Single-particle reconstruction can be used to perform three-dimensional (3D) imaging of homogeneous populations of nano-sized objects, in particular viruses and proteins. Here, it is demonstrated that it can also be used to obtain 3D reconstructions of heterogeneous populations of inorganic nanoparticles. An automated acquisition scheme in a scanning transmission electron microscope is used to collect images of thousands of nanoparticles. Particle images are subsequently semi-automatically clustered in terms of their properties and separate 3D reconstructions are performed from selected particle image clusters. The result is a 3D dataset that is representative of the full population. The study demonstrates a methodology that allows 3D imaging and analysis of inorganic nanoparticles in a fully automated manner that is truly representative of large particle populations.

Synthesis of Ni and Zn substituted nano-greigite, Fe3S4, is achieved from single source diethyldithiocarbamato precursor compounds, producing particles typically 50–100 nm in diameter with plate-like pseudohexagonal morphologies. Up to 12 wt.% Ni is incorporated into the greigite structure, and there is evidence that Zn is also incorporated but Co is not substituted into the lattice. The Fe L3 X-ray absorption spectra for these materials have a narrow single peak at 707.7 eV and the resulting main X-ray magnetic circular dichroism (XMCD) has the same sign at 708.75 eV. All XMCD spectra also have a broad positive feature at 711 eV, a characteristic of covalent mixing. The greigite XMCD spectra contrast with the three clearly defined XMCD site specific peaks found in the ferrite spinel, magnetite. The Fe L2,3X-ray absorption spectra and XMCD spectra of the greigite reflect and reveal the high conductivity of greigite and the very strong covalency of the Fe–S bonding. The electron hopping between Fe3+ and Fe2+ on octahedral sites results in an intermediate oxidation state of the Fe in the Oh site of Fe2.5+ producing an effective formula of [Fe3+ ↑]A-site[2Fe2.5+ ↓]B-siteS42–]. The Ni L2,3 X-ray absorption spectra and XMCD reveal substitution on the Oh site with a strongly covalent character and an oxidation state <Ni1.5+ in a representative formula [Fe3+ ↑]A[[(2 – x)Fe2.5+ ↓][Nix1.5+]]BS42–.

A new method to perform X-ray absorption correction for spherical particles in quantitative energy-dispersive X-ray spectroscopy in the scanning transmission electron microscope is presented. An absorption correction factor is derived and simulated data is presented encompassing a range of X-ray absorption conditions. Theoretical calculations are compared with experimental data of X-ray counts from Au nanoparticles to verify the derived methodology. The effect of detector elevation angle is considered and a comparison with thin-film absorption correction is included.

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.

Single wall carbon nanotubes (SWCNTs) and liquid-phase exfoliated multilayer graphene (MLG) material thin films were assembled at a polarizable organic/water interface. A simple, spontaneous route to functionalize/decorate the interfacial assembly of MLG and SWCNTs with noble metal nanoparticles, at the interface between two immiscible electrolyte solutions (ITIES), is reported. The formation of MLG- or SWCNT-based metal nanocomposites was confirmed using various microscopic (scanning electron, transmission electron, and atomic force microscopy) and several spectroscopic (energy dispersive x-ray and Raman spectroscopy) techniques. Increasing the interfacial deposition time of the metal nanoparticles on the assembled low-dimensional carbon material increased the amount of the metal particles/structures, resulting in greater coverage of the MLG or SWCNTs with metal nanoparticles. This low-cost and convenient solution chemistry based impregnation method can serve as a means to prepare nanoscale carbonaceous material-based metal nanocomposites for their potential exploitation as electro-active materials, e.g., new generation catalysts or electrode materials.