Few-Layered MoS2 Nanoparticles Covering Anatase TiO2 Nanosheets: Comparison between Ex Situ and In Situ Synthesis Approaches

MoS2/TiO2 nanostructures made of MoS2 nanoparticles covering TiO2 nanosheets have been synthesized, either via ex situ or in situ approaches. The morphology and structure of the MoS2/TiO2 hybrid nanostructures have been investigated and imaged by means of X-ray diffraction (XRD) analysis and high-resolution transmission electron microscopy (HRTEM), while the vibrational and optical properties have been investigated by Raman, Fourier-transform infrared (FTIR), and UV−visible (UV–vis) spectroscopies. Different stacking levels and MoS2 nanosheets distribution on TiO2 nanosheets have been carefully evaluated from HRTEM images. Surface sites on the main exposed faces of both materials have been established by means of in situ FTIR spectra of CO probe molecule adsorption. The results of the ex situ and in situ approaches are compared to underline the role of the synthesis processes affecting the morphology and structure of MoS2 nanosheets, such as curvature, surface defects, and stacking order. It will be shown that as a result of the in situ approach, the reactivity of the TiO2 nanosheets and hence, in turn, the MoS2–TiO2 nanosheets interaction are modified.

Few-Layered mos2 Nanoparticles Covering Anatase tio2 Nanosheets: Comparison Between Ex-Situ and in-Situ Synthesis Approaches

MoS2/TiO2 nanostructures made of MoS2 nanoparticles covering TiO2 nanosheets have been synthesized, either via ex-situ or in-situ approaches. Morphology and structure of MoS2/TiO2 hybrid nanostructures have been investigated and imaged by means of X-ray diffraction (XRD) analysis and high-resolution transmission electron microscopy (HRTEM), while the vibrational and the optical properties have been investigated by Raman, Fourier-transform infrared spectroscopy (FTIR) and UV−visible (UV-Vis) techniques. The different stacking degrees together with the size distribution of the MoS2 nanosheets, decorating the TiO2 nanosheets, have been carefully obtained from HRTEM images. The nature of the surface sites on the main exposed faces of both materials has been detected by means of in-situ FTIR spectra of adsorbed CO probe molecule. The results coming from the ex-situ and in-situ approaches will be compared, by highlighting the role of the synthesis processes in affecting morphology and structure of MoS2 nanosheets, including their curvature, surface defects, and stacking order. Some more, it will be shown that the in-situ approach is affecting the reactivity of the TiO2 nanosheets too, hence in turn affects the MoS2/TiO2 nanosheets interaction.

Ultra-Small Pd Nanoparticles on Ceria as an Advanced Catalyst for CO Oxidation

In this study, we demonstrate the preparation and characterization of small palladium nanoparticles (Pd NPs) on modified ceria support (Pd/CeO2) using wet impregnation and further reduction in an H2/Ar flow. The obtained particles had a good dispersion, but their small size made it difficult to analyze them by conventional techniques such as transmission electron microscopy (TEM) and X-ray powder diffraction (XRPD). The material demonstrated a high catalytic activity in the CO oxidation reaction: the 100% of CO conversion was achieved at ~50 °C, whereas for most of the cited literature, such a high conversion usually was observed near 100 °C or higher for Pd NPs. Diffuse reflectance infrared Fourier-transform (DRIFT) spectroscopy in combination with CO probe molecules was used to investigate the size and morphology of NPs and the ceria support. On the basis of the area ratio under the peaks attributed to bridged (B) and linear (L) carbonyls, high-dispersion Pd NPs was corroborated. Obtained results were in good agreement with data of X-ray absorption near edge structure analysis (XANES) and CO chemisorption measurements.

CO adsorption on graphite-like ZnO bilayers supported on Cu(111), Ag(111) and Au(111) surfaces

<div> <div> <div> <p>Graphitic-like ZnO bilayer films deposited on coinage metals, Cu(111), Ag(111), and Au(111) have been studied by density functional theory calculations including dispersion corrections. The scope is to compare on an equal footing the properties of the three systems and in particular the nature of the metal/oxide interface. To this end we have considered the adsorption of a CO probe molecule and the vibrational shifts induced by adsorption on ZnO/Cu(111), ZnO/Ag(111), and ZnO/Au(111) compared to adsorption on the unsupported ZnO bilayer and on the wurtzite ZnO surface. We find that while the interaction of ZnO with Ag and Au supports is dominated by dispersion interactions with little or no charge transfer at the interface, in the case of Cu a moderate electron transfer occurs towards the ZnO bilayer. As a consequence, while the stretching frequency of CO on ZnO/Au is blue-shifted, that on ZnO/Cu is red- shifted compared to free CO. CO on ZnO/Ag is intermediate. In all three cases, however, the ZnO bilayer is almost flat, with a modest rumpling found in the case of Cu as a consequence of the stronger chemical interaction. The results fully explain the CO vibrational shifts of CO on ZnO/Cu(111) [Schott, V. et al. Angew. Chem. Int. Ed. 2013, 52, 1-6] without implying major distortions in the supported film. </p> </div> </div> </div>

CO adsorption on graphite-like ZnO bilayers supported on Cu(111), Ag(111) and Au(111) surfaces

<div> <div> <div> <p>Graphitic-like ZnO bilayer films deposited on coinage metals, Cu(111), Ag(111), and Au(111) have been studied by density functional theory calculations including dispersion corrections. The scope is to compare on an equal footing the properties of the three systems and in particular the nature of the metal/oxide interface. To this end we have considered the adsorption of a CO probe molecule and the vibrational shifts induced by adsorption on ZnO/Cu(111), ZnO/Ag(111), and ZnO/Au(111) compared to adsorption on the unsupported ZnO bilayer and on the wurtzite ZnO surface. We find that while the interaction of ZnO with Ag and Au supports is dominated by dispersion interactions with little or no charge transfer at the interface, in the case of Cu a moderate electron transfer occurs towards the ZnO bilayer. As a consequence, while the stretching frequency of CO on ZnO/Au is blue-shifted, that on ZnO/Cu is red- shifted compared to free CO. CO on ZnO/Ag is intermediate. In all three cases, however, the ZnO bilayer is almost flat, with a modest rumpling found in the case of Cu as a consequence of the stronger chemical interaction. The results fully explain the CO vibrational shifts of CO on ZnO/Cu(111) [Schott, V. et al. Angew. Chem. Int. Ed. 2013, 52, 1-6] without implying major distortions in the supported film. </p> </div> </div> </div>

Can the state of platinum species be unambiguously determined by the stretching frequency of an adsorbed CO probe molecule?

The state of the platinum species may be mistaken based only on the value of the C–O stretching frequency due to overlapping regions of frequencies corresponding to different species.