Vanadium(IV) oxide thin films were synthesized via atmospheric pressure chemical vapor deposition by the reaction between vanadium(IV) chloride and ethyl acetate at 550 °C. The substrate was varied with films being deposited on glass, SnO2, and F-doped SnO2. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, UV–vis spectroscopy, scanning electron microscopy, and X-ray absorption near-edge structure. The influence of the electronic contribution of the substrate on the deposited VO2 film was found to be key to the functional properties observed. Highly electron-withdrawing substituents, such as fluorine, favored the formation of V5+ ions in the crystal lattice and so reduced the thermochromic properties. By considering both the structural and electronic contributions of the substrate, it is possible to establish the best substrate choices for the desired functional properties of the VO2 thin films synthesized.

Nanoparticles with nominal structures of Au@Ag (core@shell) and Au@Ag@Au (core@shell@shell) were prepared using the sequential citrate reduction technique and characterized using routine characterization techniques, including transmission electron microscopy. X-ray absorption spectroscopy was then carried out on the samples, and extended X-ray absorption fine structure (EXAFS) analysis was used to determine the structure of the systems. The results of the routine techniques and the X-ray absorption spectroscopy were then compared. EXAFS analysis of the nanoparticles with the Au@Ag structure revealed very limited bimetallic interactions, supporting the assignment of a core@shell structure. EXAFS analysis of the nanoparticles with Au@Ag@Au structure showed an increased proportion of bimetallic interactions. Based on the colloid composition, the other characterization techniques and the chemistry of the system, these nanoparticles were interpreted as having an Au@Au/Ag-alloy structure. The EXAFS analyses corroborated the other characterization techniques and enabled the determination of the average-structure of the entire sample.

•Formation of cordierite ceramic was investigated using time-resolved techniques.•Addition of zinc oxide to zeolite B promote the transformation of cordierite.•Formation of ZnAl2O4, appears to promote the conversion to cordierite.•MgCr2O4 spinel phase detected along with cordierite in the cordierite glass system.•The MgCr2O4 formation seem to retard the conversion of the glass to cordierite system.Time-resolved combined scattering and spectroscopic techniques were used to understand in detail the formation of cordierite ceramic from two sources, (a) zeolite B and (b) cordierite glass systems. Time-resolved in situ combined EXAFS/XRD (at the Zn K-edge) investigation of the zinc oxide mixed zeolite B reveal that a series of transformations occur before the formation of cordierite ceramic. In particular the study revealed that addition of small amounts of zinc oxide promote the transformation of cordierite, through the formation of ZnAl2O4, at lower temperatures compared to the system without zinc oxide. Using in situ time-resolved SAXS/WAXS technique chromium doped in the cordierite glass system was investigated which revealed that, in addition to the formation of phase pure cordierite phase some amount of MgCr2O4 spinel phase are also produced.

Given emerging concerns about the bioavailability and toxicity of anthropogenic platinum compounds emitted into the environment from sources including vehicle emission catalysts (VEC), the platinum species present in selected North American sourced fresh and road-aged VEC were determined by Pt and Cl X-ray absorption spectroscopy. Detailed analysis of the Extended X-ray Absorption Fine Structure at the Pt L3 and L2 edges of the solid phase catalysts revealed mainly oxidic species in the fresh catalysts and metallic components dominant in the road-aged catalysts. In addition, some bimetallic components (Pt–Ni, Pt–Pd, Pt–Rh) were observed in the road-aged catalysts from supporting Ni-, Pd-, and Rh-K edge XAS studies. These detailed analyses allow for the significant conclusion that this study did not find any evidence for the presence of chloroplatinate species in the investigated solid phase of a Three Way Catalyst or Diesel Oxidation Catalysts.

We report the structural changes that occur during the thermal removal of organic template molecules that occlude the pores of small pore nanoporous zeolitic solids, AlPO-18, SAPO-18, CoAlPO-18, ZnAlPO-18 and CoSAPO-18. The calcination process is a necessary step in the formation of active catalysts. The studies performed using time-resolved High Resolution Powder Diffraction (HRPD) and High Energy X-ray Diffraction (HEXRD) techniques at various temperatures reveal that changes that take place are dependent on the type of heteroatom present in the nanoporous solids. While time-resolved HRPD shows clear changes in lattice parameters during the removal of physisorbed water molecules and subsequent removal of the organic template, HEXRD data show changes in various near neighbour distances in AlPO-18, SAPO-18, CoAlPO-18, CoSAPO-18 and ZnAlPO-18 during the calcination process. In particular HEXRD reveals the presence of water molecules coordinated to Al(III) ions in the as-synthesised materials. Upon removal of the template and water, these solids show contraction in the cell volume at elevated temperatures while first and second neighbour distances remained almost unchanged.

