaging, the electron beam channels. When the beam becomes localized in this way, the relationship between the concentration of a particular element and its spectroscopic X-ray signal is generally nonlinear. Here, we discuss the combined effect of both spatial integration and sample tilt for ameliorating the effects of channeling and improving the accuracy of EDX quantification. Both simulations and experimental results will be presented for a perovskite-based oxide interface. We examine how the scattering and spreading of the electron beam can lead to erroneous interpretation of interface compositions, and what approaches can be made to improve our understanding of the underlying atomic structure.

Electron tomography has been widely applied to three-dimensional (3D) morphology characterization and chemical analysis at the nanoscale. A HAADF-EDS bimodal tomographic (HEBT) reconstruction technique has been developed to extract high resolution element-specific information. However, the reconstructed elemental maps cannot be directly converted to quantitative compositional information. In this work, we propose a quantification approach for obtaining elemental weight fraction maps from the HEBT reconstruction technique using the physical parameters extracted from a Monte Carlo code, MC X-ray. A similar quantification approach is proposed for the EDS-STEM tomographic reconstruction. The performance of the two quantitative reconstruction methods, using the simultaneous iterative reconstruction technique, are evaluated and compared for a simulated dataset of a two-dimensional phantom sample. The effects of the reconstruction parameters including the number of iterations and the weight of the HAADF signal are discussed. Finally, the two approaches are applied to an experimental dataset to show the 3D structure and quantitative elemental maps of a particle of flux melted metal-organic framework glass.

Computer simulations are used to assess the influence of a 20-nm-thick SiN

Semiconductor nanocrystals, or quantum dots (QDs), simultaneously benefit from inexpensive low-temperature solution processing and exciting photophysics, making them the ideal candidates for next-generation solar cells and photodetectors. While the working principles of these devices rely on light absorption, QDs intrinsically belong to the Rayleigh regime and display optical behavior limited to electric dipole resonances, resulting in low absorption efficiencies. Increasing the absorption efficiency of QDs, together with their electronic and excitonic coupling to enhance charge carrier mobility, is therefore of critical importance to enable practical applications. Here, we demonstrate a general and scalable approach to increase both light absorption and excitonic coupling of QDs by fabricating hierarchical metamaterials. We assemble QDs into crystalline supraparticles using an emulsion template and demonstrate that these colloidal supercrystals (SCs) exhibit extended resonant optical behavior resulting in an enhancement in absorption efficiency in the visible range of more than 2 orders of magnitude with respect to the case of dispersed QDs. This successful light trapping strategy is complemented by the enhanced excitonic coupling observed in ligand-exchanged SCs, experimentally demonstrated through ultrafast transient absorption spectroscopy and leading to the formation of a free biexciton system on sub-picosecond time scales. These results introduce a colloidal metamaterial designed by self-assembly from the bottom up, simultaneously featuring a combination of nanoscale and mesoscale properties leading to simultaneous photonic and excitonic coupling, therefore presenting the nanocrystal analogue of supramolecular structures.

For lignin valorization, simultaneously achieving the efficient cleavage of ether bonds and restraining the condensation of the formed fragments represents a challenge thus far. Herein, we report a two-step oxidation–hydrogenation strategy to achieve this goal. In the oxidation step, the O2/NaNO2/DDQ/NHPI system selectively oxidizes CαH–OH to Cα═O within the β-O-4 structure. In the subsequent hydrogenation step, the α-O-4 and the preoxidized β-O-4 structures are further hydrogenated over a NiMo sulfide catalyst, leading to the cleavage of Cβ–OPh and Cα–OPh bonds. Besides the transformation of lignin model compounds, the yield of phenolic monomers from birch wood is up to 32% by using this two-step strategy. The preoxidation of CαH–OH to Cα═O not only weakens the Cβ–OPh ether bond but also avoids the condensation reactions caused by the presence of Cα+ from dehydroxylation of CαH–OH. Furthermore, the NiMo sulfide prefers to catalyze the hydrogenative cleavage of the Cβ–OPh bond connecting with a Cα═O rathe...

The new generation of analytical electron microscopes with aberration correction and new EDX detectors provide improved possibilities for microanalysis. Here, we apply a new approach to quantitative EDX based on using partial cross sections. Our quantification method is applied to alloy PtCo nanoparticles, which have been acid leached to provide Pt enrichment or rather Co depletion at the particle surface. Such surface Co depletion is absent at the vertices of the more facetted nanoparticles. The leaching process demonstrates very little change in Co composition when investigating the whole particle but produces a localised surface depletion, which can only be determined by the high-resolution EDX elemental maps.

