Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 2. -- A fourier-transform infrared spectroscopy study of methanol adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methanol adsorbed at 295 K on ZnO/SiO 2, on reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methanol on ZnO/SiO2 gave methoxy species on ZnO and SiO, in addition to both strongly and weakly physisorbed methanol on SiO2. The corresponding adsorption of methanol on reduced Cu/ZnO/SiO2 also gave methoxy species on Cu and a small amount of bridging formate. Reaction of methanol with a reoxidised Cu/ZnO/SiO2 catalyst resulted in an enhanced quantity of methoxy species on Cu. Heating adsorbed species on Cu/ZnO/SiO2 at 393 K led to the loss of methoxy groups on Cu and the concomitant formation of formate species on both ZnO and Cu. The comparable reaction on a reoxidised Cu/ZnO/SiO2 catalyst gave an increased amount of formate species on ZnO and this correlated with an increased quantity of methoxy groups lost from Cu. An explanation is given in terms of adsorption of formate and formaldehyde species at special sites located at the copper/zinc oxide interface.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces: Part 1. -- A Fourier-transform infrared study of formic acid and formaldehyde adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

Fourier-transform infrared (FTIR) spectra are reported of formic acid and formaldehyde on ZnO/SiO2, reduced Cu/ZnO/SiO2 and reoxidised Cu/ZnO/SiO2 catalyst. Formic acid adsorption on ZnO/SiO2 produced mainly bidentate zinc formate species with a lesser quantity of unidentate zinc formate. Formic acid on reduced Cu/ZnO/SiO2 catalyst resulted not only in the formation of bridging copper formate structures but also in an enhanced amount of formate relative to that for ZnO/SiO2 catalyst. Formic acid on reoxidised Cu/ZnO/SiO2 gave unidentate formate species on copper in addition to zinc formate moieties. The interaction of formaldehyde with ZnO/SiO2 catalyst resulted in the formation of zinc formate species. The same reaction on reduced Cu/ZnO/SiO2 catalyst gave bridging formate on copper and a remarkable increase in the quantity of formate species associated with the zinc oxide. Adsorption of formaldehyde on a reoxidised Cu/ZnO/SiO2 catalyst produced bridging copper formate and again an apparent increase in the concentration of zinc formate species. An explanation in terms of the adsorption of molecules at special sites located at the interface between copper and zinc oxide is given.

Infrared study of CO, CO2, H2 and H2O interactions on potassium-promoted reduced and oxidised silica-supported copper catalysts

FTIR spectra are reported of CO, CO2, H2 and H2O on silica-supported potassium, copper and potassium-copper catalysts. Adsorption of CO on a potassium/silica catalyst resulted in the formation of complexed CO moieties. Whereas exposure of CO2 to the same catalyst produced bands ascribed to CO2 -, bidentate carbonate and complexed CO species. Fully oxidised copper/silica surfaces gave bands due to CO on CuO and isolated Cu2+ cations on silica. Addition of potassium to this catalyst removed a peak attributed to CO adsorption on isolated Cu2+ cations and red-shifted the maximum ascribed to CO adsorbed on CuO. For a reduced copper/silica catalyst bands due to adsorbed CO on both high and low index planes were red-shifted by 10 cm-1 in the presence of potassium, although the strength of the Cu - CO bond did not appear to be increased concomitantly. An explanation in terms of an electrostatic effect between potassium and adsorbed CO is forwarded. A small maximum at ca. 1510 cm-1 for the reduced catalyst increased substantially upon exposing CO to a reoxidised promoted catalyst. Correspondingly, CO2 adsorption allowed the identification of two distinct carboxylate species, one of which was located at an interfacial site between copper and potassium oxide. Carboxylate species reacted with hydrogen at 295 K, on a reduced copper surface, to produce predominantly unidentate formate on potassium. In contrast no interaction was detected on a reoxidised copper catalyst at 295 K until a fraction of the copper surface was in a reduced state. Furthermore the interaction of polar water molecules with carboxylate species resulted in a perturbation of this structure which gave lower C----O stretching frequencies.