The PdO–Pd phase transformation in a 4 wt% Pd/Al2O3 catalyst has been investigated using in situ X-ray absorption spectroscopy (XAS) and in situ X-ray total scattering (also known as high-energy X-ray diffraction) techniques. Both the partial and total pair distribution functions (PDF) from these respective techniques have been analysed in depth. New information from PDF analysis of total scattering data has been garnered using the differential PDF (d-PDF) approach where only correlations orginating from PdO and metallic Pd are extracted. This method circumvents problems encountered in characerising the catalytically active components due to the diffuse scattering from the disordered γ-Al2O3 support phase. Quantitative analysis of the palladium components within the catalyst allowed for the phase composition to be established at various temperatures. Above 850 °C it was found that PdO had converted to metallic Pd, however, the extent of reduction was of the order ca. 70% Pd metal and 30% PdO. Complementary in situ XANES and EXAFS were performed, with heating to high temperature and subsequent cooling in air, and the results of the analyses support the observations, that residual PdO is detected at elevated temperatures. Hysteresis in the transformation upon cooling is confirmed from XAS studies where reoxidation occurs below 680 °C.

The phosphine-stabilized gold cluster [Au6(Ph2P-o-tolyl)6](NO3)2 is converted into an active nanocatalyst for the oxidation of benzyl alcohol through low-temperature peroxide-assisted removal of the phosphines, avoiding the high-temperature calcination process. The process was monitored using in situ X-ray absorption spectroscopy, which revealed that after a certain period of the reaction with tertiary butyl hydrogen peroxide, the phosphine ligands are removed to form nanoparticles of gold which matches with the induction period seen in the catalytic reaction. Density functional theory calculations show that the energies required to remove the ligands from the [Au6Ln]2+ increase significantly with successive removal steps, suggesting that the process does not occur at once but sequentially. The calculations also reveal that ligand removal is accompanied by dramatic rearrangements in the topology of the cluster core.Keywords: density functional theory; EXAFS; gold catalysts; molecular clusters; oxidation; X-ray absorption spectroscopy; XANES;

Zinc oxide (ZnO) is a wide bandgap semiconducting oxide with many potential applications in various optoelectronic devices such as light emitting diodes (LEDs) and field effect transistors (FETs). Much effort has been made to understand the ZnO structure and its defects. However, one major issue in determining whether it is Zn or O deficiency that provides ZnO its unique properties remains. X-ray absorption spectroscopy (XAS) is an ideal, atom specific characterization technique that is able to probe defect structure in many materials, including ZnO. In this paper, comparative studies of bulk and aqueous solution grown (≤90 °C) ZnO powders using XAS and x-ray pair distribution function (XPDF) techniques are described. The XAS Zn–Zn correlation and XPDF results undoubtedly point out that the solution grown ZnO contains Zn deficiency, rather than the O deficiency that were commonly reported. This understanding of ZnO short range order and structure will be invaluable for further development of solid state lighting and other optoelectronic device applications.Graphical abstractHighlights► ZnO powders have been synthesized through an aqueous solution method. ► Defect structure studied using XAS and XPDF. ► Zn–Zn correlations are less in the ZnO powders synthesized in solution than bulk. ► Zn vacancies are present in the powders synthesized. ► EXAFS and XPDF, when used complementary, are useful characterization techniques.

We followed the formation of metal ion substituted aluminophosphate, a redox molecular sieve, using a newly developed in situ simultaneous X-ray diffraction and X-ray absorption spectroscopic technique. The study showed that a cobalt–phosphorous network forms prior to the crystallisation.

Herein, we report the rapid single step hydrothermal synthesis of phase pure Bi2MoO6 (koechlinite) and Bi2Mo3O12, via a continuous hydrothermal flow synthesis (CHFS) reactor, which uses supercritical water of 375–450 °C at a pressure of 24.1 MPa as a crystallising medium. The product being obtained as highly crystalline nano-materials with high surface area. Simple variation in synthesis condition and appropriate solution stoichiometry were shown to be sufficient to select the phase of the product. The materials synthesised showed significant photcatalytic activity towards the decolourisation of methylene blue in comparison to a commercial gold standard photocatalyst.

Combination of in situRaman scattering with high-resolution XRD and XAS techniques has proven to be a powerful tool to elucidate the crystal growth of γ-Bi2MoO6 under hydrothermal conditions.

This paper reported results of in situ XANES/EXAFS studies of iron substituted AlPO-5. Fe-AlPO-5s were synthesized with different templates. These materials were also studied using XRD, SEM, EDX and in situ XRD/EXAFS. Here the aim is to investigate the influence of template on the state of iron in the as-synthesized and calcined form. It was found that, depending on the nature of template, the coordination of Fe(III) ions changes from octahedral to tetrahedral at different temperatures.Download full-size imageHighlights► Investigate the influence of template on the state of iron in the prepared samples. ► With different templates, coordination of Fe changes from VI to IV at different t°C. ► Different template doesn't affect the nature of Fe sites. ► Different template leads to different behaviors of Fe ions in redox chemistry. ► Different templates affect mechanism of crystal growth.

