Investigation of process variables and intensification effects of ultrasound applied in oxidative desulfurization of model diesel over MoO3/Al2O3 catalyst

A new heterogeneous sonocatalytic system consisting of a MoO₃/Al₂O₃ catalyst and H₂O₂ combined with ultrasonication was studied to improve and accelerate the oxidation of model sulfur compounds of diesel, resulting in a significant enhancement in the process efficiency. The influence of ultrasound on properties, activity and stability of the catalyst was studied in detail by means of GC-FID, PSD, SEM and BET techniques. Above 98% conversion of DBT in model diesel containing 1000 μg/g sulfur was obtained by new ultrasound-assisted desulfurization at H₂O₂/sulfur molar ratio of 3, temperature of 318 K and catalyst dosage of 30 g/L after 30 min reaction, contrary to the 55% conversion obtained during the silent process. This improvement was considerably affected by operation parameters and catalyst properties. The effects of main process variables were investigated using response surface methodology in silent process compared to ultrasonication. Ultrasound provided a good dispersion of catalyst and oxidant by breakage of hydrogen bonding and deagglomeration of them in the oil phase. Deposition of impurities on the catalyst surface caused a quick deactivation in silent experiments resulting only 5% of DBT oxidation after 6 cycles of silent reaction by recycled catalyst. Above 95% of DBT was oxidized after 6 ultrasound-assisted cycles showing a great improvement in stability by cleaning the surface during ultrasonication. A considerable particle size reduction was also observed after 3 h sonication that could provide more dispersion of catalyst in model fuel.     

Advanced oxidation of Reactive Blue 181 solution: A comparison between Fenton and Sono-Fenton Process

In this work, the decolorization of C.I. Reactive Blue 181 (RB181), an anthraquinone dye, by Ultrasound and Fe²⁺ H₂O₂ processes was investigated. The effects of operating parameters, such as Fe²⁺ dosage, H₂O₂ dosage, pH value, reaction time and temperature were examined. Process optimisation [pH, ferrous ion (Fe²⁺), hydrogen peroxide (H₂O₂), and reaction time], kinetic studies and their comparison were carried out for both of the processes. The Sono-Fenton process was performed by indirect sonication in an ultrasonic water bath, which was operated at a fixed 35-kHz frequency. The optimum conditions were determined as [Fe²⁺] = 30 mg/L, [H₂O₂] = 50 mg/L and pH = 3 for the Fenton process and [Fe²⁺] = 10 mg/L, [H₂O₂] = 40 mg/L and pH = 3 for the Sono-Fenton process. The colour removals were 88% and 93.5% by the Fenton and Sono-Fenton processes, respectively. The highest decolorization was achieved by the Sono-Fenton process because of the production of some oxidising agents as a result of sonication. The paper also discussed kinetic parameters. The decolorization kinetic of RB181 followed pseudo-second-order reaction (Fenton study) and Behnajady kinetics (Sono-Fenton study).     

Sonochemical reactions with mesoporous alumina

Herein, we report the sonochemical reactions with MSU-X mesoporous alumina (m-Al₂O₃) in aqueous solutions. Sonication (f = 20 kHz, I = 30 W cm^?2, W_aq = 0.67 W mL^?1, T = 36–38 °C, Ar) causes significant acceleration of m-Al₂O₃ dissolution in the pH range of 4–11. Moreover, power ultrasound has a dramatic effect on the textural properties and phase composition of m-Al₂O₃. Short-time sonication at pH = 4 leads to the formation of nanorods and nanofibers of boehmite, AlO(OH). Prolonged ultrasonic treatment causes high aspect morphology transformation to aggregated nanosheets in weakly acid solutions or plated nanocrystals in alkaline solutions. Sonochemical products in alkaline medium are composed principally from boehmite and small amounts of bayerite, Al(OH)₃. Silent hydrolysis of m-Al₂O₃ yields boehmite at pH = 4 and bayerite at pH = 11. The effect of ultrasound on the textural properties of mesoporous alumina as well as on the transformation of nanosized bayerite to boehmite can be consistently attributed to the transient strong heating of the liquid shell surrounding the cavitation bubble which caused the chemical processes similar to those occurred during hydrothermal treatment.     

