A cell design for correlative hard X-ray nanoprobe and electron microscopy studies of catalysts under in situ conditions.

To improve the understanding of catalysts, and ultimately the ability to design better materials, it is crucial to study them during their catalytic active states. Using in situ or operando conditions allows insights into structure-property relationships, which might not be observable by ex situ characterization. Spatially resolved X-ray fluorescence, X-ray diffraction and X-ray absorption near-edge spectroscopy are powerful tools to determine structural and electronic properties, and the spatial resolutions now achievable at hard X-ray nanoprobe beamlines make them an ideal complement to high-resolution transmission electron microscopy studies in a multi-length-scale analysis approach. The development of a system to enable the use of a commercially available gas-cell chip assembly within an X-ray nanoprobe beamline is reported here. The novel in situ capability is demonstrated by an investigation of the redox behaviour of supported Pt nanoparticles on ceria under typical lean and rich diesel-exhaust conditions; however, the system has broader application to a wide range of solid-gas reactions. In addition the setup allows complimentary in situ transmission electron microscopy and X-ray nanoprobe studies under identical conditions, with the major advantage compared with other systems that the exact same cell can be used and easily transferred between instruments. This offers the exciting possibility of studying the same particles under identical conditions (gas flow, pressure, temperature) using multiple techniques.

Strain effects in core-shell PtCo nanoparticles: a comparison of experimental observations and computational modelling.

Strain in Pt nanoalloys induced by the secondary metal has long been suggested as a major contributor to the modification of catalytic properties. Here, we investigate strain in PtCo nanoparticles using a combination of computational modelling and microscopy experiments. We have used a combination of molecular dynamics (MD) and large-scale density functional theory (DFT) for our models, alongside experimental work using annular dark field scanning transmission electron microscopy (ADF-STEM). We have performed extensive validation of the interatomic potential against DFT using a Pt568Co18 nanoparticle. Modelling gives access to 3 dimensional structures that can be compared to the 2D ADF-STEM images, which we use to build an understanding of nanoparticle structure and composition. Strain has been measured for PtCo and pure Pt nanoparticles, with MD annealed models compared to ADF-STEM images. Our analysis was performed on a layer by layer basis, where distinct trends between the Pt and PtCo alloy nanoparticles are observed. To our knowledge, we show for the first time a way in which detailed atomistic simulations can be used to augment and help interpret the results of ADF-STEM strain mapping experiments, which will enhance their use in characterisation towards the development of improved catalysts.

Predicting the Oxygen-Binding Properties of Platinum Nanoparticle Ensembles by Combining High-Precision Electron Microscopy and Density Functional Theory.

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 morphological diversity in real commercial oxygen reduction reaction (ORR) catalysts used in fuel-cell cathodes. Here we introduce an approach that combines 3D nanoparticle structures obtained from high-throughput high-precision electron microscopy with density functional theory. Discrepancies between experimental observations and cuboctahedral/truncated-octahedral particles are revealed and discussed 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.

Quantitative Energy-Dispersive X-Ray Analysis of Catalyst Nanoparticles Using a Partial Cross Section Approach.

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.

Tomographic heating holder for in situ TEM: study of Pt/C and PtPd/Al2O3 catalysts as a function of temperature.

A tomographic heating holder for transmission electron microscopy that can be used to study supported catalysts at temperatures of up to ~1,500°C is described. The specimen is placed in direct thermal contact with a tungsten filament that is oriented perpendicular to the axis of the holder without using a support film, allowing tomographic image acquisition at high specimen tilt angles with minimum optical shadowing. We use the holder to illustrate the evolution of the active phases of Pt nanoparticles on carbon black and PtPd nanoparticles on γ-alumina with temperature. Particle size distributions and changes in active surface area are quantified from tilt series of images acquired after subjecting the specimens to increasing temperatures. The porosity of the alumina support and the sintering mechanisms of the catalysts are shown to depend on distance from the heating filament.

High-precision atomic-scale strain mapping of nanoparticles from STEM images.

