Infrared study of methyl formate and formaldehyde adsorption on reduced and oxidised silica-supported copper catalysts

Infrared spectra are reported of methyl formate and formaldehyde adsorbed at 300 K on silica, Cu/SiO2 reduced in hydrogen and Cu/SiO2 which had been oxidised by exposure to nitrous oxide after reduction. Silanol groups on silica form hydrogen bonds with carbonyl groups in weakly adsorbed methyl formate molecules. Methyl formate ligates via its carbonyl groups to Cu atoms in the surface of reduced copper. A low residual concentration of surface oxygen on copper promoted the slow reaction of ligated methyl formate to give a bridging formate species on copper and adsorbed methoxy groups. Methyl formate did not ligate to an oxidised copper surface but was rapidly chemisorbed to give unidentate formate and methoxy species. Formaldehyde slowly polymerises on silica to form trioxane and other oxymethylene species. The reaction is faster over Cu/SiO2 which, in the reduced state, also catalyses the formation of bridging formate anions adsorbed on copper. The reaction between formaldehyde and oxidised Cu/SiO2 leads to both unidentate and bidentate formate and adsorbed water.

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.

Thermal stability and hot-stage Raman spectroscopic study of Ca-montmorillonite modified with different surfactants : a comparative study

Three long chain cationic surfactants were intercalated into Ca-montmorillonite through ion exchangeand the obtained organoclays were characterized by X-ray diffraction (XRD), high resolution thermo-gravimetric analysis (TG) and Raman spectroscopy. The intercalation of surfactants not only changes thesurface properties of clay from hydrophilic to hydrophobic but also greatly increases the basal spacing ofthe interlayers based on XRD analysis. The thermal stability of organoclays intercalated with three sur-factants (TTAB, DTAB and CTAB) and the different arrangements of the surfactant molecules intercalatedinto Ca-montmorillonite were determined by TG-DTG analysis. A Raman spectroscopic study on the Ca-montmorillonite modified by three surfactants prepared at different concentrations provided the detailedconformational ordering of different intercalated long-chain surfactants under different conditions. Thewavenumber of the antisymmetric stretching mode is more sensitive than that of the symmetric stretch-ing mode to the mobility of the tail of the amine chain. At room temperature, the conformational orderingis more easily affected by the packing density in the lateral model. With the increase of the temperature,the positions of both the antisymmetric and symmetric stretching bands shift to higher wavenumbers,which indicates a decrease of conformational ordering. This study offers new insights into the struc-ture and properties of Ca-montmorillonite modified with different long chain surfactants. Moreover, theexperimental results confirm the potential applications of organic Ca-montmorillonites for the removalof organic impurities from aqueous media.

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.

Development of modified inorganic adsorbents for radioactive iodine removal and biomolecule adsorption

Development and application of inorganic adsorbent materials have been continuously investigated due to their variability and versatility. This Master thesis has expanded the knowledge in the field of adsorption targeting radioactive iodine waste and proteins using modified inorganic materials. Industrial treatment of radioactive waste and safety disposal of nuclear waste is a constant concern around the world with the development of radioactive materials applications. To address the current problems, laminar titanate with large surface area (143 m2 g−1) was synthesized from inorganic titanium compounds by hydrothermal reactions at 433 K. Ag2O nanocrystals of particle size ranging from 5–30 nm were anchored on the titanate lamina surface which has crystallographic similarity to that of Ag2O nanocrystals. Therefore, the deposited Ag2O nanocrystals and titanate substrate could join together at these surfaces between which there forms a coherent interface. Such coherence between the two phases reduces the overall energy by minimizing surface energy and maintains the Ag2O nanocrystals firmly on the outer surface of the titanate structure. The combined adsorbent was then applied as efficient adsorbent to remove radioactive iodine from water (one gram adsorbent can capture up to 3.4 mmol of I- anions) and the composite adsorbent can be recovered easily for safe disposal. The structure changes of the titanate lamina and the composite adsorbent were characterized via various techniques. The isotherm and kinetics of iodine adsorption, competitive adsorption and column adsorption using the adsorbent were studied to determine the iodine removal abilities of the adsorbent. It is shown that the adsorbent exhibited excellent trapping ability towards iodine in the fix-bed column despite the presence of competitive ions. Hence, Ag2O deposited titanate lamina could serve as an effective adsorbent for removing iodine from radioactive waste. Surface hydroxyl group of the inorganic materials is widely applied for modification purposes and modification of inorganic materials for biomolecule adsorption can also be achieved. Specifically, γ-Al2O3 nanofibre material is converted via calcinations from boehmite precursor which is synthesised by hydrothermal chemical reactions under directing of surfactant. These γ-Al2O3 nanofibres possess large surface area (243 m2 g-1), good stability under extreme chemical conditions, good mechanical strength and rich surface hydroxyl groups making it an ideal candidate in industrialized separation column. The fibrous morphology of the adsorbent also guarantees facile recovery from aqueous solution under both centrifuge and sedimentation approaches. By chemically bonding the dyes molecules, the charge property of γ-Al2O3 is changed in the aim of selectively capturing of lysozyme from chicken egg white solution. The highest Lysozyme adsorption amount was obtained at around 600 mg/g and its proportion is elevated from around 5% to 69% in chicken egg white solution. It was found from the adsorption test under different solution pH that electrostatic force played the key role in the good selectivity and high adsorption rate of surface modified γ-Al2O3 nanofibre adsorbents. Overall, surface modified fibrous γ-Al2O3 could be applied potentially as an efficient adsorbent for capturing of various biomolecules.