Ultrasound-assisted mineralization of organic contaminants using a recyclable LaFeO3 and Fe3+/persulfate Fenton-like system

A recyclable heterogeneous catalyst has been successfully developed for application in a Fenton-type advanced oxidation process without adding external H₂O₂. LaFeO₃ was prepared from Fe(NO₃)₃·9H₂O and La(NO₃)·6H₂O by a simple sol-gel method and its catalytic efficiency was evaluated for mineralization of 4-chlorophenol using a Fenton-like process. The mineralization process was carried out under ultrasonication in presence of heterogeneous LaFeO₃ catalyst with H₂O₂ that was produced during ultrasonication. The mineralization process was monitored through total organic carbon (TOC) analysis. Very importantly, utmost 5-fold synergism was evidenced by the ultrasound mediated LaFeO₃-catalyzed system. Besides, more than twofold synergism was observed by combining the ultrasound assisted LaFeO₃ catalytic process and potassium persulfate (KPS) assisted advanced oxidation process. It is worth to mention that complete mineralization (∼96%) of 4-chlorophenol (initial concentration of 1.25 × 10⁻⁴ M) was observed within 1 h in the presence of LaFeO₃ (0.5 g L⁻¹) and KPS (1.0 mmol) under ultrasonication (40 kHz). Even after four cycles, the activity of LaFeO₃ remained intact which proved its recyclability. Extremely reusable heterogeneous LaFeO₃ catalyst makes the system more interesting from both economic and environmental points of view.     

Sonochemically preparation and characterization of bimetallic Ni-Co/Al2O3-ZrO2 nanocatalyst: Effects of ultrasound irradiation time and power on catalytic properties and activity in dry reforming of CH4

The catalytic performance of nanostructured Ni-Co/Al₂O₃-ZrO₂ catalysts, prepared by ultrasound-assisted impregnation method was examined in the dry reforming of methane. The effect of irradiation power and irradiation time have been studied by changing time (0, 20, 80 min) and power of the sonication (30, 60, 90 W) during the synthesis which resulted in different physiochemical properties of the nanocatalyst. The nanocatalysts were characterized by XRD, FESEM, PSD, EDX, TEM, TPR-H₂, BET, FTIR and TG analyses. Based on the characterization results, ultrasound treatment endowed the sample with more uniform and smaller nanoparticles; higher surface area, stronger metal-support interaction and more homogenous dispersion. Moreover, the analyses exhibited smaller particles with higher surface area and less population of particle aggregates at longer and highly irradiated nanocatalysts. The nanocatalyst irradiated at 90 W for 80 min (the longest irradiation time and the most intense power) showed a uniform morphology and a very narrow particles size distribution. More than 65% of particles of this nanocatalyst were in the range of 10–30 nm. Activity tests demonstrated that employing ultrasound irradiation during impregnation improves feed conversion and products yield, reaching values close to equilibrium. Among sonicated nanocatalysts, with increasing power and time of irradiation, the nanocatalyst represents higher activity. The superior performance amongst the various bimetallic catalysts tested was observed over the catalyst with 90 W and 80 min ultrasonic irradiation which is stable in 24 h time on stream test. The excellent anti-coking performance of this bimetallic catalyst, confirmed by TG and FESEM analyses of spent catalyst, is closely related to the promoting effect of sonication on the metal-support interaction, Ni dispersion and particle size; and probably, the synergy between metallic species.     

A simultaneous,direct microwave/ultrasound-assisted digestion procedure for the determination of total Kjeldahl nitrogen

