Understanding silica-supported metal catalysts: Pd/silica as a case study

Supported metal catalysts, particularly noble metals supported on SiO₂, have attracted considerable attention due to the importance of the silica–metal interface in heterogeneous catalysis and in electronic device fabrication. Several important issues, e.g., the stability of the metal–oxide interface at working temperatures and pressures, are not well-understood. In this review, the present status of our understanding of the metal–silica interface is reviewed. Recent results of model studies in our laboratories on Pd/SiO₂/Mo(1 1 2) using LEED, AES and STM are reported. In this work, epitaxial, ultrathin, well-ordered SiO₂ films were grown on a Mo(1 1 2) substrate to circumvent complications that frequently arise from the silica–silicon interface present in silica thin films grown on silicon.     

Cover Picture: Arresting,Fixing, and Separating Dimers Composed of Uniform Silica Colloidal Spheres (Adv. Funct. Mater. 12/2006)

In colloidal suspensions of silica, particles undergo constant collisions. By controlling various parameters, the repulsive barrier can be reduced, thereby substantially increasing the number of collision‐induced dimerization events. Xia and co‐workers report on p. 1627 that the dimers could be arrested and then permanently fixed by introducing a small amount of fresh tetraethylorthosilicate into the colloidal suspension, with monodisperse dimer yields of up to 50 %. This yield could be increased to 80 % by centrifugation in a density gradient medium. When fresh tetraethylorthosilicate is introduced into a colloidal suspension of silica spheres, it hydrolyzes and condenses in situ to arrest and fix the dimers resulting from constant collisions between the spheres. By optimizing the experimental parameters (including the length of aging time) and the diameter of the silica spheres, as well as the concentrations of counterions, water, and ammonia, it is possible to routinely produce monodisperse dimers with a yield as high as 50 %. When combined with centrifugation using a density gradient medium, the yield of such dimers could be further increased to 80 %. It is believed that this method will provide a simple and versatile approach to the high‐volume production of dimers from spherical colloids composed of different materials. These dimers may find widespread use in a range of applications such as fabrication of photonic crystals and fundamental studies related to colloidal science.     

A new approach to modelling of single droplet drying

A model was developed to predict the change in droplet mass and temperature when it is exposed to hot air, as in spray drying of droplets containing solids. The droplet was assumed first to undergo sensible rapid heating with no mass change. Then the droplet experiences some shrinkage, with no temperature change but rapid mass losses, followed by a period of crust formation with a significant change in droplet mass and temperature and finally a short period of sensible heating of the dried particle. The model, unlike previous models, accounts for shrinkage and for the temperature distribution in the droplet. It provided a good prediction for the change in droplet temperature and mass for some of the experimental measurements available in the literatures.     

Synthesis and characterization of zeolite NaY from rice husk silica

Rice husk silica (RHS) in amorphous phase with 98% purity was prepared from a waste rice husk from rice milling by leaching with hydrochloric acid and calcination. The RHS was used effectively as a silica source for the synthesis of zeolite Y in sodium form (NaY). The zeolite in pure phase was obtained from a two-step synthetic route in which the starting gels were mixed, aged for 24 h at room temperature and crystallized for 24 h at 90 °C. The diameter of single crystal particles from a scanning electron microscope was approximately 1.0 μm, whereas the average particle diameter from laser diffraction particle size analyzer was approximately 10 μm because of the agglomeration of small crystals. Longer crystallization time in this route resulted in a mixed phase containing NaY and zeolite P in sodium form (NaP). In addition, a one-step synthetic route (no aging) was studied and the product was also a mixed phase zeolite.     

Characterization and modification of fillers for paints and coatings

This paper highlights the possibility of inverse gas chromatography for the surface characterization of common fillers (CaCO₃, talc, SiO₂,) for paints and coatings. Divided solids are described, on the one hand, by the dispersive component of their surface energy and, on the other, by a specific parameter indicating their acid-base interaction potential. The role of the surface morphology at a molecular level is also examined. It is demonstrated that steric effects play an important role in the adsorption of probes on lamellar solids like talc. The consequences of surface treatments as well as examples of practical applications are also reported.     

Silica removal from Mokai, New Zealand, geothermal brine by treatment with lime and a cationic precipitant

Preliminary experiments using two chemicals (CaO, a quicklime, and a cationic nitrogen-bearing precipitant, EC-004) to remove silica from geothermal brine were undertaken at the Mokai geothermal plant, New Zealand. The brine was mixed with the reagent (CaO or EC-004). The reaction was studied from the start of the experiment (NRT, 0 min, no retaining time) and after 15 min (15RT) at 90 °C. The concentration of silica in the brine was initially 954 mg/l, and decreased linearly with increasing reagent concentration. When CaO is added, the silica concentration at 15RT was 200 mg/l lower than at NRT and became almost zero on addition of 1.5 g/l. In contrast, when EC-004 is added, the total silica concentration nearly reaches the solubility of amorphous silica at 90 °C. In order to prevent silica scaling in Mokai brines cooled to 90 °C, the CaO and EC-004 added should be individually adjusted to 0.5 g/l and 80 mg/l, respectively.     

Eight-year exploration of shrinkage in high-performance concrete

In this paper, an experimental and analytical exploration on the effect of water-binder ratio (w/b), silica fume and age on autogenous, carbonation, drying and total shrinkage of high-performance concrete (HPC) is outlined. Eight types of HPC were studied. Carbonation, internal relative humidity (RH) and strength were studied on specimens from the same batch of HPC that was used in the studies of shrinkage. The results indicate fairly good correlation between carbonation, shrinkage, w/b and RH. The type and amount of silica fume affected shrinkage.     

EFFECTS OF SUBMICROMETER PARTICULATE SILICA ADDENDA ON THE ADHESION OF MICROMETER-SIZE PARTICLES TO A POLYESTER-COMPOSITE SUBSTRATE

The force needed to detach five sets of different size particles, having number-averaged diameters between 3.6 and 8.5 µm, from a composite substrate was measured using an ultracentrifuge. In addition to size variations, the asperity concentration for each size particle was adjusted by varying the silica concentration, adjusted so that the surface area concentration at each level was kept constant for the five sizes of particles. Due to the changing silica concentration and particle size, the charge per particle also varied. It was found that the detachment force appeared to be virtually independent of charge, with any correlation actually appearing slightly negative, if anything. However, the detachment force increased monotonically with increasing particle diameter and decreased monotonically with increasing silica concentration. Moreover, upon normalizing the detachment force to the particle diameter and the silica concentration to the surface area concentration of silica, it was found that the detachment force clustered into groups in which the force needed to separate the particle from the substrate depended only on the silica concentration. These results suggest that van der Waals interaction, rather than electrostatic forces, are the dominant mechanism controlling toner adhesion in this instance.     

Uses of Ozone in a Three-Phase System for Water Treatment: Ozone Adsorption

A new technique of using ozone for water treatment is presented. This new technique consists of using a three-step-process composed firstly of ozone adsorption on an appropriate adsorbent, secondly water treatment, and thirdly regeneration of the adsorbent. Results regarding ozone adsorption (the first step) are presented in this paper. Different types of silica gel and a type of TiO₂ have been tested for ozone adsorption. It was found that the physical characteristics of the silica gel affect its capacity for ozone. Titanium dioxide has shown ozone decomposition instead of adsorption as it contains Lewis acid sites. An exponential decrease of the silica gel capacity with its moisture content has been found. Linear isotherms in the range of ozone concentrations less than 100?g/m³ NTP have been found. A particle diffusion model with linear equilibrium isotherm has been used to model the breakthrough curves in fixed bed columns.