Capacitive Removal of Pb ions via Electrosorption on Novel Willow Biochar - Manganese Dioxide Composites.

AbstractBiochar derived from lignocellulosic biomass has been used as a low-cost adsorbent in wastewater treatment applications. Due to its rich porous structure and good electrical conductivity, biochar can be used as a cost-effective electrode material for capacitive deionization of water. In this work, willow biochar was prepared through carbonization of shrub willow chips, activated with potassium hydroxide, and loaded with manganese dioxide (WBC-K-MnO2 nanocomposite). The prepared materials were used to electrochemically adsorb Pb2+ from aqueous solutions. Under the applied potential of 1.0 V, the WBC-K-MnO2 electrode exhibited a high Pb2+ specific electrosorption capacity (23.3 mg/g) as compared to raw willow biochar (4.0 mg/g) and activated willow biochar (9.2 mg/g). KOH activation followed by MnO2 loading on the surface of raw biochar enhanced its BET surface area (178.7 m2/g) and mesoporous volume ratio (42.1%). Moreover, the WBC-K-MnO2 nanocomposite exhibited the highest specific capacitance value of 234.3 F/g at a scan rate of 5 mV/s. The electrosorption isotherms and kinetic data were well explained by the Freundlich and pseudo-second order models, respectively. The WBC-K-MnO2 electrode demonstrated excellent reusability with a Pb2+ electrosorption efficiency of 76.3% after 15 cycles. Thus, the WBC-K-MnO2 nanocomposite can serve as a promising candidate for capacitive deionization of heavy metal contaminated water.

Defect engineering of oxide perovskites for catalysis and energy storage: synthesis of chemistry and materials science.

Oxide perovskites have emerged as an important class of materials with important applications in many technological areas, particularly thermocatalysis, electrocatalysis, photocatalysis, and energy storage. However, their implementation faces numerous challenges that are familiar to the chemist and materials scientist. The present work surveys the state-of-the-art by integrating these two viewpoints, focusing on the critical role that defect engineering plays in the design, fabrication, modification, and application of these materials. An extensive review of experimental and simulation studies of the synthesis and performance of oxide perovskites and devices containing these materials is coupled with exposition of the fundamental and applied aspects of defect equilibria. The aim of this approach is to elucidate how these issues can be integrated in order to shed light on the interpretation of the data and what trajectories are suggested by them. This critical examination has revealed a number of areas in which the review can provide a greater understanding. These include considerations of (1) the nature and formation of solid solutions, (2) site filling and stoichiometry, (3) the rationale for the design of defective oxide perovskites, and (4) the complex mechanisms of charge compensation and charge transfer. The review concludes with some proposed strategies to address the challenges in the future development of oxide perovskites and their applications.

Enhanced degradation of organic contaminants using catalytic activity of carbonaceous structures: A strategy for the reuse of exhausted sorbents.

Generation of hydroxyl radicals (⋅OH) is the basis of advanced oxidation process (AOP). This study investigates the catalytic activity of microporous carbonaceous structure for in-situ generation of ⋅OH radicals. Biochar (BC) was selected as a representative of carbon materials with a graphitic structure. The work aims at assessing the impact of BC structure on the activation of H2O2, the reinforcement of the persistent free radicals (PFRs) in BC using heavy metal complexes, and the subsequent AOP. Accordingly, three different biochars (raw, chemically- and physiochemically-activated BCs) were used for adsorption of two metal ions (nickel and lead) and the degradation of phenol (100 mg/L) through AOP. The results demonstrated four outcomes: (1) The structure of carbon material, the identity and the quantity of the metal complexes in the structure play the key roles in the AOP process. (2) the quantity of PFRs on BC significantly increased (by 200%) with structural activation and metal loading. (3) Though the Pb-loaded BC contained a larger quantity of PFRs, Ni-loaded BC exhibited a higher catalytic activity. (4) The degradation efficiency values for phenol by modified biochar in the presence of H2O2 was 80.3%, while the removal efficiency was found to be 17% and 22% in the two control tests, with H2O2 (no BC) and with BC (no H2O2), respectively. Overall, the work proposes a new approach for dual applications of carbonaceous structures; adsorption of metal ions and treatment of organic contaminants through in-situ chemical oxidation (ISCO).