Strain is a crucial factor that influences the physicochemical properties of nanoparticles. Being able to precisely measure strain is important in understanding the intrinsic mechanism of the enhanced performance of nanoparticles. Techniques that have been developed for strain analysis using scanning transmission electron microscopy (STEM) images can be categorized into diffraction-based method and imaging-based method. Here, using image simulation techniques, it is found that the measured two-dimensional (2D) displacements from annular dark field (ADF) STEM images of a nanoparticle are a good approximation to a projection of the actual three-dimensional (3D) displacements. A methodology for deformation analysis is presented which is based on the detection of atomic columns from atomic-resolution STEM images in real space. Elastic deformation parameters such as strain are usually defined on the basis of a continuum of deformation. The appropriateness of various deformation parameters for atomic-scale investigation on STEM images is explored and a method for determining these is presented. We found that the local lattice parameter and principal strain components are the most physically meaningful parameters to express the materials distortion behaviour. Apart from the local lattice parameter, the other deformation parameters such as normal strains, shear strains and displacements, heavily rely on the choice of reference lattice. It is also found that different reference grids add a series of uniform offsets to these strain variations. Finally, this approach is applied to a PtCo3 bimetallic nanoparticle to quantify its deformation behaviour.

Visualization and Chemical Characterization of the Cathode Electrolyte Interphase Using He-Ion Microscopy and In Situ Time-of-Flight Secondary Ion Mass Spectrometry.

Unstable cathode electrolyte interphase (CEI) formation increases degradation in high voltage Li-ion battery materials. Few techniques couple characterization of nano-scale CEI layers on the macroscale with in situ chemical characterization, and thus, information on how the underlying microstructure affects CEI formation is lost. Here, the process of CEI formation in a high voltage cathode material, LiCoPO4, has been investigated for the first time using helium ion microscopy (HIM) and in situ time-of-flight (ToF) secondary ion mass spectrometry (SIMS). The combination of HIM and Ne-ion ToF-SIMS has been used to correlate the cycle-dependent morphology of the CEI layer on LiCoPO4 with a local cathode microstructure, including position, thickness, and chemistry. HIM imaging identified partial dissolution of the CEI layer on discharge resulting in in-homogenous CEI coverage on larger LiCoPO4 agglomerates. Ne-ion ToF-SIMS characterization identified oxyfluorophosphates from HF attack by the electrolyte and a Li-rich surface region. Variable thickness of the CEI layer coupled with inactive Li on the surface of LiCoPO4 electrodes contributes to severe degradation over the course of 10 cycles. The HIM-SIMS technique has potential to further investigate the effect of microstructures on CEI formation in cathode materials or solid electrolyte interphase formation in anodes, thus aiding future electrode development.

γ-Alumina-supported Pt17 cluster: controlled loading, geometrical structure, and size-specific catalytic activity for carbon monoxide and propylene oxidation.

Although Pt is extensively used as a catalyst to purify automotive exhaust gas, it is desirable to reduce Pt consumption through size reduction because Pt is a rare element and an expensive noble metal. In this study, we successfully loaded a Pt17 cluster on γ-alumina (γ-Al2O3) (Pt17/γ-Al2O3) using [Pt17(CO)12(PPh3)8]Cl n (n = 1, 2) as a precursor. In addition, we demonstrated that Pt is not present in the form of an oxide in Pt17/γ-Al2O3 but instead has a framework structure as a metal cluster. Moreover, we revealed that Pt17/γ-Al2O3 exhibits higher catalytic activity for carbon monoxide and propylene oxidation than γ-Al2O3-supported larger Pt nanoparticles (PtNP/γ-Al2O3) prepared using the conventional impregnation method. Recently, our group discovered a simple method for synthesizing the precursor [Pt17(CO)12(PPh3)8]Cl n . Furthermore, Pt17 is a Pt cluster within the size range associated with high catalytic activity. By combining our established synthesis and loading methods, other groups can conduct further research on Pt17/γ-Al2O3 to explore its catalytic activities in greater depth.

Understanding the mechanochemical synthesis of the perovskite LaMnO3 and its catalytic behaviour.

Mechanochemistry offers a solventless, 'waste free' route to preparing metal oxide catalysts, however, there is limited information on the chemical steps involved. In this work, the perovskite LaMnO3 has been successfully synthesized via mechanochemistry from metal oxide powders, La2O3 and Mn2O3, at room temperature, using a planetary ball mill. Separate ex situ'time slices' were taken during the milling procedure to provide insights into the underlying chemistry. The crystalline material was assessed using XRD, which identified 100% perovskite phase after 3 h of milling. Conversely, characterization by X-ray absorption spectroscopy (XAS) at both the Mn K-edge and La L3-edge provides a very different picture. The XAS data shows that there are significant structural alterations as early as 30 min of milling, with the La precursor dispersed over Mn2O3. Increasing milling time then allows for mechanical activation of both precursors and the formation of powdered LaMnO3, with no calcination step required. The XAS highlights that there is a significant amount of amorphous, oxygen deficient, content even when XRD has identified 100% perovskite phase. The samples were tested for the decomposition of the environmental pollutant N2O; at a milling time of 3 h, the LaMnO3 catalyst displays a much early onset production of N2 compared to a traditional sol-gel synthesized LaMnO3, resulting from increased oxygen deficiency at the surface, confirmed by XPS and STEM-EELS. This is an encouraging sign that mechanochemical routes can be harnessed to provide a sustainable route to preparing mixed metal oxide catalysts with enhanced catalytic performance.

