Synthesis of CuO nanoparticles through green route using Citrus limon juice and its application as nanosorbent for Cr(VI) remediation: Process optimization with RSM and ANN-GA based model

In present investigation, an attempt has been made for the synthesis of cupric oxide nanoparticles (CuONPs) through a green route by utilizing lemon juice extract as a bioreductant. The synthesized CuONPs were characterized through UV–visible spectroscopy, Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The CuONPs were utilized for Cr(VI) removal from water through adsorption method in batch mode at different initial Cr(VI) concentration, pH, temperature and CuONPs dosage. The maximum uptake capacity of CuONPs was found to be 16.63 mg of Cr(VI)/g at pH 4.0. Implementation of response surface methodology (RSM) followed by artificial neural network hybridized with genetic algorithm (ANN-GA) approach has resulted maximum Cr(VI) adsorption of 98.8% under the optimized conditions of initial metal concentration 22.5 mg/L, pH 3.81, CuONPs dose 1.28 g/L and temperature 37.1 °C. Under optimum conditions, adsorption isotherm study was conducted, which showed that the fitness of experimental data was well achieved with Langmuir isotherm model illustrating monolayer pattern of adsorption. Thermodynamic study revealed that the process was spontaneous and endothermic in nature, while adsorption kinetics was best explained by pseudo-second order kinetic model.     

Simultaneous photocatalytic treatment of Cr(VI), Ni(II) and SDBS in aqueous solutions: Evaluation of removal efficiency and energy consumption

Simultaneous photocatalytic reduction of poisonous Cr(VI) and Ni(II) ions, coupled with photocatalytic oxidation of sodium dodecyl benzene sulfonate (SDBS) were studied with a trace amount of commercial titania nanoparticles and by means of a direct-photo-irradiation reactor. The co-presence of metal ions and SDBS causes metal ions reduction as well as SDBS oxidation to enhance and energy efficiency to improve. XRD, XPS and FTIR analysis were used to characterize TiO₂ particles before and after usage with the aim of evaluating the mechanism of reactions. The effect of major operating parameters, pH and temperature, was investigated. Under conditions of [Cr(VI)]₀ = [Ni(II)]₀ = 5 mg/L, [SDBS]₀ = 10 mg/L, [TiO₂] = 40 mg/L, pH 6 and T = 35 °C; the removal efficiencies of 55.4%, 71.2% and 57.2% were obtained, respectively, for Cr(VI) and Ni(II) reduction, as well as for SDBS oxidation, after 110 min operation. The relevant kinetic model jointed with the Arrhenius equation was introduced. Pseudo-first-order reactions are relevant. Energy consumption (electrical and thermal) evaluations revealed that operations at higher temperatures provide significant cost reduction. Meantime, a criterion was proposed for a consistent assessment of this kind of processes.     

Feasibility of honeycomb monolith supported sugar catalyst to produce biodiesel from palm fatty acid distillate (PFAD)

Carbon coated monolith was prepared by sucrose solution 65 wt.% via dip-coating method. Sulfonation of incomplete carbonized carbon coated monolith was carried out in order to synthesize solid acid catalyst. The textural structure characteristics of the solid acid catalyst demonstrated a low surface area and pore volume. Palm fatty acid distillate (PFAD), a by-product of palm oil refineries, was utilized as oil source in biodiesel production. The esterification reaction subjected to different reaction conditions was performed by using the sulfonated carbon coated monolith as heterogeneous catalyst. The sulfonation process had been performed by using vapour of concentrated H₂SO₄ that was much easier and efficient than liquid phase sulfonation. Total acidity value of carbon coated monolith was measured for unsulfonated sample (0.5 mmol/g) and sulfonated sample (4.2 mmol/g). The effect of methanol/oil ratio, catalyst amount and reaction time were examined. The maximum methyl ester content was 89% at the optimum condition, i.e. methanol/oil molar ratio (15:1), catalyst amount (2.5 wt.% with respect to PFAD), reaction time (240 min) and temperature 80 °C. The sugar catalyst supported on the honeycomb monolith showed comparable reactivity compared with the sugar catalyst powder. However, the catalyst reusability studies showed decrease in FFA% conversion from 95.3% to 68.8% after four cycles as well as the total acidity of catalyst dropped from the value 4.2 to 3.1 mmol/g during these cycles. This might be likely due to the leaching out of SO₃H group from the sulfonated carbon coated monolith surface. The leaching of active species reached a plateau state after fourth cycle.     