Urea functionalization of ultrasound-treated biochar: A feasible strategy for enhancing heavy metal adsorption capacity.

The main objective of a series of our researches is to develop a novel acoustic-based method for activation of biochar. This study investigates the capability of biochar in adsorbing Ni(II) as a hazardous contaminant and aims at enhancing its adsorption capacity by the addition of extra nitrogen and most probably phosphorous and oxygen containing sites using an ultrasono-chemical modification mechanism. To reach this objective, biochar physically modified by low-frequency ultrasound waves (USB) was chemically treated by phosphoric acid (H3PO4) and then functionalized by urea (CO(NH2)2). Cavitation induced by ultrasound waves exfoliates and breaks apart the regular shape of graphitic oxide layers of biochar, cleans smooth surfaces, and increases the porosity and permeability of biochar's carbonaceous structure. These phenomena synergistically combined with urea functionalization to attach the amine groups onto the biochar surface and remarkably increased the adsorption of Ni(II). It was found that the modified biochar could remove > 99% of 100 mg Ni(II)/L in only six hours, while the raw biochar removed only 73.5% of Ni(II) in twelve hours. It should be noted that physical treatment of biochar with ultrasound energy, which can be applied at room temperature for a very short duration, followed by chemical functionalization is an economical and efficient method of biochar modification compared with traditional methods, which are usually applied in a very severe temperature (>873 K) for a long duration. Such modified biochars can help protect human health from metal-ion corrosion of degrading piping in cities with aging infrastructure.

Sono assisted electrocoagulation process for the removal of pollutant from pulp and paper industry effluent.

In the present work, the efficiency of the sonication, electrocoagulation, and sono-electrocoagulation process for removal of pollutants from the industrial effluent of the pulp and paper industry was compared. The experimental results showed that the sono-electrocoagulation process yielded higher pollutant removal percentage compared to the sonication and electrocoagulation process alone. The effect of the operating parameters in the sono-electrocoagulation process such as electrolyte concentration (1-5 g/L), current density (1-5 A/dm2), effluent pH (3-11), COD concentration (1500-6000 mg/L), inter-electrode distance (1-3 cm), and electrode combination (Fe and Al) on the color removal, COD removal, and power consumption were studied. The maximum color and COD removal percentages of 100 and 95 %, respectively, were obtained at the current density of 4 A/dm2, electrolyte concentration of 4 g/L, effluent pH of 7, COD concentration of 3000 mg/L, electrode combination of Fe/Fe, inter-electrode distance of 1 cm, and reaction time of 4 h, respectively. The color and COD removal percentages were analyzed by using an UV/Vis spectrophotometer and closed reflux method. The results showed that the sono-electrocoagulation process could be used as an efficient and environmental friendly technique for complete pollutant removal.

Investigation of mass transfer intensification under power ultrasound irradiation using 3D computational simulation: A comparative analysis.

This paper aims at investigating the influence of acoustic streaming induced by low-frequency (24kHz) ultrasound irradiation on mass transfer in a two-phase system. The main objective is to discuss the possible mass transfer improvements under ultrasound irradiation. Three analyses were conducted: i) experimental analysis of mass transfer under ultrasound irradiation; ii) comparative analysis between the results of the ultrasound assisted mass transfer with that obtained from mechanically stirring; and iii) computational analysis of the systems using 3D CFD simulation. In the experimental part, the interactive effects of liquid rheological properties, ultrasound power and superficial gas velocity on mass transfer were investigated in two different sonicators. The results were then compared with that of mechanical stirring. In the computational part, the results were illustrated as a function of acoustic streaming behaviour, fluid flow pattern, gas/liquid volume fraction and turbulence in the two-phase system and finally the mass transfer coefficient was specified. It was found that additional turbulence created by ultrasound played the most important role on intensifying the mass transfer phenomena compared to that in stirred vessel. Furthermore, long residence time which depends on geometrical parameters is another key for mass transfer. The results obtained in the present study would help researchers understand the role of ultrasound as an energy source and acoustic streaming as one of the most important of ultrasound waves on intensifying gas-liquid mass transfer in a two-phase system and can be a breakthrough in the design procedure as no similar studies were found in the existing literature.