Simultaneous direct irradiation with microwaves and ultrasound was used to determine total Kjeldahl nitrogen. The method involves chemical digestion in two steps, mineralization with sulfuric acid and oxidation with H₂O₂. The most influential variables for the microwave/ultrasound (MW/US)-assisted digestion were optimized using tryptophan as the model substance. The optimum conditions were: H₂SO₄ volume, 10 mL; H₂O₂ volume, 5 mL; weight of sample, 0.05 g; MW power, 500 W; US power, 50 W; digestion time, 7 min (i.e., 5 min mineralization and 2 min oxidation). A modification of the classical Kjeldahl (Hach) method and an US-assisted digestion method were used for comparison. The latter was also optimized; the optimum conditions were: H₂SO₄ volume, 10 mL; H₂O₂ volume, 5 mL; sonication time with H₂SO₄, 15 min; sonication time with H₂O₂,10 min; US power, 50 W; weight of sample, 0.05 g. Five pure amino acids and two certified reference materials (NIST standard reference materials 1547 (peach leaves), and soil, NCS DC 73322) were analyzed to assess the accuracy of our new MW/US-assisted digestion method, that was successfully applied to five real samples. The significant reduction in digestion time (being 30 min and 25 min for classical Kjeldahl and US-assisted digestion methods, respectively) and consumption of reagents show that simultaneous and direct MW/US irradiation is a powerful and promising tool for low-pressure digestion of solid and liquid samples.     

Ultrasonic assisted-Fenton-like degradation of nitrobenzene at neutral pH using nanosized oxides of Fe and Cu

Ultrasonic-assisted heterogeneous Fenton reaction was used for degradation of nitrobenzene (NB) at neutral pH conditions. Nano-sized oxides of α-Fe₂O₃ and CuO were prepared, characterized and tested in degradation of NB (10 mg L⁻¹) under sonication of 20 kHz at 25 °C. Complete degradation of NB was effected at pH 7 in presence of 10 mM H₂O₂ after 10 min of sonication in presence of α-Fe₂O₃ (1.0 g L⁻¹), (k = 0.58 min⁻¹) and after 25 min in case of CuO (k = 0.126 min⁻¹). α-Fe₂O₃ showed also effective degradation under the conditions of 0.1 g L⁻¹ oxide and 5.0 mM of H₂O₂, even though with a lower rate constant (0.346 min⁻¹). Sonication plays a major role in enhancing the production of hydroxyl radicals in presence of solid oxides. Hydroxyl radicals-degradation pathway is suggested and adopted to explain the differences noted in rate constants recorded on using different oxides.     

Degradation of C.I. Direct Black 168 from aqueous solution by fly ash/H2O2 combining ultrasound

Degradation of C.I. Direct Black 168 from aqueous solution using Fenton-like reactions combining ultrasound was investigated. In the presence of H₂O₂, the effect of the heterogeneous catalysts, such as fly ash, kaolinite or diatomaceous earth on the degradation of Direct Black 168 was observed under ultrasound. The fly ash was the most efficient catalyst. It is apparent that ultrasound can prompt the reaction to take place and give in higher degradation. In the combination of ultrasound and fly ash/H₂O₂, the effect of different system variables namely concentration of the dye, dosage of fly ash, concentration of H₂O₂, pH of solution and the addition of NaCl were studied. 99.0% removal ratio was achieved at initial concentration 100 mg/L, pH 3.0, and dosage of fly ash 2.0 g/L, as well as 2.94 mM H₂O₂. NaCl exhibited only a minor effect on the dye removal.     

Dual frequency cavitation event sensor with iodide dosimeter

The inertial cavitation activity depends on the sonication parameters. The purpose of this work is development of dual frequency inertial cavitation meter for therapeutic applications of ultrasound waves. In this study, the chemical effects of sonication parameters in dual frequency sonication (40 kHz and 1 MHz) were investigated in the progressive wave mode using iodide dosimetry. For this purpose, efficacy of different exposure parameters such as intensity, sonication duration, sonication mode, duty factor and net ultrasound energy on the inertial cavitation activity have been studied. To quantify cavitational effects, the KI dosimeter solution was sonicated and its absorbance at a wavelength of 350 nm was measured. The absorbance values in continuous sonication mode was significantly higher than the absorbance corresponding to the pulsed mode having duty factors of 20–80% (p < 0.05). Among different combination modes (1 MHz_100% + 40 kHz_100%, 1 MHz_100% + 40 kHz_80%, 1 MHz_80% + 40 kHz_100%, 1 MHz_80% + 40 kHz_80%), the continuous mode for dual frequency sonication is more effective than other combinations (p < 0.05). The absorbance for this combined dual frequency mode was about 1.8 times higher than that obtained from the algebraic summation of single frequency sonications. It is believed that the optimization of dual frequency sonication parameters at low-level intensity (<3 W/cm²) by optically assisted cavitation event sensor can be useful for ultrasonic treatments.     