The efficient cleavage of lignin β-O-4 ether bonds to produce aromatics is a challenging and attractive topic. Recently a growing number of studies have revealed that the initial oxidation of CαHOH to CαO can decrease the β-O-4 bond dissociation energy (BDE) from 274.0 kJ mol−1 to 227.8 kJ mol−1, and thus the β-O-4 bond is more readily cleaved in the subsequent transfer hydrogenation, or acidolysis. Here we show that the first reaction step, except in the above-mentioned pre-oxidation methods, can be a Cα–OH bond dehydroxylation to form a radical intermediate on the acid-redox site of a NiMo sulfide catalyst. The formation of a Cα radical greatly decreases the Cβ–OPh BDE from 274.0 kJ mol−1 to 66.9 kJ mol−1 thereby facilitating its cleavage to styrene, phenols and ethers with H2 and an alcohol solvent. This is supported by control experiments using several reaction intermediates as reactants, analysis of product generation and by radical trap with TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) as well as by density functional theory (DFT) calculations. The dehydroxylation–hydrogenation reaction is conducted under non-oxidative conditions, which are beneficial for stabilizing phenol products.

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. We illustrate the retrieval of the atomic scale diffusion process in an Al1-xInxN alloy grown on GaN and the surface oxidation state of perovskite nanocatalysts. The improved SNR of the EELS dataset also allows the retrieval of atomically resolved oxidation maps considering the fine structure absorption edge of LaMnO3 nanoparticles. Ministry of Education (MOE) This work was supported by Ministry of Education Academic Research Fund Tier 1 grants RG101/17 (Nanyang Technological University). This research was supported under the Discovery Projects funding scheme (Project DP140102538) of the Australian Research Council and by the Alexander von Humboldt Foundation. The authors at AICES RWTH Aachen University were funded in part by the Excellence Initiative of the German Federal and State Governments through grant GSC 111.

Quantitative annular dark field scanning transmission electron microscopy (ADF STEM) has become a powerful technique to characterise nano-particles on an atomic scale. Because of their limited size and beam sensitivity, the atomic structure of such particles may become extremely challenging to determine. Therefore keeping the incoming electron dose to a minimum is important. However, this may reduce the reliability of quantitative ADF STEM which will here be demonstrated for nano-particle atom-counting. Based on experimental ADF STEM images of a real industrial catalyst, we discuss the limits for counting the number of atoms in a projected atomic column with single atom sensitivity. We diagnose these limits by combining a thorough statistical method and detailed image simulations.

Many studies of heterogeneous catalysis, both experimental and computational, make use of idealized structures such as extended surfaces or regular polyhedral nanoparticles. This simplification neglects the morphologicaldiversity in real commercial oxygen reduction reaction (ORR) catalysts used infuel-cell cathodes. Here we introduce an approach that combines 3Dnanoparticle structures obtained from high-throughput high-precision electronmicroscopy with density functional theory. Discrepancies between experimentalobservations and cuboctahedral/truncated-octahedral particles are revealed anddiscussed using a range of widely used descriptors, such as electron-density, d-band centers, and generalized coordination numbers. We use this new approach to determine the optimum particle size for which both detrimental surface roughness and particle shape effects are minimized.

Advances in microscope stability, aberration correction and detector design now make it readily possible to achieve atomic resolution energy dispersive X-ray mapping for dose resilient samples. These maps show impressive atomic-scale qualitative detail as to where the elements reside within a given sample. Unfortunately, while electron channelling is exploited to provide atomic resolution data, this very process makes the images rather more complex to interpret quantitatively than if no electron channelling occurred. Here we propose small sample tilt as a means for suppressing channelling and improving quantification of composition, whilst maintaining atomic-scale resolution. Only by knowing composition and thickness of the sample is it possible to determine the atomic configuration within each column. The effects of neighbouring atomic columns with differing composition and of residual channelling on our ability to extract exact column-by-column composition are also discussed.

Solar devices based on semiconductor nanoparticles require the use of conductive ligands; however, replacing the native, insulating ligands with conductive metal chalcogenide complexes introduces structural defects within the crystalline nanostructure that act as traps for charge carriers. We utilized atomically thin semiconductor nanoplatelets as a convenient platform for studying, both microscopically and spectroscopically, the development of defects during ligand exchange with the conductive ligands Na4SnS4 and (NH4)4Sn2S6. These defects can be repaired via mild chemical or thermal routes, through the addition of L-type ligands or wet annealing, respectively. This results in a higher-quality, conductive, colloidally stable nanomaterial that may be used as the active film in optoelectronic devices.

Several distinct mixing processes and resulting microstructures have recently been reported in multicomponent glasses prepared from multiple metal-organic frameworks. Here, two illustrative examples of multicomponent zeolitic imidazolate framework (ZIF) glasses, the (aTZIF-4-Co)0.5(agZIF-62)0.5 blend and the ag[(ZIF-67)0.2(ZIF-62)0.8] flux melted glass, are studied. These materials are characterized by quantitative X-ray energy dispersive spectroscopy in the scanning transmission electron microscope. By advancing a partial ionization cross section methodology using standards of arbitrary morphology, quantitative nanoscale elemental analysis throughout the glass volume is achieved. In turn, phase diagrams describing the mixing states are presented, offering mechanistic insight into the formation of the observed microstructures. Significant miscibility was observed in ag[(ZIF-67)0.2(ZIF-62)0.8]. These findings establish phase-segregation and interdiffusion as two processes in multicomponent glass formation, which explains the different outcomes observed in blending and flux melting.