A comparative fluid flow characterisation in a low frequency/high power sonoreactor and mechanical stirred vessel.

This study aims at analysing the jet-like acoustic streaming generated under low-frequency and high-power ultrasound irradiation and comparing it with fluid streaming generated by traditional mechanical mixing. The main characteristics of fluid flow, which include radial, axial and tangential terms of velocity and their effects on fluid flow pattern, pressure distribution, axial mixing time and turbulence intensity were considered at different power inputs. Both 3D CFD simulation and Particle Image Velocimetry (PIV) were used in this study. The CFD results indicated that the jet-like acoustic streaming reached the velocity magnitude of 145 cm/s at 400 W, which reduced the mixing time to 1.38 s. However, the minimum mixing time of 3.18 s corresponding to the impeller rotational speed of 800 RPM was observed for mechanical stirring. A uniform axial flow pattern was generated under ultrasound irradiation whereas the tangential flow pattern was more prominent in the stirred vessel. Besides, the highest turbulence was observed in the vicinity of the ultrasound transducer and impeller with the values of 138% and 82% for the ultrasonicator and stirred vessel, respectively. The predicted fluid flow pattern under ultrasound irradiation was in a reasonable agreement with that obtained from PIV, with a reasonable accuracy.

Influence of ultrasound power on acoustic streaming and micro-bubbles formations in a low frequency sono-reactor: mathematical and 3D computational simulation.

This paper aims at investigating the influence of ultrasound power amplitude on liquid behaviour in a low-frequency (24 kHz) sono-reactor. Three types of analysis were employed: (i) mechanical analysis of micro-bubbles formation and their activities/characteristics using mathematical modelling. (ii) Numerical analysis of acoustic streaming, fluid flow pattern, volume fraction of micro-bubbles and turbulence using 3D CFD simulation. (iii) Practical analysis of fluid flow pattern and acoustic streaming under ultrasound irradiation using Particle Image Velocimetry (PIV). In mathematical modelling, a lone micro bubble generated under power ultrasound irradiation was mechanistically analysed. Its characteristics were illustrated as a function of bubble radius, internal temperature and pressure (hot spot conditions) and oscillation (pulsation) velocity. The results showed that ultrasound power significantly affected the conditions of hotspots and bubbles oscillation velocity. From the CFD results, it was observed that the total volume of the micro-bubbles increased by about 4.95% with each 100 W-increase in power amplitude. Furthermore, velocity of acoustic streaming increased from 29 to 119 cm/s as power increased, which was in good agreement with the PIV analysis.

Mechanistic analysis of cavitation assisted transesterification on biodiesel characteristics.

The influence of sonoluminescence transesterification on biodiesel physicochemical properties was investigated and the results were compared to those of traditional mechanical stirring. This study was conducted to identify the mechanistic features of ultrasonication by coupling statistical analysis of the experiments into the simulation of cavitation bubble. Different combinations of operational variables were employed for alkali-catalysis transesterification of palm oil. The experimental results showed that transesterification with ultrasound irradiation could change the biodiesel density by about 0.3kg/m(3); the viscosity by 0.12mm(2)/s; the pour point by about 1-2°C and the flash point by 5°C compared to the traditional method. Furthermore, 93.84% of yield with alcohol to oil molar ratio of 6:1 could be achieved through ultrasound assisted transesterification within only 20min. However, only 89.09% of reaction yield was obtained by traditional macro mixing/heating under the same condition. Based on the simulated oscillation velocity value, the cavitation phenomenon significantly contributed to generation of fine micro emulsion and was able to overcome mass transfer restriction. It was found that the sonoluminescence bubbles reached the temperature of 758-713K, pressure of 235.5-159.55bar, oscillation velocity of 3.5-6.5cm/s, and equilibrium radius of 17.9-13.7 times greater than its initial size under the ambient temperature of 50-64°C at the moment of collapse. This showed that the sonoluminescence bubbles were in the condition in which the decomposition phenomena were activated and the reaction rate was accelerated together with a change in the biodiesel properties.