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Binary nanocrystal superlattices, that is, ordered structures of two sorts of nanocolloids, hold promise for a series of functional materials with novel collective properties. Here we show that based on electron tomography a comprehensive, quantitative, three-dimensional characterization of these systems down to the single nanocrystal level can be achieved, which is key in understanding the emerging materials properties. On four binary lattices composed of PbSe, CdSe, and Au nanocrystals, we illustrate that ambiguous interpretations based on two-dimensional transmission electron microscopy can be prevented, nanocrystal sizes and superlattice parameters accurately determined, individual crystallographic point and plane defects studied, and the order/disorder at the top and bottom surfaces imaged. Furthermore, our results suggest that superlattice nucleation and growth occurred at the suspension/air interface and that the unit cells of some lattices are anisotropically deformed upon drying.

Two practical methods are proposed to measure the tortuosity of a porous or permeable material from its tomographic reconstruction. The first method is based on the direct measurement of the shortest distance between two points in the pores, and the second is based on the geodesic reconstruction of the pore or permeation space. Unlike the first method, the second can be directly applied to gray-tone tomograms, without the need of a segmentation step. The methods are illustrated with an electron tomogram of clay/plastic nanocomposite, an X-ray microtomogram of sandstone, and a series of model morphologies consisting of penetrable random spheres. For the latter series, the measured tortuosities compare very well with those derived independently from the theoretical effective diffusion coefficients. V

Electron tomography and image analysis are combined to characterize ordered mesoporous silica SBA-15. The morphology of the mesopores with average diameter 6 nm is analyzed in terms of cylinders having variable radii and centers that are statistically centered on the points of a distorted hexagonal lattice. The variations in the mesopore centers and radii add up and result in pore wall corrugation with amplitude of 1.6 nm. The correlation length of the corrugation along the pore axis was found to be 4-5 nm. The amplitude of the corrugation compared well with the 1.9 nm thick microporous corona obtained from X-ray diffraction (XRD). In general, the present approach provides a detailed microscopic 3D model of nanostructured materials that complements macroscopic measurements such as physisorption and XRD.

A major cause of supported metal catalyst deactivation is particle growth by Ostwald ripening. Nickel catalysts, used in the methanation reaction, may suffer greatly from this through the formation of [Ni(CO)4 ]. By analyzing catalysts with various particle sizes and spatial distributions, the interparticle distance was found to have little effect on the stability, because formation and decomposition of nickel carbonyl rather than diffusion was rate limiting. Small particles (3-4 nm) were found to grow very large (20-200 nm), involving local destruction of the support, which was detrimental to the catalyst stability. However, medium sized particles (8 nm) remained confined by the pores of the support displaying enhanced stability, and an activity 3 times higher than initially small particles after 150 h. Physical modeling suggests that the higher [Ni(CO)4 ] supersaturation in catalysts with smaller particles enabled them to overcome the mechanical resistance of the support. Understanding the interplay of particle size and support properties related to the stability of nanoparticles offers the prospect of novel strategies to develop more stable nanostructured materials, also for applications beyond catalysis.

A main reason for catalyst deactivation in supported catalysts for methanol synthesis is copper particle growth. We have functionalized the support surface in order to suppress the formation and/or transport of mobile copper species and thereby catalyst deactivation. A Stöber silica support was functionalized by treatment with aminopropyl­triethoxysilane, which introduces aminopropyl groups on the surface. Copper was deposited on both unfunctionalized and functionalized Stöber silica via incipient wetness impregnation with aqueous copper nitrate solutions followed by drying and calcination. Similar particle size distributions (1–5 nm) were obtained for both supports by changing the flow of N2 to a flow of 2% NO/N2 during calcination of the unfunctionalized and amine-functionalized silica, respectively. The effect of support functionalization with aminopropyl groups was an increased stability in the methanol synthesis reaction (40 bar, 260 °C, 23% CO/7% CO2/60% H2/10% Ar, 3% CO x conversion) due to more limited copper particle growth as determined by transmission electron microscopy (TEM). Changing the interparticle distance did not have an influence on the deactivation rate, while the addition of few very large copper particles did, indicating that Ostwald ripening was most probably the dominant particle growth mechanism for these samples. In situ TEM images showed the contact angle between the reduced copper particles and the support. As shape and size was similar on silica as on amine-functionalized silica, the thermodynamic stability of the copper particles was unaltered. The driving force for copper particle growth was thus unchanged upon functionalization. We therefore suggest that Ostwald ripening in methanol synthesis catalysts was retarded by inhibiting the transport of copper species over the support surface. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) revealed a decrease in the number of surface groups (hydroxyl, methoxy, and aminopropyl) upon functionalization because aminopropyl­triethoxysilane reacted with multiple hydroxyl groups. Because of that, the distance between neighboring functional groups was increased, suppressing the mobility of Ostwald ripening species from one copper particle to another.

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Time-resolved small-angle X-ray scattering (SAXS) measurements performed during the formation of tetraethyl orthosilicate (TEOS) based silica gels in alcohol with 3-(2-aminoethylamino)propyltrimethoxysilane (EDAS) as an additive are reported. The measurements reveal no discontinuity of the nanostructure at the gel point. A chemically induced spinodal phase separation is found to give a coherent picture of the collected data. Increasing the amount of EDAS induces the phase separation on a smaller length scale, which finally leads to a modified gel morphology. The SAXS measurements and the electron micrographs associated with the dry gels could be interpreted in terms of the suggested wet gel formation mechanism.