energy-dispersive-x-ray-tomography-for-3d-elemental-mapping

Energy Dispersive X-ray Tomography for 3D Elemental Mapping of Individual Nanoparticles

Energy dispersive X-ray spectroscopy within the scanning transmission electron microscope (STEM) provides accurate elemental analysis with high spatial ...

University of Manchester

Significant elemental segregation is shown to exist within individual hollow silver-gold (Ag-Au) bimetallic nanoparticles obtained from the galvanic reaction between Ag particles and AuCl4(-). Three-dimensional compositional mapping using energy dispersive X-ray (EDX) tomography within the scanning transmission electron microscope (STEM) reveals that nanoparticle surface segregation inverts from Au-rich to Ag-rich as Au content increases. Maximum Au surface coverage was observed for nanoparticles with approximately 25 atom % Au, which correlates to the optimal catalytic performance in a three-component coupling reaction among cyclohexane carboxyaldehyde, piperidine, and phenylacetylene.

Correlating catalytic activity of Ag-Au nanoparticles with 3D compositional variations.

A new design of in situ liquid cells is demonstrated, providing the first nanometer resolution elemental mapping of nanostructures in solution. The technique has been applied to investigate dynamic liquid-phase synthesis of core-shell nanostructures and to simultaneously image the compositional distribution for multiple elements within the resulting materials.

Real-time imaging and local elemental analysis of nanostructures in liquids.

The passage of an electric current through graphite or few-layer graphene can result in a striking structural transformation, but there is disagreement about the precise nature of this process. Some workers have interpreted the phenomenon in terms of the sublimation and edge reconstruction of essentially flat graphitic structures. An alternative explanation is that the transformation actually involves a change from a flat to a three-dimensional structure. Here we describe detailed studies of carbon produced by the passage of a current through graphite which provide strong evidence that the transformed carbon is indeed three-dimensional. The evidence comes primarily from images obtained in the scanning transmission electron microscope using the technique of high-angle annular dark-field imaging, and from a detailed analysis of electron energy loss spectra. We discuss the possible mechanism of the transformation, and consider potential applications of 'three-dimensional bilayer graphene'.

Bilayer graphene formed by passage of current through graphite: evidence for a three-dimensional structure.

New AgAu tadpole nanocrystals were synthesized in a one-step reaction involving simultaneous galvanic replacement between Ag nanospheres and AuCl4(-)(aq.) and AuCl4(-)(aq.) reduction to Au in the presence of citrate. The AgAu tadpoles display nodular polycrystalline hollow heads, while their undulating tails are single crystals. The unusual morphology suggests an oriented attachment growth mechanism. Remarkably, a 1 nm thick Ag layer was found to segregate so as to cover the entire surface of the tadpoles. By varying the nature of the seeds (Au NPs), double-headed Au tadpoles could also be obtained. The effect of a number of reaction parameters on product morphology were explored, leading to new insights into the growth mechanisms and surface segregation behavior involved in the synthesis of bimetallic and anisotropic nanomaterials.

Surface Segregated AgAu Tadpole-Shaped Nanoparticles Synthesized Via a Single Step Combined Galvanic and Citrate Reduction Reaction.

In this work, a simple but powerful method for controlling the size and surface morphology of AgAu nanodendrites is presented. Control of the number of Ag nanoparticle seeds is found to provide a fast and effective route by which to manipulate the size and morphology of nanoparticles produced via a combined galvanic replacement and reduction reaction. A lower number of Ag nanoparticle seeds leads to larger nanodendrites with the particles' outer diameter being tunable in the range of 45-148 nm. The size and surface morphology of the nanodendrites was found to directly affect their catalytic activity. Specifically, we report on the activity of these AgAu nanodendrites in catalyzing the gas-phase oxidation of benzene, toluene and o-xylene, which is an important reaction for the removal of these toxic compounds from fuels and for environmental remediation. All produced nanodendrite particles were found to be catalytically active, even at low temperatures and low metal loadings. Surprisingly, the largest nanodendrites provided the greatest percent conversion efficiencies.

Controlling Size, Morphology, and Surface Composition of AgAu Nanodendrites in 15 s for Improved Environmental Catalysis under Low Metal Loadings.

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.

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

This paper presents an investigation of the limitations and optimisation of energy dispersive X-ray (EDX) tomography within the scanning transmission electron microscope, focussing on application of the technique to characterising the 3D elemental distribution of bimetallic AgAu nanoparticles. The detector collection efficiency when using a standard tomography holder is characterised using a tomographic data set from a single nanoparticle and compared to a standard low background double tilt holder. Optical depth profiling is used to investigate the angles and origin of detector shadowing as a function of specimen field of view. A novel time-varied acquisition scheme is described to compensate for variations in the intensity of spectrum images at each sample tilt. Finally, the ability of EDX spectrum images to satisfy the projection requirement for nanoparticle samples is discussed, with consideration of the effect of absorption and shadowing variations.

Article	Year
Correlating catalytic activity of Ag-Au nanoparticles with 3D compositional variations. Nano letters\| PubMed ID: 24579934	2014
Real-time imaging and local elemental analysis of nanostructures in liquids. Chemical communications (Cambridge, England)\| PubMed ID: 24831648	2014
Bilayer graphene formed by passage of current through graphite: evidence for a three-dimensional structure. Nanotechnology\| PubMed ID: 25354780	2014
Surface Segregated AgAu Tadpole-Shaped Nanoparticles Synthesized Via a Single Step Combined Galvanic and Citrate Reduction Reaction. Chemistry (Weinheim an der Bergstrasse, Germany)\| PubMed ID: 26227074	2015
Controlling Size, Morphology, and Surface Composition of AgAu Nanodendrites in 15 s for Improved Environmental Catalysis under Low Metal Loadings. ACS applied materials & interfaces\| PubMed ID: 26544682	2015
Quantitative Energy-Dispersive X-Ray Analysis of Catalyst Nanoparticles Using a Partial Cross Section Approach. Microscopy and microanalysis : the official journal of Microscopy Society of America, Microbeam Analysis Society, Microscopical Society of Canada\| PubMed ID: 26754480	2016
STEM-EDX tomography of bimetallic nanoparticles: A methodological investigation. Ultramicroscopy\| PubMed ID: 26780684	2016

Thomas J. A. Slater

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