Three-dimensional shapes and structures of lamellar-twinned fcc nanoparticles using ADF STEM.

Small particles with face-centred cubic structures can have non-single-crystallographic shapes. Here, an approach based on annular dark-field scanning transmission electron microscopy (STEM) is used to obtain information about the crystal sub-units that make up supported and unsupported twinned Pt, Pt alloy and Au nanoparticles. The three-dimensional shapes of two types of lamellar-twinned particles (LTPs) of Pt are obtained using high-angle annular dark-field STEM. Possible growth mechanisms of the LTPs and origins for the contrast features in the recorded images are discussed.

Determining EDS and EELS partial cross-sections from multiple calibration standards to accurately quantify bi-metallic nanoparticles using STEM.

Spectroscopic signals such as EDS and EELS provide an effective way of characterising multi-element samples such as Pt-Co nanoparticles in STEM. The advantage of spectroscopy over imaging is the ability to decouple composition and mass-thickness effects for thin samples, into the number of various types of atoms in a sample. This is currently not possible for multi element samples using conventional ADF quantification techniques alone. With recent developments in microscope hardware and software, it is now possible to acquire the ADF, EDS and EELS signals simultaneously and at high speed. However, the methods of quantifying the signals emitted from the sample vary greatly. Most approaches use pure-element standards in the form of needles, nanoparticles and wedges to quantify the spectroscopic signal into either partial scattering cross-sections, zeta-factors or k-factors. But self-consistency between the different methods has not been verified and the units of the quantification are not standardised. We present a robust approach for measuring and combining ADF, EDS and EELS signals using needle and nanoparticle standards in units of the partial scattering cross-section. The partial scattering cross-section allows an easy interpretation of the signals emitted from the sample and enables accurate atom-counting of the sample.

Ideal versus real: simulated annealing of experimentally derived and geometric platinum nanoparticles.

Platinum nanoparticles find significant use as catalysts in industrial applications such as fuel cells. Research into their design has focussed heavily on nanoparticle size and shape as they greatly influence activity. Using high throughput, high precision electron microscopy, the structures of commercially available Pt catalysts have been determined, and we have used classical and quantum atomistic simulations to examine and compare them with geometric cuboctahedral and truncated octahedral structures. A simulated annealing procedure was used both to explore the potential energy surface at different temperatures, and also to assess the effect on catalytic activity that annealing would have on nanoparticles with different geometries and sizes. The differences in response to annealing between the real and geometric nanoparticles are discussed in terms of thermal stability, coordination number and the proportion of optimal binding sites on the surface of the nanoparticles. We find that annealing both experimental and geometric nanoparticles results in structures that appear similar in shape and predicted activity, using oxygen adsorption as a measure. Annealing is predicted to increase the catalytic activity in all cases except the truncated octahedra, where it has the opposite effect. As our simulations have been performed with a classical force field, we also assess its suitability to describe the potential energy of such nanoparticles by comparing with large scale density functional theory calculations.

A simple algorithm for measuring particle size distributions on an uneven background from TEM images.

Nanoparticles have a wide range of applications in science and technology. Their sizes are often measured using transmission electron microscopy (TEM) or X-ray diffraction. Here, we describe a simple computer algorithm for measuring particle size distributions from TEM images in the presence of an uneven background. The approach is based on adaptive thresholding, making use of local threshold values that change with spatial coordinate. The algorithm allows particles to be detected and characterized with greater accuracy than using more conventional methods, in which a global threshold is used. Its application to images of heterogeneous catalysts is presented.

Core@shell bimetallic nanoparticle synthesis via anion coordination.

Core@shell structured bimetallic nanoparticles are currently of immense interest due to their unique electronic, optical and catalytic properties. However, their synthesis is non-trivial. We report a new supramolecular route for the synthesis of core@shell nanoparticles, based on an anion coordination protocol--the first to function by binding the shell metal to the surface of the pre-formed primary metal core before reduction. The resultant gold/palladium and platinum/palladium core@shell nanoparticles have been characterized by aberration-corrected scanning transmission electron microscopy (as well as other techniques), giving striking atomic-resolution images of the core@shell architecture, and the unique catalytic properties of the structured nanoparticles have been demonstrated in a remarkable improvement of the selective production of industrially valuable chloroaniline from chloronitrobenzene.