Efficient H2O2/CH3COOH oxidative desulfurization/denitrification of liquid fuels in sonochemical flow-reactors

The oxidative desulfurization/denitrification of liquid fuels has been widely investigated as an alternative or complement to common catalytic hydrorefining. In this process, all oxidation reactions occur in the heterogeneous phase (the oil and the polar phase containing the oxidant) and therefore the optimization of mass and heat transfer is of crucial importance to enhancing the oxidation rate. This goal can be achieved by performing the reaction in suitable ultrasound (US) reactors. In fact, flow and loop US reactors stand out above classic batch US reactors thanks to their greater efficiency and flexibility as well as lower energy consumption. This paper describes an efficient sonochemical oxidation with H₂O₂/CH₃COOH at flow rates ranging from 60 to 800 ml/min of both a model compound, dibenzotiophene (DBT), and of a mild hydro-treated diesel feedstock. Four different commercially available US loop reactors (single and multi-probe) were tested, two of which were developed in the authors’ laboratory. Full DBT oxidation and efficient diesel feedstock desulfurization/denitrification were observed after the separation of the polar oxidized S/N-containing compounds (S ⩽ 5 ppmw, N ⩽ 1 ppmw). Our studies confirm that high-throughput US applications benefit greatly from flow-reactors.     

Mechanistic study on ultrasound assisted pretreatment of sugarcane bagasse using metal salt with hydrogen peroxide for bioethanol production

This study presents the ultrasound assisted pretreatment of sugarcane bagasse (SCB) using metal salt with hydrogen peroxide for bioethanol production. Among the different metal salts used, maximum holocellulose recovery and delignification were achieved with ultrasound assisted titanium dioxide (TiO₂) pretreatment (UATP) system. At optimum conditions (1% H₂O₂, 4 g SCB dosage, 60 min sonication time, 2:100 M ratio of metal salt and H₂O₂, 75 °C, 50% ultrasound amplitude and 70% ultrasound duty cycle), 94.98 ± 1.11% holocellulose recovery and 78.72 ± 0.86% delignification were observed. The pretreated SCB was subjected to dilute acid hydrolysis using 0.25% H₂SO₄ and maximum xylose, glucose and arabinose concentration obtained were 10.94 ± 0.35 g/L, 14.86 ± 0.12 g/L and 2.52 ± 0.27 g/L, respectively. The inhibitors production was found to be very less (0.93 ± 0.11 g/L furfural and 0.76 ± 0.62 g/L acetic acid) and the maximum theoretical yield of glucose and hemicellulose conversion attained were 85.8% and 77%, respectively. The fermentation was carried out using Saccharomyces cerevisiae and at the end of 72 h, 0.468 g bioethanol/g holocellulose was achieved. Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analysis of pretreated SCB was made and its morphology was studied using scanning electron microscopy (SEM). The compounds formed during the pretreatment were identified using gas chromatography–mass spectrometry (GC–MS) analysis.     

Synthesis of nanocomposites of iron oxide/gold (Fe3O4/Au) loaded on activated carbon and their application in water treatment by using sonochemistry: Optimization study

This paper focuses on the finding best operational conditions using response surface methodology (RSM) for Rhodamine123 (R123) and Disulfine blue (DSB) dyes removal by ultrasound assisted adsorption onto Au-Fe₃O₄ nanoparticles loaded on activated carbon (Au-Fe₃O₄ NPs-AC). The influences of variables such as initial R123 (X₁) and DSB concentration (X₂), pH (X₃), adsorbent mass (X₄) and sonication time (X₅) on their removal were investigated by small central composite design (CCD) under response surface methodology. The significant variables and the possible interactions among variables were investigated and estimated accordingly. The best conditions were set as: 4 min, 4.0, 0.025 g, 13.5 and 26.5 mg L⁻¹ for sonication time, pH, adsorbent weight, initial R123 and DSB concentration, respectively. At above conditions, the adsorption equilibrium and kinetic follow the Langmuir isotherm and pseudo-second-order kinetic model, respectively. The maximum monolayer capacity (Q_max) of 71.46 and 76.38 mg g⁻¹ for R123 and DSB show sufficiency of model for well presentation of experimental data.     