Optimizing the preparation parameters of mesoporous nanocrystalline titania and its photocatalytic activity in water: Physical properties and growth mechanisms

Titania nanomaterial with an anatase structure and 5.6 nm crystallite size and 280.7 m² g⁻¹ specific surface areas had been successfully prepared by sol–gel/hydrothermal route. The effect of pH as a type of autoclave and calcination was studied. Crystallite size and phase composition of the prepared samples were identified. X-ray diffraction analyses showed the presence of anatase with little or no rutile phases. The crystallite size of the prepared TiO₂ with acidic catalyst was both smaller than that prepared with basic catalyst, and was increasing after acidic calcinations by a factor 4–5. Basic calcinations produced a specific increase of 1.5. Rutile ratio and the particle size were increased after calcination at 500 °C. However, TiO₂ powder synthesized using a basic catalyst persisted the anatase phase and a loosely aggregation of particles. Anatase TiO₂ as prepared with acidic catalyst in Teflon lined stainless steel autoclave demonstrated the highest photocatalytic activity for degradation of 2,6-dichlorophenol-indophenol under ultraviolet irradiation with t_½ 0.8 min.     

Mesoporous simonkolleite–TiO2 nanostructured composite for simultaneous photocatalytic hydrogen production and dye decontamination

In the present work, mesoporous simonkolleite–TiO₂ composite was prepared with sol–gel method. The composite photocatalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), and Raman spectroscopy. Also, surface area and particle size were analyzed using BET equation. The photocatalytic hydrogen production with simultaneous decolorization of Remazole Red (F3B) dye was investigated over TiO₂ and simonkolleite–TiO₂ composite under UV–vis light irradiation. It was worthy to be noted that the rate of hydrogen production over simonkolleite–TiO₂ is higher that produced over TiO₂. The maximum amount of photocatalytic-produced hydrogen was 2.1 mmol and 3.3 mmol within 240 min using TiO₂ and simonkolleite–TiO₂ composite, respectively. The specific production rate of hydrogen from photocatalytic conversion of dye was calculated. Improvement of apparent quantum yield (22.07%) after 5 h was achieved upon addition of simonkolleite to TiO₂. This high apparent quantum yield proves that the system proposed in this study could be a hopeful approach toward using sunlight energy as outlook energy source. The obtained results suggested that a new process for H₂ production from wastewater could be achieved. The process also provides a method for degradation of organic pollutants with simultaneous H₂ production.     

Decolorization and degradation of acid dye with immobilized titania nanoparticles

This paper addresses the decolorization and degradation of acid dye by a heterogeneous photocatalytic process using immobilized nano-sized TiO₂ particles as the photocatalyst. Sackcloth fiber was used as a support to immobilize the nano-sized TiO₂ photocatalyst. The structural properties of the immobilized photocatalyst were characterized by XRD, SEM and EDX. UV–Vis absorption spectroscopy and the measurement of the chemical oxygen demand (COD) were also used for the process performance studies. The XRD results did not show significant changes in the structure of P25 as a consequence of the immobilization procedure. The formation of titania crystallites in the sackcloth fiber was confirmed by SEM/EDX. The photocatalytic activities of TiO₂-coated sackcloth fiber catalyst were evaluated using Acid Black 26 as a model organic contaminant and using UV-A radiation. Experimental results showed that after 60 min, the degradation of Acid Black 26 with the immobilized TiO₂ particles was higher than that with plain TiO₂. Based on the COD results, after 3 h, the TiO₂-coated sackcloth fiber effectively decomposed all of the organic compounds present in dye solution under the studied experimental conditions. The effects of the oxidant H₂O₂, initial dye concentration and pH on the photocatalytic degradation were also investigated. The presence of CO₃^2? as a dissolved inorganic anion had the highest inhibitory effect on the decolorization of the dye, when compared with the other anions investigated. Kinetics analysis indicates that the photocatalytic decolorization rate of Acid Black 26 can be described by a pseudo-first-order model.     

