Octahedral anatase particles (OAPs) were prepared by an ultrasonication (US)-hydrothermal (HT) reaction of partially proton-exchanged potassium titanate nanowires (TNWs). The structural/physical properties of OAP-containing samples, including specific surface area, crystallinity, crystallite size, particle aspect ratio, composition and total OAP content, were analyzed. Photocatalytic activities of samples were measured under irradiation (>290 nm) for oxidative decomposition of acetic acid (CO2 system) and dehydrogenation of methanol (H2 system) under aerobic and deaerated conditions, respectively. Total density of electron traps (ETs) was measured by double-beam photoacoustic spectroscopy (DB-PAS). Mobility and lifetime of charge carriers (electrons) were investigated by the time-resolved microwave conductivity (TRMC) method. The effects of synthesis parameters, i.e., HT duration, HT temperature and US duration, on properties and photocatalytic activities of final products were examined in detail. The sample prepared with 1 h US duration and 6 h HT duration at 433 K using 267 mg of TNWs in 80 mL of Milli-Q water exhibited the highest photocatalytic activity. It was found that change in HT duration or HT temperature while keeping the other conditions the same resulted in changes in all properties and photocatalytic activity. On the other hand, duration of US treatment, before HT reaction, influenced the morphology of both the reagent (by TNWs breaking) and final products (change in total OAP content); samples prepared with various US durations exhibited almost the same structural/physical properties evaluated in this study but were different in morphology and photocatalytic activity. This enabled clarification of the correlation between morphology and photocatalytic activity, i.e., the higher the total OAP content was, the higher was the level of photocatalytic activity, especially in the CO2 system. Although the decay after maximum TRMC signal intensity (Imax) was almost constant for all samples used in this study, photocatalytic activities were roughly proportional to Imax, which tended to be proportional to total OAP content. Assuming that Imax corresponds to the product of density of electrons in mobile shallow ETs and their mobility, the results suggest that OAP particles have beneficial shallow ETs in higher density and thereby the OAP content governs the photocatalytic activities. Thus, morphology-dependent photocatalytic activity of OAP-containing particles was reasonably interpreted by density of ETs presumably located on the exposed {101} facets.
This paper presents visual observations aiming to clarify the underlying physics of surfactant effects on clathrate hydrate crystal growth at the interface between methane gas and water with surfactant. Sodium dodecyl sulfate (SDS), which is commonly used in industrial processes, was used in this study. Various SDS mass fractions from 0 to w SDS = 100 ppm with a step of size 10 ppm were examined, where w SDS represents the mass fraction of SDS aqueous solution. The crystal growth behavior and the crystal morphology of the methane hydrate at the interface varied depending on surfactant concentration and ΔT sub. In systems with w SDS ≤ 20 ppm, the nucleation occurred on the droplet surface (gas/liquid interface), then grew laterally, and finally covered the whole droplet surface. On the contrary, at w SDS ≥ 30 ppm, the droplet shape was not maintained and enhanced hydrate crystal growth was observed compared to those systems with w SDS ≤ 20 ppm. Individual hydrate crystals at w SDS = 20 ppm were observed to be smaller than those in a pure water system at a given ΔT sub, which is ascribed to the enhanced hydrate nucleation by the addition of SDS.
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