Synthesis, characterisation and application of organic surfactants modified clays for water purification

This thesis offered a step forward in the development of cheap and effective materials for water treatment. It described the modification of naturally abundant clay minerals with organic molecules, and used the modified clays as effective adsorbents for the removal of recalcitrant organic water pollutants. The outcome of the study greatly extended our understanding of the synthesis and characteristic properties of clay and modified clay minerals, provided optimistic evaluation of the modified clays for environmental remediation and offered potential utility for clay minerals in the industry and environment.

Modified alumina nanofiber membranes for protein separation

Large-scale purification/separation of bio-substances is a key technology required for rapid production of biological substances in bioengineering. Membrane filtration is a new separation process and has potential to be used for concentration (removal of solvent), desalting (removal of low molecular weight compounds), clarification (removal of particles), and fractionation (protein-protein separation). In this study, we developed an efficient membrane for protein separation based on ceramic nanofibers. Alumina nanofibers were prepared on a porous support and formed large flow passages. The radical changes in membrane structure provided new ceramic membranes with a large porosity (more than 70%) due to the replacement of bulk particles with fine fibers as building components. The pore size had an average of 11 nm and pure water flux was approximately 360 L•h-1•m-2•bar-1. Further surface modification with a self-assembled monolayer of (3-aminopropyl) triethoxysilane enhanced the membrane filtration properties. Characterization with SEM, FTIR, contact angle, and proteins separation tests indicated that the fibril layers uniformly spread on the surface of the porous support. Moreover, the membrane surface was changed from hydrophilic to hydrophobic after silane groups were grafted. It demonstrated that the silane-grafted alumina fiber membrane can reject 100% BSA protein and 92% cellulase protein. It was also able to retain 75% trypsin protein while maintaining a permeation flux of 48 L•h-1•m-2•bar-1.

Clinical practice guidelines for nurse-administered procedural sedation and analgesia in the cardiac catheterisation laboratory : A modified Delphi study

Aim To develop clinical practice guidelines for nurse-administered procedural sedation and analgesia in the cardiac catheterisation laboratory. Background Numerous studies have reported that nurse-administered procedural sedation and analgesia is safe. However, the broad scope of existing guidelines for the administration and monitoring of patients who receive sedation during medical procedures without an anaesthetist presents means there is a lack of specific guidance regarding optimal nursing practices for the unique circumstances in which nurse-administered procedural sedation and analgesia is used in the cardiac catheterisation laboratory. Methods A sequential mixed methods design was utilised. Initial recommendations were produced from three studies conducted by the authors: an integrative review; a qualitative study; and a cross-sectional survey. The recommendations were revised in accordance with responses from a modified Delphi study. The first Delphi round was completed by nine senior cardiac catheterisation laboratory nurses. All but one of the draft recommendations met the pre-determined cut-off point for inclusion. There were a total of 59 responses to the second round. Consensus was reached on all recommendations. Implications for nursing The guidelines that were derived from the Delphi study offer twenty four recommendations within six domains of nursing practice: Pre-procedural assessment; Pre-procedural patient and family education; Pre-procedural patient comfort; Intra-procedural patient comfort; Intra-procedural patient assessment and monitoring; and Post-procedural patient assessment and monitoring. Conclusion These guidelines provide an important foundation towards the delivery of safe, consistent and evidence-based nursing care for the many patients who receive sedation in the cardiac catheterisation laboratory setting.