Growing Carbon Nanotube on Aluminum Oxides: An Inherently Safe Approach for Environmental Applications

Using micron-sized Al₂O₃ particles as carriers to grow carbon nanotubes (CNTs) under 700°C atmosphere of methane and hydrogen after pre-planted catalysts of Fe–Ni nanoparticles, those composite CNTs (CCNTs) have demonstrated several unique properties compared to CNTs—medium specific surface area and zeta potential, high adsorption capacity for metal ions, high recovery rate by acids, low decomposition heat for exothermal reaction, and so on. The adsorption behaviours of Pb²⁺, Cu²⁺ and Cd²⁺ in aqueous solutions by CCNTs are in good agreement with the Langmuir adsorption isotherm and second order kinetic model with maximum individual adsorption capacities of 67.11, 26.59 and 8.89 mg g⁻¹. The individual and competitive adsorption behaviours indicated that the preference order of adsorption were Pb²⁺ > Cu²⁺ > Cd²⁺ for aluminum oxides, activated carbon, commercial CNTs, and CCNTs as well as other researchers’ CNTs. We suggest that future development of CNTs to combine with metals and/or other materials, such as TiO₂, should consider attached to carriers or surface in order to avoid concerns on environment, health and safety. Thus, growing CNTs on Al₂O₃ particles to form CCNTs is an inherently safe approach for many promising environmental applications.     

Preparation of iodine doped titanium dioxide to photodegrade aqueous bisphenol A under visible light

Highly photoactive iodine-doped titanium dioxide (I-doped TiO₂) photocatalysts were synthesized to degrade aqueous bisphenol A (BPA) under irradiation by visible light and sunlight. The band gap energies of TiO₂ and I-doped TiO₂ (I/Ti mole ratio = 0.5%) were 3.01 and 3.04, and the BPA photodegradation rate constants were 1.61, and 5.11 h⁻¹, respectively. The most probable reaction mechanism was proposed to involve IO₄⁻ and IO₃⁻ as electron acceptors that generate an inductive effect, increasing the photocatalytic efficiency of TiO₂. Results indicated that I-doped TiO₂ not only acted favorably as a photocatalyst, but also exhibited considerable mineralization effects. In addition, a recycling test after ten experiments demonstrated the stability and reusability of the photocatalyst.     

Calorimetric behaviors of N2H4 by DSC and superCRC

The objective of this study is to obtain information about the thermal decomposition behaviors of hydrazine (N₂H₄) caused by metals, using differential scanning calorimeter (DSC) and SuperCRC. The DSC measurements revealed that the exothermic reactions of N₂H₄ were caused by the reaction conditions such as the type of cells; the T_DSC with a gold pan is 485.2 K and that with a glass capillary is 620.5 K. Besides, the activation energy of the thermal decomposition of N₂H₄, calculated from the Kissinger and Ozawa methods, were found to be about 38±2 kJ mol⁻¹ in the gold pan and 141±8 kJ mol⁻¹ in the glass capillary. Moreover, a heat flow profile was observed with SuperCRC during the mixing of N₂H₄ and the metal ion solution at 298 K. The maximum heat flow was related to the metal ion oxidative characters. The higher oxidative characters would provide a faster acceleration for the exothermic behavior than the lower oxidative ions. Based on this study, Mn(VII) and Cr(VI) were considered to exhibit strongly oxidative characteristics during mixing with N₂H₄.     

