Graeme J. Millar

Synthesis and characterization of highly ordered MCM-41 in an alkali-free system and its catalytic activity

MCM-41 mesoporous molecular sieve materials are synthesised using aqueous ammonia solution to adjust the pH of the reactant gel. Highly ordered MCM-41 with Si/Al ratio as low as 14 was obtained and characterised by27A1 MAS NMR, XRD, N2-adsorption, benzene sorption, and NH3-TPD measurements. The acidity of MCM-41 materials obtained in this system was conveniently generated through straightforward calcination of the as-synthesised sample. More mild acidic sites generated could be due to the avoidance of the multiple calcination procedure and/or the trace sodium species which are the poisons to Brønsted acid. The catalytic activities forn-heptane cracking and isomerization ofm-xylene were investigated, and these were in accordance with the known properties of MCM-41.

An in situ high pressure FT-IR study of CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol synthesis catalysts

In situ FT-IR spectroscopy allows the methanol synthesis reaction to be investigated under actual industrial conditions of 503 K and 10 MPa. On Cu/SiO2 catalyst formate species were initially formed which were subsequently hydrogenated to methanol. During the reaction a steady state concentration of formate species persisted on the copper. Additionally, a small quantity of gaseous methane was produced. In contrast, the reaction of CO2 and H2 on ZnO/SiO2 catalyst only resulted in the formation of zinc formate species: no methanol was detected. The interaction of CO2 and H2 with Cu/ZnO/SiO2 catalyst gave formate species on both copper and zinc oxide. Methanol was again formed by the hydrogenation of copper formate species. Steady-state concentrations of copper formate existed under actual industrial reaction conditions, and copper formate is the pivotal intermediate for methanol synthesis. Collation of these results with previous data on copper-based methanol synthesis catalysts allowed the formulation of a reaction mechanism.

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.

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 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.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm–1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIIIO sites formed on silver atoms modified by the presence of subsurface oxygen and O2– species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm–1) and adsorbed methoxy species.Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIIIO species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIIIO sites.

Effective Diffusivity and Evaporative Cooling in Convective Drying of Food Material

This article presents mathematical models to simulate coupled heat and mass transfer during convective drying of food materials using three different effective diffusivities: shrinkage dependent, temperature dependent, and the average of those two. Engineering simulation software COMSOL Multiphysics was utilized to simulate the model in 2D and 3D. The simulation results were compared with experimental data. It is found that the temperature-dependent effective diffusivity model predicts the moisture content more accurately at the initial stage of the drying, whereas the shrinkage-dependent effective diffusivity model is better for the final stage of the drying. The model with shrinkage-dependent effective diffusivity shows evaporative cooling phenomena at the initial stage of drying. This phenomenon was investigated and explained. Three-dimensional temperature and moisture profiles show that even when the surface is dry, the inside of the sample may still contain a large amount of moisture. Therefore, the drying process should be dealt with carefully; otherwise, microbial spoilage may start from the center of the dried food. A parametric investigation was conducted after validation of the model.

Spectroscopic evidence for adsorption sites located at Cu/ZnO interfaces

FTIR spectra are reported of CO and formic acid adsorption on a series of Cu/ZnO/SiO2 catalysts. Peaks due to linear CO adsorbed on copper diminished in intensity as the loading of ZnO was increased. This behaviour was explained in terms of ZnO island growth on the copper surface. Similarly, reduction of the copper concentration while maintaining a constant ZnO loading also resulted in further attenuation in bands ascribed to CO chemisorbed on copper. Formic acid exposure to a Cu/SiO2 sample produced a formate species displaying a νas(COO) mode at 1585 cm−1. Addition of a small quantity of ZnO to the catalyst resulted in substantial promotion of formate growth, which was accompanied by a shift (and broadening) of the νas(COO) vibration to 1660–1600 cm−1. Since further ZnO incorporation poisoned formate creation it was concluded that formate species bonded to Cu and Zn sites located at interfacial positions had been formed. The role of such species in methanol synthesis is discussed.

A combined infrared, temperature programmed desorption and temperature programmed reaction spectroscopy study of CO2 and H2 interactions on reduced and oxidized silica-supported copper catalysts

The nature and strength of bonding of carbon dioxide to a high area (136 m2g-1) polycrystalline copper supported on silica has been determined by the combined techniques of Fourier transform infrared spectroscopy (FTIR) and temperature programmed desorption (TPD). These show the room temperature interaction to be initially dissociative producing carbon monoxide (bonded both on a CuI site and on a stepped, high index surface) and surface oxygen. Further carbon dioxide adsorption interacts with the surface oxygen to produce a symmetric carbonate species. The adsorption and surface reaction of co-adsorbed hydrogen and carbon dioxide has also been studied by the combined techniques. At room temperature the adsorption of both is simply dissociative producing adsorbed hydrogen atoms and the symmetric carbonate species. Heating these adsorbates to 388K causes them to react producing a surface formate species—the dominant intermediate when methanol is synthesized from these reactants. This paper therefore elucida...

Effect of strong acids on red mud structural and fluoride adsorption properties.

The removal of fluoride using red mud has been improved by acidifying red mud with hydrochloric, nitric and sulphuric acid. The acidification of red mud causes sodalite and cancrinite phases to dissociate, confirmed by the release of sodium and aluminium into solution as well as the disappearance of sodalite bands and peaks in infrared and X-ray diffraction data. The dissolution of these mineral phases increases the amount of available iron and aluminium oxide/hydroxide sites that are accessible for the adsorption of fluoride. However, concentrated acids have a negative effect on adsorption due to the dissolution of these iron and aluminium oxide/hydroxide sites. The removal of fluoride is dependent on the charge of iron and aluminium oxide/hydroxides on the surface of red mud. Acidifying red mud with hydrochloric, nitric and sulphuric acid resulted in surface sites of the form ≡SOH2(+) and ≡SOH. Optimum removal is obtained when the majority of surface sites are in the form ≡SOH2(+) as the substitution of a fluoride ion does not cause a significant increase in pH. This investigation shows the importance of having a low and consistent pH for the removal of fluoride from aqueous solutions using red mud.