Metallic nanoparticles are of great importance because of their unique physical, chemical, antimicrobial, diagnostic, therapeutic, biomedical, sensing, biosensing, catalytic and optical properties. Detailed knowledge of the atomic scale structure of these materials is essential for understanding their activities and for exploiting their potential. This paper reports structural studies of silicasupported silver, gold, palladium and platinum nanoparticles using X-ray diffraction and high-resolution transmission electron microscopy. Electron microscopy observation allowed the determination of nanoparticle sizes, which were estimated to be in the range of 45-470 Å , and their distribution. The obtained histograms exhibit a multimodal distribution of the investigated nanoparticle sizes. The X-ray diffraction data were analyzed using the Rietveld method in the form of Williamson-Hall plots, the PDFgui fitting procedure and model-based simulation. The Williamson-Hall plots provide evidence for the presence of strain in all investigated samples. The PDFgui fitting results indicate that the investigated nanoparticles consist of atomic clusters with different sizes and degrees of disorder as well as slightly different lattice parameters. The detailed structural characterization performed via model-based simulations proves that all samples exhibit a face-centered cubic type structure with paracrystalline distortion. The degree of disorder predicted by the paracrystalline theory is correlated with the sizes of the nanoparticles. The catalytic properties of the investigated noble metals are discussed in relation to their disordered structure. research papers J. Appl. Cryst. (2018). 51, 411-419 Karolina Jurkiewicz et al. Paracrystalline structure of metallic nanoparticles 415 research papers J. Appl. Cryst. (2018). 51, 411-419 Karolina Jurkiewicz et al. Paracrystalline structure of metallic nanoparticles 417 research papers J. Appl. Cryst. (2018). 51, 411-419 Karolina Jurkiewicz et al. Paracrystalline structure of metallic nanoparticles 419
The structures of the plastic crystal (PC), orientational glass (OTG), liquid (LQ) and ordinary glass (OG) phases of 1,6-anhydro-β-D-glucopyranose (levoglucosan) have been investigated using X-ray diffraction and molecular modeling. The experimental diffraction data in the forms of static structure factors and pair distribution functions are analyzed in reciprocal and real spaces and compared with results of model-based simulations. A new approach to modeling the structure of the disordered phases, taking into account the intermolecular scattering contribution in the form of sharp Bragg peaks, the slowly varying intensity associated with intramolecular correlations and the diffusive component resulting from structural disorder, is applied. In the case of the LQ and OG samples, reverse Monte Carlo simulations are also used. The PC and OTG phases show long-range ordering of the hexagonal close-packed (hcp)-type structure up to 120 Å with random orientation of the molecules. Assuming a rigid molecular skeleton, isotropic free rotations of the molecules about their geometrical center in full and limited angular ranges are generated in theoretical models of the structure. It is demonstrated that the adoption of free rotations of the molecules leads to the best fits to experimental data for each studied phase of levoglucosan. The diffraction patterns of the LQ and OG samples show a relatively sharp first peak originating from quasi-Bragg planes of the densely packed face-centered cubic (fcc) type molecular arrangement. Moreover, the slowly varied intensity component of LQ and OG is practically the same as that of PC and OTG, suggesting that the intramolecular structure of these four phases does not change. Interestingly, structural correlations for the disordered LQ and OG states extend surprisingly far, up to about 50 Å. In addition, for all levoglucosan phases investigated, the paracrystalline disorder imposed on the generated models resulted in better compliance with the experimental data.
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