Optimization of novel pyrazolium ionic liquid catalysts for transesterification of bitter apple oil

In the present study, 4 different functionalized pyrazoliums based on sulfoalkyl-pyrazolium hydrogensulfate and alkylsulfo-alakylpyrazolium hydrogensulfate were explored to catalyze biodiesel production from bitter apple oil (BAO). The results demonstrated that a longer chains catalyst of 2-(4-sulfobutyl) pyrazolium hydrogensulfate (SBPHSO₄) exhibited the highest catalytic activity, which is attributed to its strong acidity. The highest yield of esters was up to 89.5% when the reaction was carried out under the conditions of 5.2 wt% of SBPHSO₄, molar ratio of methanol to BAO of 15:1, 170 °C, and 800 rpm for 6 h. These results demonstrated that ionic liquids offer a promising new type of pyrazolium catalyst for biodiesel production. The use of clean ionic liquids in preparing clean biodiesel could solve the drawbacks associated with using the old conventional catalysts and might be employed as an efficient catalyst for such relevance.     

Modeling and optimization of a sono-assisted photocatalytic water treatment process via central composite design methodology

This work focuses on modeling and optimization of a sono-assisted photocatalytic decolorization process of a model pollutant, azo dye C.I. direct red 16 (DR16). In the process, a high temperature thermal decomposition nano synthesized titanium dioxide (TD-TiO₂) was applied as photocatalyst. Central composite design (CCD) methodology was used for designing the experiments, modeling and optimization of the process. A quadratic model was established to describe dependency of the decolorization efficiency (DE), as the model response, to some effective operational parameters, i.e. the catalyst dosage, pH and the dye initial concentration. The ANOVA analysis confirmed that all of the variables have significant influence on the model response. Under the established optimum conditions, 92.4% DE was achieved after 45 min; however, to access desirable mineralization efficiency, the process should be continued up to 120 min. All withdrawn samples from the reaction media during the process showed no antibacterial activity, which indicates safety of the treated effluent for disposal into the environment. Also studies showed that the process proceeds via two parallel branches of photolysis and photocatalysis, where propagation of the ultrasonic waves into the reaction media plays a vital promoting role on the latter branch.     

Refinery wastewater degradation with titanium dioxide,zinc oxide,and hydrogen peroxide in a photocatalytic reactor

This paper presents the photo-catalytic degradation of real refinery wastewater from National Refinery Limited (NRL) in Karachi, Pakistan, using TiO₂, ZnO, and H₂O₂. The pretreatment of the refinery effluent was carried out on site and pretreated samples were tested at 32–37 °C in a stirrer bath reactor by using ultra-violet photo oxidation process. The degradation of wastewater was measured as a change in initial chemical oxygen demand (COD) and with time. Optimal conditions were obtained for catalyst type, and pH. The titanium dioxide proved to be very effective catalysts in photo-catalytic degradation of real refinery wastewater. The maximum degradation achieved was 40.68% by using TiO₂ at 37 °C and pH of 4, within 120 min of irradiations. When TiO₂ was combined with H₂O₂ the degradation decreased to 25.35%. A higher reaction rate was found for titanium dioxide. The results indicate that for real refinery wastewater, TiO₂ is comparatively more effective than ZnO and H₂O₂. The experiments indicated that first-order kinetics can successfully describe the photo-catalytic reaction. The ANOVA results for the model showed satisfactory and reasonable adjustment of the second-order regression model with the experimental data. The ANOVA results also showed that pH is significant than reaction time and catalyst dosage of TiO₂; and in case of ZnO, reaction time is significant than pH and catalyst dosage. This study proves that real refinery wastewater reacts differently than synthetic refinery wastewater, oil field produced water or oil water industrial effluent.     

Disintegration of waste activated sludge by different applications of Fenton process

Oxidative disintegration of municipal waste activated sludge (WAS) using conventional Fenton (Fe²⁺ + H₂O₂, CFP) and Fenton type (Fe⁰ + H₂O₂, FTP) processes was investigated and compared in terms of the efficiency of sludge disintegration and enhancement of anaerobic biodegradability. The influences of different operational variables namely sludge pH, initial concentration of Fe²⁺ or Fe⁰, and H₂O₂ were studied in detail. The optimum conditions have been found as catalyst iron dosage = 4 g/kg TS, H₂O₂ dosage = 40 g/kg TS and pH = 3 within 1 h oxidation period for both CFP and FTP. Kinetics studies were performed under optimal conditions. It was determined that the sludge disintegration was happened in two stages by both processes: rapid and subsequent slow disintegration stages and rapid sludge disintegration stage can be described by a zero-order kinetic model. The effects of oxidative sludge disintegration under the optimum conditions on anaerobic digestion were experienced with biochemical methane potential (BMP) assay in batch anaerobic reactors. Total methane production in the CFP and FTP pre-treated reactors increased by 26.9% and 38.0%, relative to the untreated reactor (digested the raw WAS). Furthermore, the total chemical oxygen demand reductions in the pre-treated reactors were improved as well.     