A combined temperature-programmed reaction spectroscopy and Fourier-transform infrared spectroscopy study of CO2/H2 and CO/CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol-synthesis catalysts

The reaction of CO2 and H2 with ZnO/SiO2 catalyst at 295 K gave predominantly hydrogencarbonate on zinc oxide and a small quantity of formate was evolved after heating at 393 K. Elevation of the reaction temperature to 503 K enhanced the rate of formation of zinc formate species. Significantly these formate species decomposed at 573 K almost entirely to CO2 and H2. Even after exposure of CO2-H2 or CO-CO2-H2 mixtures to highly defected ZnO/SiO2 catalyst, the formate species produced still decomposed to give CO2 and H2. It was concluded that carboxylate species which were formed at oxygen anion vacancies on polar Zn planes were not significantly hydrogenated to formate. Consequently it was proposed that the non-polar planes on zinc oxide contained sites which were specific for the synthesis of methanol. The interaction of CO2 and H2 with reduced Cu/ZnO/SiO2 catalyst at 393 K gave copper formate species in addition to substantial quantities of formate created at interfacial sites between copper and zinc oxide. It was deduced that interfacial formate species were produced from the hydrogenation of interfacial bidentate carbonate structures. The relevance of interfacial formate species in the methanol synthesis reaction is discussed. Experiments concerning the reaction of CO2-H2 with physical mixtures of Cu/SiO2 and ZnO/SiO2 gave results which were simply characteristic of the individual components. By careful consideration of previous data a detailed proposal regarding the role of spillover hydrogen is outlined. Admission of CO to a gaseous CO2-H2 feedstock resulted in a considerably diminished amount of formate species on copper. This was ascribed to a combination of over-reduction of the surface and site-blockage.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 3. -- Fourier-transform infrared study of methyl formate adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methyl formate adsorbed at 295 K on ZnO/SiO2, reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methyl formate on ZnO/SiO2 gave adsorbed zinc formate species and strongly physisorbed molecular methanol on silica. The comparable reaction of methyl formate with reduced Cu/ZnO/SiO2 catalyst produced bridging formate species on copper and a diminished quantity of zinc formate relative to that formed on ZnO/SiO2 catalyst. This effect is explained in terms of site blockage on the ZnO surface by small copper clusters. Addition of methyl formate to a reoxidised Cu/ZnO/SiO2 catalyst produced a considerably greater amount of formate species on zinc oxide and methoxy groups on copper were detected. The increase in concentration of zinc formate species was rationalised in terms of rearrangement of unidentate copper formate species to become bonded to copper and zinc oxide sites located at the interface between these two components.

In situ observation of structural changes in polycrystalline silver catalysts by environmental scanning electron microscopy

Morphology changes induced in polycrystalline silver catalysts as a result of heating in either oxygen, water or oxygen-methanol atmospheres have been investigated by environmental scanning electron microscopy (ESEM), FT-Raman spectroscopy and temperature programmed desorption (TPD). The silver catalyst of interest consisted of two distinct particle types, one of which contained a significant concentration of sub-surface hydroxy species (in addition to surface adsorbed atomic oxygen). Heating the sample to 663 K resulted in the production of 'pin-holes' in the silver structure as a consequence of near-surface explosions caused by sub-surface hydroxy recombination. Furthermore, 'pin-holes' were predominantly found in the vicinity of surface defects, such as platelets and edge structures. Reaction between methanol and oxygen also resulted in the formation of 'pin-holes' in the silver surface, which were inherently associated with the catalytic process. A reaction mechanism is suggested that involves the interaction of methanol with sub-surface oxygen species to form sub-surface hydroxy groups. The sub-surface hydroxy species subsequently erupt through the silver surface to again produce 'pin-holes'.

Characterisation of SiO2-supported nickel catalysts for carbon dioxide reforming of methane

The CO2-methane reformation reaction over Ni/SiO2 catalysts has been extensively studied using a range of temperature-programmed techniques and characterisation of the catalysts by thermogravimetry (TG), X-ray diffraction (XRD) and electron microscopy (TEM). The results indicate a strong correlation between the microstructure of the catalyst and its performance. The role of both CO2 and CH4 in the reaction has been investigated and the role of methyl radicals in the reaction mechanism highlighted. A reaction mechanism involving dissociatively adsorbed CO2 and methyl radicals has been proposed.