Homogeneous sonophotolysis of food processing industry wastewater: Study of synergistic effects,mineralization and toxicity removal

The mineralization of industrial wastewater coming from food industry using an emerging homogeneous sonophotolytic oxidation process was evaluated as an alternative to or a rapid pretreatment step for conventional anaerobic digestion with the aim of considerably reducing the total treatment time. At the selected operation conditions ([H₂O₂] = 11,750 ppm, pH = 8, amplitude = 50%, pulse length (cycles) = 1), 60% of TOC is removed after 60 min and 98% after 180 min when treating an industrial effluent with 2114 ppm of total organic carbon (TOC). This process removed completely the toxicity generated during storing or due to intermediate compounds.An important synergistic effect between sonolysis and photolysis (H₂O₂/UV) was observed. Thus the sonophotolysis (ultrasound/H₂O₂/UV) technique significantly increases TOC removal when compared with each individual process.Finally, a preliminary economical analysis confirms that the sono-photolysis with H₂O₂ and pretreated water is a profitable system when compared with the same process without using ultrasound waves and with no pretreatment.     

The structure and extinction of nonpremixed methane/nitrous oxide and ethane/nitrous oxide flames

Knowledge of combustion of hydrocarbon fuels with nitrogen-containing oxidizers is a first step in understanding key aspects of combustion of hypergolic and gun propellants. Here an experimental and kinetic-modeling study is carried out to elucidate aspects of nonpremixed combustion of methane (CH₄) and nitrous oxide (N₂O), and ethane (C₂H₆) and N₂O. Experiments are conducted, at a pressure of 1 atm, on flames stabilized between two opposing streams. One stream is a mixture of oxygen (O₂), nitrogen (N₂), and N₂O, and the other a mixture of CH₄ and N₂ or C₂H₆ and N₂. Critical conditions for extinction are measured. Kinetic-modeling studies are performed with the San Diego Mechanism. Experimental data and results of kinetic-modeling show that N₂O inhibits the flame by promoting extinction. Analysis of the flame structure shows that H radicals are produced in the overall chain-branching step 3H₂ + O₂ ? 2H₂O + 2H, in which molecular hydrogen is consumed. Hydrogen is also consumed in the overall step N₂O + H₂ ? N₂ + H₂O where stable products are formed. Inhibition of the flames by N₂O is attributed to competition between these two overall steps.     

Sonocatalytic rapid degradation of Congo red dye from aqueous solution using magnetic Fe0/polyaniline nanofibers

Nano-sized magnetic Fe⁰/polyaniline (Fe⁰/PANI) nanofibers were used as an effective material for sonocatalytic degradation of organic anionic Congo red (CR) dye. Fe⁰/PANI_, was synthesized via reductive deposition of nano-Fe⁰ onto the PANI nanofibers at room temperature. Prepared catalyst was characterized using HR-TEM, FE-SEM, XRD, FTIR instruments. The efficacy of catalyst in removing CR was assessed colorimetrically using UV–visible spectroscopy under different experimental conditions such as % of Fe⁰ loading into the composite material, solution pH, initial concentration of dye, catalyst dosage, temperature and ultrasonic power. The optimum conditions for sonocatalytic degradation of CR were obtained at catalyst concentrations = 500 mg.L⁻¹, concentration of CR = 200 ppm, solution pH = neutral (7.0), temperature = 30 °C, % of Fe⁰ loading = 30% and 500 W ultrasonic power. The experimental results showed that ultrasonic process could remove 98% of Congo red within 30 min with higher Q_max value (Q_max = 446.4 at 25 °C). The rate of degradation of CR dye was much faster in this ultrasonic technique rather than conventional adsorption process. The degradation efficiency declined with the addition of common inorganic salts (NaCl, Na₂CO₃, Na₂SO₄ and Na₃PO₄). The rate of degradation suppressed more with increasing salt concentration. Kinetic and isotherm studies indicated that the degradation of CR provides pseudo-second order rate kinetic and Langmuir isotherm model compared to all other models tested. The excellent high degradation capacity of Fe⁰/PANI under ultrasonic irradiation can be explained on the basis of the formation of active hydroxyl radicals (OH) and subsequently a series of free radical reactions.     

