Infrared study of the adsorption of formic acid on silica-supported copper and oxidised copper catalysts

Infrared spectra are reported of formic acid adsorbed at 300 K on a reduced copper catalyst (Cu/SiO2) and a copper surface which had been oxidised by exposure to nitrous oxide. Formic acid was weakly adsorbed on the silica support. Ligation of formic acid to the copper surface occurred only on the reduced catalyst. Dissociative adsorption resulted in the formation of unidentate formate on the oxidised catalyst. The presence of reduced copper metal instigated a rapid reorientation to a bidentate formate species.

Infrared study of CO adsorption on reduced and oxidised silica-supported copper catalysts

FTIR spectra are reported of CO adsorbed on silica-supported copper catalysts prepared from copper(II) acetate monohydrate. Fully oxidised catalyst gave bands due to CO on CuO, isolated Cu2+ cations on silica and anion vacancy sites in CuO. The highly dispersed CuO aggregated on reduction to metal particles which gave bands due to adsorbed CO characteristic of both low-index exposed planes and stepped sites on high-index planes. Partial surface oxidation with N2O or H2O generated Cu+ adsorption sites which were slowly reduced to Cu° by CO at 300 K. Surface carbonate initially formed from CO was also slowly depleted with time with the generation of CO2. The results are consistent with adsorbed carbonate being an intermediate in the water-gas shift reaction of H2O and CO to H2 and CO2.

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.

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.

Validating SMPS-measured size distribution of double-mode spherical Silica nanoparticles by Transmission Electron Microscope (TEM)

A nanoparticles size is one of their key physical characteristics that can affect their fate in a human’s respiratory tract (in case of inhalation) and also in the environment. Hence, measuring the size distribution of nanoparticles is absolutely essential and contributes greatly to their characterization. For years, Scanning Mobility Particle Sizers (SMPS), which rely on measuring the electrical mobility diameter of particles, have been used as one of the most reliable real-time instruments for the size distribution measurement of nanoparticles. Despite its benefits, this instrument has some drawbacks, including equivalency problems for non-spherical particles (i.e. assuming a non-spherical particle is equal to a spherical particle of diameter d due to the same electrical mobility), as well as limitations in terms of its use in workplaces, because of its large size and the complexity of its operation...

Modeling the co-precipitation of silica and calcium oxalate in sugar solutions

Solution chemistry plays a significant role in the rate and type of foulant formed on heated industrial surfaces. This paper describes the effect of sucrose, silica (SiO2), Ca2+ and Mg2+ ions, and trans-aconitic acid on the kinetics and solubility of SiO2 and calcium oxalate monohydrate (COM) in mixed salt solutions containing sucrose and refines models previously proposed. The developed SiO2 models show that sucrose and SiO2 concentrations are the main parameters that determine apparent order (n) and apparent rate of reaction (k) and SiO2 solubility over a 24 h period. The calcium oxalate solubility model shows that while increasing [Mg2+] increases COM solubility, the reverse is so with increasing sucrose concentrations. The role of solution species on COM crystal habit is discussed and the appearance of the uncommon (001) face is explained.

The influence of cellular source on periodontal regeneration using calcium phosphate coated polycaprolactone scaffold supported cell sheets

Cell-based therapy is considered a promising approach to achieving predictable periodontal regeneration. In this study, the regenerative potential of cell sheets derived from different parts of the periodontium (gingival connective tissue, alveolar bone and periodontal ligament) were investigated in an athymic rat periodontal defect model. Periodontal ligament (PDLC), alveolar bone (ABC) and gingival margin-derived cells (GMC) were obtained from human donors. The osteogenic potential of the primary cultures was demonstrated in vitro. Cell sheets supported by a calcium phosphate coated melt electrospun polycaprolactone (CaP-PCL) scaffold were transplanted to denuded root surfaces in surgically created periodontal defects, and allowed to heal for 1 and 4 weeks. The CaP-PCL scaffold alone was able to promote alveolar bone formation within the defect after 4 weeks. The addition of ABC and PDLC sheets resulted in significant periodontal attachment formation. The GMC sheets did not promote periodontal regeneration on the root surface and inhibited bone formation within the CaP-PCL scaffold. In conclusion, the combination of either PDLC or ABC sheets with a CaP-PCL scaffold could promote periodontal regeneration, but ABC sheets were not as effective as PDLC sheets in promoting new attachment formation.

Liquid metal marbles

Liquid metal marbles that are droplets of liquid metal encapsulated by micro- or nanoparticles are introduced. Droplets of galinstan liquid metal are coated with insulators (including Teflon and silica) and semiconductors (including WO3, TiO2, MoO3, In2O3 and carbon nanotubes) by rolling over a powder bed and also by submerging in colloidal suspensions. It is shown that these marbles can be split and merged, can be suspended on water, and are even stable when moving under the force of gravity and impacting a flat solid surface. Furthermore, the marble coating can operate as an active electronic junction and the nanomaterial coated liquid metal marble can act as a highly sensitive electrochemical based heavy metal ion sensor. This new element thus represents a significant platform for the advancement of research into soft electronics.

Electrochromic properties of TiO2 nanotubes coated with electrodeposited MoO3

Despite a favourable morphology, anodized and ordered TiO2 nanotubes are incapable of showing electrochromic properties in comparison to many other metal oxide counterparts. To tackle this issue, MoO3 of 5 to 15 nm thickness was electrodeposited onto TiO2 nanotube arrays. A homogenous MoO3 coating was obtained and the crystal phase of the electrodeposited coating was determined to be α-MoO3. The electronic and optical augmentations of the MoO3 coated TiO2 platforms were evaluated through electrochromic measurements. The MoO3/TiO2 system showed a 4-fold increase in optical density over bare TiO2 when the thickness of the MoO3 coating was optimised. The enhancement was ascribed to (a) the α-MoO3 coating reducing the bandgap of the composite material, which shifted the band edge of the TiO2 platform, and subsequently increased the charge carrier transfer of the overall system and (b) the layered morphology of α-MoO3 that increased the intercalation probability and also provided direct pathways for charge carrier transfer.

