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Zinc oxide (ZnO) is a largely investigated semiconducting nanomaterial for photocatalytic applications and is an excellent active layer candidate in photovoltaics. Among native defects, having a primary role in ZnO optoelectronic properties, the influence of nearly ubiquitous planar faults of wurtzite sequences in ultrasmall (≤5 nm) nanocrystals (NCs) remains poorly understood. Here, we present a thorough study of ZnO NCs prepared under morphological control of covalently grafted vinyltrimethoxysilane (VTMS) and exhibiting either narrowing or widening of the band gap upon NCs downsizing, depending on the NC growth rate. By using synchrotron X-ray total scattering data, atomistic models and the Debye Scattering Equation (DSE) method, complemented by spectroscopic (FTIR and UV–vis) investigations, we provide a comprehensive quantitative picture in which effects from planar defects are disentangled from those due to NC size, morphology, and lattice strain (here controlled by preferential binding of VTMS on the ZnO basal faces). When faults occur in high concentration (linear density up to 1.6 × 10⁶ cm–¹), NCs exhibit optical band gap narrowing (3.27 eV vs 3.37 eV in bulk ZnO), whereas gap widening (3.52 eV) is observed at a lower density (0.8 × 10⁶ cm–¹), at which quantum-size confinement effects prevail. Supported by photoluminescence and photodegradation experiments, surface defect passivation by VTMS, affecting visible emissions and photocatalytic properties of ZnO, is also discussed in relation to silane coating and fault-driven bandgap. This work sheds light on the complex interplay among planar defects, quantum size effect, and surface modifications in ultrasmall ZnO NCs and on the importance of advanced X-ray total scattering methods toward atomically precise control of defects in nanostructures.

Highly anisotropic colloidal CsPbBr3 nanoplatelets (NPLs) represent an appealing class of colloidal quantum wells with enhanced light emissivity. Strong quantum confinement imposed by the small platelet thickness and atomic flatness gives rise to enhanced oscillator strength, higher exciton binding energy, and narrow emission linewidth. While discrete thicknesses manifest themselves in discrete bandgap energies, fine-tuning of the emission energy can be achieved by compositional modulations. Here we address one of the most debated aspects of perovskite nanoplatelets: their crystal structure. Starting with the direct imaging by high-resolution electron microscopy (providing a clue on the pseudocubic faceting of the NPLs), we focus the study on X-ray total scattering techniques, based on the Debye scattering equation (DSE) approach, to obtain better atomistic insight. The nanoplatelets are six-monolayers thick and exhibit an orthorhombic structure. A thorough structure–morphology characterization unveils a specific orientation of the axial and equatorial bromides of the PbBr6 octahedra versus the NPLs thickness; we found that {010} and {101} planes of the orthorhombic CsPbBr3 lattice (Pnma space group) correspond to the six facets of the NPL, with basal planes being of {101} type. The NPLs undergo a lattice relaxation in comparison to cuboidal CsPbBr3 NCs; the major deformation is observed in the axial direction, which suggests a structural origin of the higher compliance along the b axis. The DSE-based analysis also supports a CsBr surface termination model, with half Cs sites and a half (or slightly more) Br sites vacant., ACS Nano, 13 (12), ISSN:1936-0851, ISSN:1936-086X

Realisation of the tetragonal phase of $Cs_2CuCl_4$ is possible using specific crystal growth conditions at a temperature below $281K$. This work deals with the comparison of the magnetic susceptibility and the magnetization of this new tetragonal compound with the magnetic behaviour of tetragonal $Cs_2CuCl_{2.9}Br_{1.1}$, $Cs_2CuCl_{2.5}Br_{1.5}$, $Cs_2CuCl_{2.2}Br_{1.8}$ and presents consistent results for such quasi $2-D$ antiferromagnets. Structural investigation at low temperature for $Cs_2CuCl_{2.2}Br_{1.8}$ shows no phase transition. The structure remains in the tetragonal symmetry $I4/mmm$. Furthermore, several magnetic reflections corresponding to the propagation vector $k = (0, 0, 0)$ are observed for this tetragonal compound through neutron diffraction experiments below the magnetic phase transition at $T_N = 11.3K$ confirming its antiferromagnetic nature., Comment: Preprint

Recent literature on Pt/CeO2 catalysts reveals that ionic Pt species could be incorporated into the CeO2 lattice. Here we present a detailed study of Pt segregation in air and under a reducing atmosphere conducted on thermally treated samples by high resolution X ray diffraction (XRD) and X ray absorption spectroscopy. We further perform a kinetic study by in situ XRD measurements with the aim of estimating the activation energy for Pt cluster segregation and coalescence in air which was found to be ~3.88 eV. This high activation energy indicates that Pt clusters are strongly anchored on the CeO2 surface and that their mobility is activated only at >900 °C. We clearly show the correlation between the nature of the segregated Pt particles and the applied thermal treatment for Pt/CeO2 nanomaterials prepared by the wet chemical route. On the basis of thorough characterization we present a possible segregation pathway under oxidizing conditions as opposed to a mere surface reduction during a reducing treatment leading to the coalescence of less anchored Pt. The catalytic performances confirm the remarkable activity and thermal stability of entities obtained via an incorporation–segregation mechanism.

Ceria-based materials have many interesting applications including catalysis, fuel cells, and biology. The size- and shape-dependent changes in the catalytic properties of nanoceria are often attributed to stabilization Ce3+ defects on the nanoparticle surface. In this paper, we have performed a systematic analysis of the structure of polyhedral CeO2 nanoparticles of 2–10 nm, under ambient conditions, using a combination of transmission electron microscopy, X-ray diffraction, and X-ray spectroscopy at Ce K- and L-edges. We reveal that under ambient conditions Ce3+ concentration does not depend on the size; however, the unit cell parameter and the pseudo Debye–Waller factors systematically change due to size-dependent surface contribution. The presence of Ce3+ traces relates to the use of Ce3+ precursors during synthesis. Exposure of nanoparticles to an intense beam of X-ray radiation causes reduction of Ce4+ ions, the extent of which is size-dependent.

Nanocrystalline TiO(2) samples, prepared for smart textiles applications by the sol-gel technique in acidic or basic media, have been characterized by synchrotron X-ray powder diffraction and total scattering methods based on a fast implementation of the Debye function and original algorithms for sampling interatomic distances. Compared to the popular and widely used Rietveld-based approaches, our method is able to simultaneously model both Bragg and diffuse contributions and to quantitatively extract either sizes and size distribution information from the experimental data. The photocatalytic activity of the investigated samples is here systematically correlated to the average sizes and size distributions of anisotropically shaped coherent domains, modeled according to bivariate populations of nanocrystals grown along two normal directions.