Correlation between iodide dosimetry and terephthalic acid dosimetry to evaluate the reactive radical production due to the acoustic cavitation activity

Acoustic cavitation plays an important role in sonochemical processes and the rate of sonochemical reaction is influenced by sonication parameters. There are several methods to evaluate cavitation activity such as chemical dosimetry. In this study, to comparison between iodide dosimetry and terephthalic acid dosimetry, efficacy of sonication parameters in reactive radical production has been considered by iodide and terephthalic acid dosimetries. For this purpose, efficacy of different exposure parameters on cavitations production by 1 MHz ultrasound has been studied. The absorbance of KI dosimeter was measured by spectrophotometer and the fluorescence of terephthalic acid dosimeter was measured using spectrofluorometer after sonication. The result of experiments related to sonication time and intensity showed that with increasing time of sonication or intensity, the absorbance is increased. It has been shown that the absorbance for continuous mode is remarkably higher than for pulsing mode (p-value < 0.05). Also results show that with increasing the duty cycles of pulsed field, the inertial cavitation activity is increased. With compensation of sonication time or intensity in different duty cycles, no significant absorbance difference were observed unless 20% duty cycle. A significant correlation between the absorbance and fluorescence intensities (count) at different intensity (R = 0.971), different sonication time (R = 0.999) and different duty cycle (R = 0.967) were observed (p-value < 0.05). It is concluded that the sonication parameters having important influences on reactive radical production. These results suggest that there is a correlation between iodide dosimetry and terephthalic acid dosimetry to examine the acoustic cavitation activity in ultrasound field.     

Insights into the novel application of Fe-MOFs in ultrasound-assisted heterogeneous Fenton system: Efficiency,kinetics and mechanism

In this work, as a new strategy, ultrasound/H₂O₂/MOF system was firstly applied by environmental-benign Fe-MOFs (MIL-53, MIL-88B and MIL-101) for tetracycline hydrochloride removal. The synthetic Fe-MOFs were characterized by XRD, FTIR, SEM, XPS, N₂ sorption-desorption isotherms and CO-FTIR. MIL-88B demonstrated the best catalytic performance because of its highest amount of Lewis acid sites. Influencing factors, contrast experiment, and corresponding dynamics were carried out to obtain the best experimental conditions and reaction system. Under optimal conditions ([Tetracycline hydrochloride] = 10 mg/L, [MIL-88B] = 0.3 g/L, [H₂O₂] = 44 mM, [ultrasound power] = 60 W, and pH = 5.0), the-first-order kinetic rate constant k was calculated to be 0.226 min⁻¹, higher than the simple combination of the ultrasound system (0.004) and MIL-88B/H₂O₂ system (0.163), indicating the importance of synergistic effect between ultrasound and Fenton reaction. EPR test and quenching experiment proved that ·OH is mainly responsible for tetracycline hydrochloride removal. The major reaction path is the adsorption and decomposition of H₂O₂ by coordinative unsaturated iron sites on Fe-MOF, but it is not the only path. The direct decomposition of H₂O₂ and the cavitation effect caused by ultrasound also contribute to the generation of OH.     