Colloidal drug probe : method development and validation for adhesion force measurement using atomic force microscopy

This study demonstrates a novel technique of preparing drug colloid probes to determine the adhesion force between the drug salbutamol sulphate (SS) and the surfaces of polymer microparticles to be used as carriers for the dispersion of drug particles from a dry powder inhaler (DPI) formulation. Initially model silica probes of approximately 4 μm size, similar to a drug particle used in DPI formulations, were coated with a saturated SS solution with the aid of capillary forces acting between the silica probe and the drug solution. The developed method of ensuring a smooth and uniform layer of SS on the silica probe was validated using X-Ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Using the same technique, silica microspheres preattached on the AFM cantilever were coated with SS. The adhesion forces between the silica probe and drug coated silica (drug probe) and polymer surfaces (hydrophilic and hydrophobic) were determined. Our experimental results showed that the technique for preparing the drug probe was robust and can be used to determine the adhesion force between hydrophilic/hydrophobic drug probe and carrier surfaces to gain a better understanding on drug carrier adhesion forces in DPI formulations.

Spin-coated carbon

We describe a novel and facile approach to covalently graft molecules containing stable free radicals onto carbon surfaces including graphene, carbon nanotubes, glassy carbon and carbon fibres. The new technique employs a stable aryl nitroxide radical diazonium tetrafluoroborate salt. The salt may be isolated and added to carbon surfaces in solution, suspension or electrochemically and represents a convenient, versatile and highly efficient means to adorn graphitic materials with large numbers of free radical spin systems

A comparison study on hydrogen sensing performance of MoO3 nanoplatelets coated with a thin layer of Ta2O5 or La2O3

There has been significant interest in developing metal oxide films with high surface area-to-volume ratio nanostructures particularly in substantially increasing the performance of Pt/oxide/semiconductor Schottky-diode gas sensors. While retaining the surface morphology of these devices, they can be further improved by modifying their nanostructured surface with a thin metal oxide layer. In this work, we analyse and compare the electrical and hydrogen-sensing properties of MoO3 nanoplatelets coated with a 4 nm layer of tantalum oxide (Ta2O5) or lanthanum oxide (La2O3). We explain in our study, that the presence of numerous defect traps at the surface (and the bulk) of the thin high-� layer causes a substantial trapping of charge during hydrogen adsorption. As a result, the interface between the Pt electrode and the thin oxide layer becomes highly polarised. Measurement results also show that the nanoplatelets coated with Ta2O5 can enable the device to be more sensitive (a larger voltage shift under hydrogen exposure) than those coated with La2O3.

Ultrasensitive strain sensors made from metal-coated carbon nanofiller/epoxy composites

A set of resistance-type strain sensors has been fabricated from metal-coated carbon nanofiller (CNF)/epoxy composites. Two nanofillers, i.e., multi-walled carbon nanotubes and vapor growth carbon fibers (VGCFs) with nickel, copper and silver coatings were used. The ultrahigh strain sensitivity was observed in these novel sensors as compared to the sensors made from the CNFs without metal-coating, and conventional strain gauges. In terms of gauge factor, the sensor made of VGCFs with silver coating is estimated to be 155, which is around 80 times higher than that in a metal-foil strain gauge. The possible mechanism responsible for the high sensitivity and its dependence with the networks of the CNFs with and without metal-coating and the geometries of the CNFs were thoroughly investigated.

Preparation of mesoporous bioglass coated zirconia scaffold for bone tissue engineering

Porous yttria-stabilized zirconia (YSZ) has been regarded as a potential candidate for bone substitute due to its high mechanical strength. However, porous YSZ is biologically inert to bone tissue. It is therefore necessary to introduce bioactive coatings onto the walls of the porous structures to enhance its bioactivity. In this study, porous YSZ scaffolds were prepared using a replication technique and then coated with mesoporous bioglass due to its excellent bioactivity. The microstructures were examined using scanning electron microscopy and the mechanical strength was evaluated via compression test. The biocompatibility and bioactivity were also evaluated using bone marrow stromal cell (BMSC) proliferation test and simulated body fluid test.

Monitoring phase behavior of sub- and supercritical CO2 confined in porous fractal silica with 85% porosity

Phase behavior of CO2 confined in porous fractal silica with volume fraction of SiO2 φs = 0.15 was investigated using small-angle neutron scattering (SANS) and ultrasmall-angle neutron scattering (USANS) techniques. The range of fluid densities (0<(FCO2)bulk<0.977 g/cm3) and temperatures (T=22 °C, 35 and 60 °C) corresponded to gaseous, liquid, near critical and supercritical conditions of the bulk fluid. The results revealed formation of a dense adsorbed phase in small pores with sizes D<40 A° at all temperatures. At low pressure (P <55 bar, (FCO2)bulk <0.2 g/cm3) the average fluid density in pores may exceed the density of bulk fluid by a factor up to 6.5 at T=22 °C. This “enrichment factor” gradually decreases with temperature, however significant fluid densification in small pores still exists at temperature T=60°C, i.e., far above the liquid-gas critical temperature of bulk CO2 (TC=31.1 °C). Larger pores are only partially filled with liquid-like adsorbed layer which coexists with unadsorbed fluid in the pore core. With increasing pressure, all pores become uniformly filled with the fluid, showing no measurable enrichment or depletion of the porous matrix with CO2.