Characterization of precursors to methanol synthesis catalysts Cu/ZnO system

The composition of a series of hydroxycarbonate precursors to copper/zinc oxide methanol synthesis catalysts prepared under conditions reported as optimum for catalytic activity has been studied. Techniques employed included thermogravimetry (TG), temperature-programmed decomposition (TPD), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman and FTIR spectroscopies. Evidence was obtained for various structural phases including hydrozincite, copper hydrozincite, aurichalcite, zincian malachite and malachite (the concentrations of which depended upon the exact Cu/Zn ratio used). Significantly, previously reported phases such as gerhardite and rosasite were not identified when catalysts were synthesized at optimum solution pH and temperature values, and after appropriate aging periods. Calcination of the hydroxycarbonate precursors resulted in the formation of catalysts containing an intimate mixture of copper and zinc oxides. Temperature-programmed reduction (TPR) revealed that a number of discrete copper oxide species were present in the catalyst, the precise concentrations of which were determined to be related to the structure of the catalyst precursor. Copper hydrozincite decomposed to give zinc oxide particles decorated by highly dispersed, small copper oxide species. Aurichalcite appeared to result ultimately in the most intimately mixed catalyst structure whereas zincian malachite decomposed to produce larger copper oxide and zinc oxide grains. The reason for the stabilization of small copper oxide and zinc oxide clusters by aurichalcite was investigated by using carefully selected calcination temperatures. It was concluded that the unique formation of an 'anion-modified' oxide resulting from the initial decomposition stage of aurichalcite was responsible for the 'binding' of copper species to zinc moieties.

A fourier-transform infrared study of CO2 and CO2/H2 interactions with caesium-doped copper catalysts

FTIR spectra are reported of CO2 and COi/Hi on a silica-supported caesium-doped copper catalyst. Adsorption of COj on a "caesium"/silica surface resulted in the formation of COj and complexed CO species. Exposure of CO2 to' a caesium-doped reduced copper catalyst produced not only these species but also two forms of adsorbed carboxylate giving bands at 1550, 1510, 1365 and 1345 cm"1. Reaction of carboxylate species with hydrogen at 388 K gave formate species on copper and caesium oxide in addition to methoxy groups associated with caesium oxide. Methoxy species were not detected on undoped copper catalyst suggesting that caesium may be a promoter for the methanol synthesis reaction. Methanol decomposition on a caesium-doped copper catalyst produced a small number of formate species on copper and caesium oxide. Methoxy groups on caesium oxide decomposed to CO and U.2, and subsequent reaction between CO and adsorbed oxygen resulted in carboxylate formation. Methoxy species located at interfacial sites appeared to exhibit unusual adsorption properties.

Influence of oxidation and reduction conditions upon the morphology of silica-supported polycrystalline silver catalysts

The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.

Efficient catalysts of zeolite nanocrystals grown with a preferred orientation on nanofibers

An innovative structure — nanozeolites (as shell) grown with preferred orientation on ceramic nanofibers (as core) was proposed. The Y-zeolite nanocrystals on TiO2 nanofibers exhibited superior ability to catalyze acetalization and carboxylation reaction, achieving high conversions to desired products with selectivity of 100% under moderate conditions.

Metal hexaborides with Sc, Ti or Mn

Comparison of well-determined single crystal data for stoichiometric, or near-stoichiometric, metal hexaborides con-firm previously identified lattice parameter trends using powder diffraction. Trends for both divalent and trivalent forms suggest that potential new forms for synthesis include Sc and Mn hexaborides. Density Functional Theory (DFT) calculations for KB6, CaB6, YB6, LaB6, boron octahedral clusters and Sc and Mn forms, show that the shapes of bonding orbitals are defined by the boron framework. Inclusion of metal into the boron framework induces a reduction in energy ranging from 1 eV to 6 eV increasing with ionic charge. For metals with d1 character, such a shift in energy brings a doubly degenerate band section along the G-M reciprocal space direction within the conduction bands tangential to the Fermi surface. ScB6 band structure and density of states calculations show directional and gap characteristics similar to those of YB6 and LaB6. These calculations for ScB6 suggest it may be possible to realize superconductivity in this compound if synthesized.