Enhanced performance of bi-layer Nb2O5 coated TiO2 nanoparticles/nanowires composite photoanode in dye-sensitized solar cells

Dye sensitized solar cells (DSSCs) were fabricated based on coumarin NKX-2700 dye sensitized bi-layer photoanode and quasi-solid state electrolyte sandwiched together with cobalt sulfide coated counter electrode. A novel bi-layer photoanode has been prepared using composite mixtures of 90 wt.% TiO₂ nanoparticles + 10 wt.% TiO₂ nanowires (TNPWs) as active layer and Nb₂O₅ is coated on the active layer, which acts as scattering layer. Hafnium oxide (HfO₂) was applied over the TNPWs/Nb₂O₅ photoanode film, as a blocking layer. TiO₂ nanoparticles (TNPs), TiO₂ nanowires (TNWs) and TNPWs/Nb₂O₅ were characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). The sensitizing organic dye coumarin NKX-2700 displayed maximum absorption wavelength (λ_max) at 525 nm, which could be observed from the UV–vis spectrum. DSSC-1 fabricated with composite bi-layer photoanode revealed enhanced photo-current efficiency (PCE) as compared to other DSSCs and illustrated photovoltaic parameters; short-circuit current J_SC = 18 mA/cm², open circuit voltage (V_OC) = 700 mV, fill factor (FF) = 64% and PCE (η) = 8.06%. The electron transport and charge recombination behaviors of DSSCs were investigated by electrochemical impedance spectra (EIS) and the results illustrated that the DSSC-1 showed the lowest charge transport resistance (R_tr) and the longest electron lifetime (τ_eff). Therefore, in the present investigation, it could be concluded that the novel bi-layer photoanode with blocking layer increased the short circuit current, electron transport and suppressed the recombination of charge carriers at the photoanode/dye/electrolyte interface in DSSC-1.     

Synthesis and electrical transport properties of Lu2+xTi2−xO7−x/2 oxide-ion conductors

The Lu_2+xTi_2−xO_7−x/2 (x = 0; 0.052; 0.096; 0.286; 0.44; 0.63; 33.3–49 mol% Lu₂O₃) nanoceramics with partly disordered pyrochlore-type structure are prepared by sintering freeze-dried powders obtained by a co-precipitation technique with 1600 °C annealing. Similar to pyrochlore-like compositions in the zirconate system, some of the new titanates are good oxide-ion conductors in air. The new solid-state electrolytes have oxide-ion conductivity in the interval of 1.0 × 10^− 3 – 2.5 × 10^− 3 S/cm at 740 °C in air. This value of conductivity is comparable with that of ZrO₂/Y₂O₃ ceramics. The conductivity of Lu_2+xTi_2−xO_7−x/2 depends on the chemical composition. The highest ionic conductivity is exhibited by nearly stoichiometric Lu_2+xTi_2−xO_7−x/2 (x = 0.096; 35.5 mol% Lu₂O₃) material containing ∼ 4.8 at.% Lu_Ti anti-site defects.     

Ultrasound-induced emulsification of subcritical carbon dioxide/water with and without surfactant as a strategy for enhanced mass transport

Pulsed ultrasound was used to disperse a biphasic mixture of CO₂/H₂O in a 1 dm³ high-pressure reactor at 30 °C/80 bar. A view cell positioned in-line with the sonic vessel allowed observation of a turbid emulsion which lasted approximately 30 min after ceasing sonication. Within the ultrasound reactor, simultaneous CO₂-continuous and H₂O-continuous environments were identified. The hydrolysis of benzoyl chloride was employed to show that at similar power intensities, comparable initial rates (1.6 ± 0.3 × 10^–3 s^–1 at 95 W cm^–2) were obtained with those reported for a 87 cm³ reactor (1.8 ± 0.2 × 10^–3 s^–1 at 105 W cm^–2), demonstrating the conservation of the physical effects of ultrasound in high-pressure systems (emulsification induced by the action of acoustic forces near an interface). A comparison of benzoyl chloride hydrolysis rates and benzaldehyde mass transport relative to the non-sonicated, ‘silent’ cases confirmed that the application of ultrasound achieved reaction rates which were over 200 times faster, by reducing the mass transport resistance between CO₂ and H₂O. The versatility of the system was further demonstrated by ultrasound-induced hydrolysis in the presence of the polysorbate surfactant, Tween, which formed a more uniform CO₂/H₂O emulsion that significantly increased benzoyl chloride hydrolysis rates. Finally, pulse rate was employed as a means of slowing down the rate of hydrolysis, further illustrating how ultrasound can be used as a valuable tool for controlling reactions in CO₂/H₂O solvent mixtures.