The physical basis for using a probe-position integrated cross section (PICS) for a single column of atoms as an effective way to compare simulation and experiment in high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) is described, and the use of PICS in order to make quantitative use of image intensities is evaluated. It is based upon the calibration of the detector and the measurement of scattered intensities. Due to the predominantly incoherent nature of HAADF STEM, it is found to be robust to parameters that affect probe size and shape such as defocus and source coherence. The main imaging parameter dependencies are on detector angle and accelerating voltage, which are well known. The robustness to variation in other parameters allows for a quantitative comparison of experimental data and simulation without the need to lit parameters. By demonstrating the application of the [PICS to the chemical identification of single atoms in a heterogeneous catalyst and in thin, layered-materials, we explore some of the experimental considerations when using this approach. (C) 2013 Elsevier B.V. All rights reserved.

Heterogeneous nanoparticle catalyst development relies on an understanding of their structure-property relationships, ideally at atomic resolution and in three-dimensions. Current transmission electron microscopy techniques such as discrete tomography can provide this but require multiple images of each nanoparticle and are incompatible with samples that change under electron irradiation or with surveying large numbers of particles to gain significant statistics. Here, we make use of recent advances in quantitative dark-field scanning transmission electron microscopy to count the number atoms in each atomic column of a single image from a platinum nanoparticle. These atom-counts, along with the prior knowledge of the face-centered cubic geometry, are used to create atomistic models. An energy minimization is then used to relax the nanoparticle's 3D structure. This rapid approach enables high-throughput statistical studies or the analysis of dynamic processes such as facet-restructuring or particle damage.

Recording HAADF STEM data on an absolute scale for image quantification is becoming increasingly common. A particular challenge with this method is that most image simulation programs model the detector as being circularly symmetric and exhibiting uniform detection sensitivity across its entire active region. For a real detector this is rarely the case; it then becomes vital to understand how far one's detector deviates from the ideal. Here we investigate a collection of detector maps recorded using hardware from each of the current major manufacturers. Using these maps we compare their different asymmetries and any non-uniformities in their sensitivity. To facilitate this we define the parameters; 'flatness', 'roundness', 'smoothness' and 'ellipticity', evaluate each hardware with respect to these and rank them. © Published under licence by IOP Publishing Ltd.

The new generation of energy-dispersive X-ray (EDX) detectors with higher count rates than ever before, paves the way for a new approach to quantitative elemental analysis in the scanning transmission electron microscope. Here we demonstrate a method of calculating partial cross sections for use in quantifying EDX data, beneficial especially because of the simplicity of its implementation. Applying this approach to acid-leached PtCo catalyst nanoparticles leads to quantitative determination of the Pt surface enrichment.

An approach towards experiment design and optimisation is proposed for achieving improved accuracy of ADF STEM quantification. In particular, improved robustness to small sample mis-tilts can be achieved by optimising detector collection and probe convergence angles. A decrease in cross section is seen for tilted samples due to the reduction in channelling, resulting in a quantification error, if this is not taken into account. At a smaller detector collection angle the increased contribution from elastic scattering, which initially increases with tilt, can be used to offset the decrease in the TDS signal.

Quantitative atomic resolution annular dark field scanning transmission electron microscopy (ADF STEM) has become a powerful technique for nanoparticle atom-counting. However, a lot of nanoparticles provide a severe characterisation challenge because of their limited size and beam sensitivity. Therefore, quantitative ADF STEM may greatly benefit from statistical detection theory in order to optimise the instrumental microscope settings such that the incoming electron dose can be kept as low as possible whilst still retaining single-atom precision. The principles of detection theory are used to quantify the probability of error for atom-counting. This enables us to decide between different image performance measures and to optimise the experimental detector settings for atom-counting in ADF STEM in an objective manner. To demonstrate this, ADF STEM imaging of an industrial catalyst has been conducted using the near-optimal detector settings. For this experiment, we discussed the limits for atomcounting diagnosed by combining a thorough statistical method and detailed image simulations.

A new method of quantifying the HAADF STEM signal on absolute scale, building on the z-contrast nature of the technique, has been developed to address the problem of characterising nanoparticles to an atomic scale. Experimental images are scaled to a fraction of the incident beam intensity from a detector map. The integrated intensity of each individual atomic column is multiplied by the pixel area yielding a more imaging-parameter robust quantity, termed a scattering cross-section. Using this cross-section approach, and simulated reference data we show how it is possible to count the number of atoms in individual columns, in order to compare against theoretical 3-dimensional structures. All this is with the aim of trying to obtain as much information as possible from a single image of these beam sensitive samples. © Published under licence by IOP Publishing Ltd.

The atomic structure and morphology of gold nanoparticles have been studied using High-Resolution Transmission Electron Microscopy (HRTEM). The structural transformations of these particles have been probed through ex-situ annealing experiments, yielding population statistics on structure as a function of particle size and annealing temperature. The results show that for an original structurally heterogeneous particle population, there is a rise in the percentage of particles with the decahedral morphology as annealing temperature is increased. This can be correlated with a reduction in the number of icosahedral particles as a function of annealing temperature. HRTEM imaging following low temperature annealing reveals a range of modified and distorted decahedral particles, giving insight into the temperature threshold of the solid state transformation and the microstructural processes occurring.