Here we demonstrate the power of in situ scattering techniques in the understanding of formation of nanoporous aluminosilicate and aluminophosphate materials. We utilised a number of X-ray techniques, in particular, in situ energy dispersive X-ray diffraction (EDXRD) and small angle and wide angle X-ray scattering (SAXS/WAXS) techniques for this purpose. The in situ SAXS measurements show the formation of homogeneous precursors in the size of ca. 10 nm, prior to the crystallization of LTA. The crystal size is estimated by fitting the SAXS patterns with an equation for a cubic particle, and it is revealed that the final crystal size of the LTA depends on the synthesis temperature. Whereas, the crystallisation of CoAlPO-5, occurs through the formation of poly-dispersed particles with an average size of the precursor particle of ca. 50 nm. Also shown the effect of temperature and structure directing organic cations on the production of CoAlPO-5 materials.

•We developed a new strategy to produce hierarchical TS-1, which is widely used for selective epoxidation reactions.•We utilized an inexpensive chitosan as a macro template to create macroscopic pores and to promote catalytic functionality.•We used a suite of techniques to establish the crystallinity, the titanium sites, and the hydrophilicity of the system.•We show pore enhancement, and relate hydrophilicity and porosity to catalytic functionality and product distribution.Hierarchical TS-1 zeolite was successfully prepared using chitosan as a sacrificial template. The X-ray diffraction showed that the presence of chitosan with the synthesis precursor had no deleterious effect on the crystallinity and phase purity of this zeolite. X-ray absorption spectroscopy at the Ti K-edge, FTIR and Raman spectroscopies revealed the titanium ions in the zeolite structure have predominantly tetrahedral coordination. However, it appears that the higher chitosan content in the synthesis gel imparted some hydrophilic character to the TS-1 system. Furthermore, the technique adopted for the preparation of the synthesis gel – e.g partially dried or fully dried – appears to affect the amount of framework titanium in the zeolite structure. The calcined form of the chitosan templated TS-1 zeolites exhibited higher cyclohexene conversion compared to the TS-1 material synthesised without this template, but these catalysts showed lower selectivity for cyclohexene epoxide.

The PdO–Pd phase transformation in a 4 wt% Pd/Al2O3 catalyst has been investigated using in situ X-ray absorption spectroscopy (XAS) and in situ X-ray total scattering (also known as high-energy X-ray diffraction) techniques. Both the partial and total pair distribution functions (PDF) from these respective techniques have been analysed in depth. New information from PDF analysis of total scattering data has been garnered using the differential PDF (d-PDF) approach where only correlations orginating from PdO and metallic Pd are extracted. This method circumvents problems encountered in characerising the catalytically active components due to the diffuse scattering from the disordered γ-Al2O3 support phase. Quantitative analysis of the palladium components within the catalyst allowed for the phase composition to be established at various temperatures. Above 850 °C it was found that PdO had converted to metallic Pd, however, the extent of reduction was of the order ca. 70% Pd metal and 30% PdO. Complementary in situ XANES and EXAFS were performed, with heating to high temperature and subsequent cooling in air, and the results of the analyses support the observations, that residual PdO is detected at elevated temperatures. Hysteresis in the transformation upon cooling is confirmed from XAS studies where reoxidation occurs below 680 °C.

We report the structural changes that occur during the thermal removal of organic template molecules that occlude the pores of small pore nanoporous zeolitic solids, AlPO-18, SAPO-18, CoAlPO-18, ZnAlPO-18 and CoSAPO-18. The calcination process is a necessary step in the formation of active catalysts. The studies performed using time-resolved High Resolution Powder Diffraction (HRPD) and High Energy X-ray Diffraction (HEXRD) techniques at various temperatures reveal that changes that take place are dependent on the type of heteroatom present in the nanoporous solids. While time-resolved HRPD shows clear changes in lattice parameters during the removal of physisorbed water molecules and subsequent removal of the organic template, HEXRD data show changes in various near neighbour distances in AlPO-18, SAPO-18, CoAlPO-18, CoSAPO-18 and ZnAlPO-18 during the calcination process. In particular HEXRD reveals the presence of water molecules coordinated to Al(III) ions in the as-synthesised materials. Upon removal of the template and water, these solids show contraction in the cell volume at elevated temperatures while first and second neighbour distances remained almost unchanged.

Combination of in situRaman scattering with high-resolution XRD and XAS techniques has proven to be a powerful tool to elucidate the crystal growth of γ-Bi2MoO6 under hydrothermal conditions.

We followed the formation of metal ion substituted aluminophosphate, a redox molecular sieve, using a newly developed in situ simultaneous X-ray diffraction and X-ray absorption spectroscopic technique. The study showed that a cobalt–phosphorous network forms prior to the crystallisation.