Synthesis and adsorption studies of NiO nanoparticles in the presence of H2acacen ligand,for removing Rhodamine B in wastewater treatment

Cost efficient NiO nanoparticles were synthesized by hydrothermal production of nano-scale Ni(OH)₂, using Ni(NO₃)₂·6H₂O and NaOH as precursors, in the presence of H₂acacen ligand, followed by calcinations of the produced Ni(OH)₂. Prepared samples were then characterized using X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), Fourier transform infrared (FT-IR) spectra, Brunauer–Emmet–Teller (BET) and transmission electron microscopy (TEM). BET analysis revealed high surface area for pure nano sized NiO, averaging 176.56 m²/g and confirming its application as an efficient adsorbent. Experimental studies for Rhodamine B (RB) removal from aqueous solutions in batch systems revealed that the adsorption equilibrium was best represented by Langmuir isotherm, with the maximum monolayer capacity of 111 mg/g for RB. The kinetic data was well described by a pseudo-second-order kinetic model, having intraparticle diffusion model as a rate limiting step.     

Thermal characterization of fly ash from one municipal solid waste incinerator (MSWI) in Shanghai

This study aims to develop a methodology for the thermal characterization of MSWI fly ash. We performed TGA–DTA and component variation analysis, microstructure transfer of sintered fly ash, as well as leaching toxicity, volatilization ratio and specification transformation of heavy metals as a function of temperature. It is found that content of crystal phases first increases between room temperature and 800 °C and then decreases between 800 °C and 1200 °C, while that of glass phases registers a reverse trend. Fly ash registers a SiO₂–Al₂O₃–metal oxides system and its content of glass phases is around 57%. Increase of sintering temperature between 600 °C and 1200 °C is conducive to the reduction of soluble As, Cd, Cu, Hg, Pb, Ni and Zn, while content of soluble Cr increases as temperature rises from 800 °C to 1200 °C.     

Development and physicochemical characterization of a new magnetic nanocomposite as an economic antibiotic remover

Maghemite (ϒ-Fe₂O₃) nanoparticles were impregnated to nanoporous carbon obtained from tomato waste (TWNC). The prepared magnetic composite (MTWNC) was characterized and used to remove tetracycline (TC) from water and then easily be separated from the medium by a magnetic technique. The morphologies and surface chemistries of both magnetic and non-magnetic nanoporous carbons were studied by FTIR, XRD, SEM, SEM-EDX, VSM, BET surface area, proximate and elemental analysis determinations. Batch adsorption studies were carried out and the effects of pH, initial TC concentration, adsorbent dose, ionic strength and temperature were investigated. The adsorption kinetics of TC on MTWNC could be expressed well by the pseudo-second order model, and sorption isotherms were described by Langmuir equation with maximum adsorption capacity of 60.60 mg/g at pH 4 and 50 °C. Thermodynamic parameters showed that the adsorption of TC onto MTWNC was feasible, spontaneous and endothermic. Furthermore, the recyclability of the adsorbent was tested with 0.01 M NaOH solution, and the results show that the synthesized composite adsorbent could be employed repeatedly in wastewater treatment.     