Role of particle size and composition in metal adsorption by solids deposited on urban road surfaces

Despite common knowledge that the metal content adsorbed by fine particles is relatively higher compared to coarser particles, the reasons for this phenomenon has gained little research attention. The research study discussed in the paper investigated the variations in metal content for different particle sizes of solids associated with pollutant build-up on urban road surfaces. Data analysis confirmed that parameters favourable for metal adsorption to solids such as specific surface area, organic carbon content, effective cation exchange capacity and clay forming minerals content decrease with the increase in particle size. Furthermore, the mineralogical composition of solids was found to be the governing factor influencing the specific surface area and effective cation exchange capacity. There is high quartz content in particles >150µm compared to particles <150µm. As particle size reduces below 150µm, the clay forming minerals content increases, providing favourable physical and chemical properties that influence adsorption.

Reply to comment on “Characterising metal build-up on urban road surfaces” by Egodawatta et al. (2013)

In the recent manuscript published by Egodawatta et al. (2013), the authors investigated the build-up process of heavy metals (HMs) associated with road-deposited sediment (RDS) on residential road surfaces, and presented empirical models for the prediction of both the surface loads and build-up rates of HMs on these surfaces...

Numerical characterization of the mechanical properties of metal nanowires

Nanowires (NWs) have attracted appealing and broad application owing to their remarkable mechanical, optical, electrical, thermal and other properties. To unlock the revolutionary characteristics of NWs, a considerable body of experimental and theoretical work has been conducted. However, due to the extremely small dimensions of NWs, the application and manipulation of the in situ experiments involve inherent complexities and huge challenges. For the same reason, the presence of defects appears as one of the most dominant factors in determining their properties. Hence, based on the experiments' deficiency and the necessity of investigating different defects' influence, the numerical simulation or modelling becomes increasingly important in the area of characterizing the properties of NWs. It has been noted that, despite the number of numerical studies of NWs, significant work still lies ahead in terms of problem formulation, interpretation of results, identification and delineation of deformation mechanisms, and constitutive characterization of behaviour. Therefore, the primary aim of this study was to characterize both perfect and defected metal NWs. Large-scale molecular dynamics (MD) simulations were utilized to assess the mechanical properties and deformation mechanisms of different NWs under diverse loading conditions including tension, compression, bending, vibration and torsion. The target samples include different FCC metal NWs (e.g., Cu, Ag, Au NWs), which were either in a perfect crystal structure or constructed with different defects (e.g. pre-existing surface/internal defects, grain/twin boundaries). It has been found from the tensile deformation that Young's modulus was insensitive to different styles of pre-existing defects, whereas the yield strength showed considerable reduction. The deformation mechanisms were found to be greatly influenced by the presence of defects, i.e., different defects acted in the role of dislocation sources, and many affluent deformation mechanisms had been triggered. Similar conclusions were also obtained from the compressive deformation, i.e., Young's modulus was insensitive to different defects, but the critical stress showed evident reduction. Results from the bending deformation revealed that the current modified beam models with the considerations of surface effect, or both surface effect and axial extension effect were still experiencing certain inaccuracy, especially for the NW with ultra small cross-sectional size. Additionally, the flexural rigidity of the NW was found to be insensitive to different pre-existing defects, while the yield strength showed an evident decrease. For the resonance study, the first-order natural frequency of the NW with pre-existing surface defects was almost the same as that from the perfect NW, whereas a lower first-order natural frequency and a significantly degraded quality factor was observed for NWs with grain boundaries. Most importantly, the <110> FCC NWs were found to exhibit a novel beat phenomenon driven by a single actuation, which was resulted from the asymmetry in the lattice spacing in the (110) plane of the NW cross-section, and expected to exert crucial impacts on the in situ nanomechanical measurements. In particular, <110> Ag NWs with rhombic, truncated rhombic, and triangular cross-sections were found to naturally possess two first-mode natural frequencies, which were envisioned with applications in NEMS that could operate in a non-planar regime. The torsion results revealed that the torsional rigidity of the NW was insensitive to the presence of pre-existing defects and twin boundaries, but received evident reduction due to grain boundaries. Meanwhile, the critical angle decreased considerably for defected NWs. This study has provided a comprehensive and deep investigation on the mechanical properties and deformation mechanisms of perfect and defected NWs, which will greatly extend and enhance the existing knowledge and understanding of the properties/performance of NWs, and eventually benefit the realization of their full potential applications. All delineated MD models and theoretical analysis techniques that were established for the target NWs in this research are also applicable to future studies on other kinds of NWs. It has been suggested that MD simulation is an effective and excellent tool, not only for the characterization of the properties of NWs, but also for the prediction of novel or unexpected properties.