YBa2Cu3O7/NdGaO3/YBa 2Cu3O7 trilayers by modified off-axis sputtering

High-quality epitaxial YBa2Cu3O7-δ (YBCO) thin films were achieved by a modified off-axis sputtering technique with high deposition rates (3.3 nm/min). The film quality and the deposition rate depended crucially on the target-to-substrate separation. Epitaxial YBCO/NdGaO3(NGO)/YBCO trilayers were successfully grown onto SrTiO3, Y-ZrO2, and LaAlO3 substrates by dc and rf sputtering. The epitaxial relations were found to be [001] YBCO//[001]NGO, [100]YBCO, or [010] YBCO//[110]NGO and [001]YBCO//[110] NGO, [100]YBCO, or [010]YBCO//[001] NGO, where the latter orientation relationship was dominating. Subsequent top YBCO layers grew c axis oriented independently of the two epitaxial orientations of the NGO. The orientation relationships between YBCO and NGO were the same. Auger electron depth profiles and transmission electron microscopy indicated that the interdiffusion at the interface between the YBCO and NGO layers was not strong even at 740°C. The superconducting transition temperatures of the top and bottom YBCO layers were about the same as that of YBCO single layers, i.e., 87-90 K. Scanning electron microscopy of the surface morphologies of the YBCO and the NGO showed that a smaller substrate-target distance resulted in smoother films.

Fabrication of metal-nanoparticle-modified semiconducting copper--and silver--TCNQ materials as substrates for the reduction of chromium (VI) using thiosulfate ions at ambient temperature

The formation of readily recoverable and reusable organic semiconducting Cu- and AgTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) microstructures decorated with Pt and Pd metallic nanoparticles is described for the effective reduction of CrVI ions in aqueous solution at room temperature using both formic acid and an environmentally friendly thiosulfate reductant. The M-TCNQ (M=metal) materials were formed by electrocrystallisation onto a glassy carbon surface followed by galvanic replacement in the presence of H2PtCl6 or PdCl2 to form the composite material. It was found that loading of the surface with nanoparticles could easily be controlled by changing the metal salt concentration. Significantly, the M-TCNQ substrates facilitated the formation of well-isolated metal nanoparticles on their surfaces under appropriate galvanic replacement conditions. The semiconductor–metal nanoparticle combination was also found to be critical to the catalyst performance, wherein the best-performing material was CuTCNQ modified by well-isolated Pt nanoparticles with both formic acid and thiosulfate ions as the reductant.

Removal of bisphenol A from wastewater by Ca-montmorillonite modified with selected surfactants

Organo Arizona SAz-2 Ca-montmorillonite was prepared with different surfactant (DDTMA and HDTMA) loadings through direct ion exchange. The structural properties of the prepared organoclays were characterized by XRD and BET instruments. Batch experiments were carried out on the adsorption of bisphenol A (BPA) under different experimental conditions of pH and temperature to determine the optimum adsorption conditions. The hydrophobic phase and positively charged surface created by the loaded surfactant molecules are responsible for the adsorption of BPA. The adsorption of BPA onto organoclays is well described by pseudo-second order kinetic model and the Langmuir isotherm. The maximum adsorption capacity of the organoclays for BPA obtained from a Langmuir isotherm was 151.52 mg/g at 297 K. This value is among the highest values for BPA adsorption compared with other adsorbents. In addition, the adsorption process was spontaneous and exothermic based on the adsorption thermodynamics study. The organoclays intercalated with longer chain surfactant molecules possessed a greater adsorption capacity for BPA even under alkaline conditions. This process provides a pathway for the removal of BPA from contaminated waters.