Use of advance oxidation process to improve the biodegradability of olive oil mill effluents

In this study, recalcitrant total phenol (TPh) and organic matter removal were investigated at olive mill wastewater (OMW) in sequential Coagulation and Fenton system. This study focused on different operational parameters such as pH, H₂O₂, and Fe²⁺ dosages, and [Fe²⁺]/[H₂O₂] ratios. The optimum conditions were determined as; pH = 3; [Fe²⁺] = 2.5 g/L; [Fe²⁺]/[H₂O₂] = 2.5. A higher treatment efficiency was achieved at sequential Coagulation and Fenton system (COD, 65.5%) and TPh, 87.2%), compared to coagulation process (COD, 51.4%; total organic carbon (TOC), 38.6% and total nitrogen (TN) 52.1%). This study demonstrated that the Coagulation and Fenton process has a potential for efficient removal of phenolic pollutants from wastewater.     

Effect of ultrasound irradiation and Ni-loading on properties and performance of CeO2-doped Ni/clinoptilolite nanocatalyst used in polluted air treatment

In this research nanocatalysts containing 5, 10 and 15 wt.% of Ni, dispersed by sonication over CeO₂–clinoptilolite composite support were compared toward total oxidation of toluene. Their catalytic performance at different temperatures between 150 and 350 °C was studied based on the oxidative destruction of toluene. The results indicated that the activity of Ni/CeO₂–clinoptilolite nanocatalyst for toluene oxidation increased from 33 to 44% at 250 °C by employing sonochemical method in synthesis of catalyst. Meanwhile, the catalytic activity was also improved when Ni content was increased from 5 to 10 and 15 wt.%. With the aid of several characterization techniques like XRD, FESEM, PSD, EDX, BET and FTIR, the correlation between nanocatalyst structure and its activity was addressed. It is indicated that sonochemical method can lift the catalytic activity due to the better dispersion of catalyst active components and also higher surface area. Among sonicated samples, 15 wt.% Ni nanocatalyst showed the highest toluene oxidation due to the better dispersion of catalyst active components and hence to more effective catalytic sites.     

Removal mechanism of trace oxytetracycline by aerobic sludge

To investigate the mechanism of removal of selected pharmaceuticals in activated sludge systems, laboratory-scale batch experiments were conducted to assess the adsorption and degradation behavior of trace oxytetracycline (OTC). The adsorption equilibrium of OTC was observed in 30 min and the adsorption process could be well described by a pseudo-second-order model with a rate of 0.362 L μg^?1 min^?1. The OTC adsorption rate decreased with increasing temperature and could be fitted by the Freundlich isotherm. The linear partition coefficients (K_d) were 1.19, 0.999, and 0.841 L g^?1 at temperatures of 15, 20, and 25 °C, respectively. Thermodynamic analysis revealed that the adsorption of OTC onto the inactivated sludge was spontaneous (ΔG = ?16.7 to ?17.0 kJ mol^?1), enthalpy-driven (ΔH = ?24.9 kJ mol^?1), entropy-retarded (ΔS = ?27.4 J (mol K)^?1), and predominantly a physical adsorption.     

Biosorption of Co(II) ions from aqueous solution using Chrysanthemum indicum: Kinetics,equilibrium and thermodynamics

The present study investigates the adsorption potential of Chrysanthemum indicum flower in its raw (CIF-R) and biochar (CIF-BC) form for the removal of cobalt ions from aqueous solution. The adsorbents were characterized for their surface area using BET analysis, surface morphology and elemental composition with SEM-EDAX and for the presence of functional groups by FTIR analysis. Batch adsorption experiments were carried out to evaluate the effect of process parameters, viz. pH, adsorbent dosage, initial metal ion concentration, contact time, stirring speed, presence of interfering ions and temperature on the adsorption of Co(II) ion using both the adsorbents. The optimum conditions for maximum removal of Co(II) ion was ascertained to be pH 5 for both adsorbents, adsorbent dose of 4 g/L and 3 g/L, equilibrium time of 60 min and 45 min, respectively, for CIF-R and CIF-BC. The maximum adsorption capacity of CIF-R and CIF-BC was found to be 14.84 mg/g and 45.44 mg/g, respectively, for the removal of Co(II) ion. The mechanism of adsorption was studied using different models of adsorption kinetics, isotherms and thermodynamics. It was inferred that Co(II) adsorption on both CIF-R and CIF-BC followed pseudo-second order kinetics and Langmuir isotherm model with the process being spontaneous and endothermic in nature.