An enhanced ferromagnetic property, visible light active TiO(2) photocatalyst was successfully synthesized by supporting strontium ferrite (SrFe(12)O(19)) onto TiO(2) doped with nitrogen (N) and compared with N-doped TiO(2). The synthesized catalysts were further characterized with X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive X-ray spectroscopy (EDS), BET surface area analysis, vibrating sample magnetometer (VSM), X-ray photon spectroscopy (XPS) and visible light spectroscopy analysis for their respective properties. The XRD and EDS revealed the structural and inorganic composition of N-TiO(2) supported on SrFe(12)O(19). The supported N-TiO(2) exhibited a strong ferromagnetic property with tremendous stability against magnetic property losses. It also resulted in reduced band gap (2.8 eV) and better visible light absorption between 400 and 800 nm compared to N-doped TiO(2). The photocatalytic activity was investigated with a recalcitrant phenolic compound namely 2,4-dichlorophenol (2,4-DCP) as a model pollutant under direct bright and diffuse sunlight exposure. A complete degradation of 2,4-DCP was achieved with an initial concentration of 50mg/L for both photocatalysts in 180 min and 270 min respectively under bright sunlight. Similarly the diffuse sunlight study resulted in complete degradation for supported N-TiO(2) and >85% degradation N-TiO(2), respectively. Finally the supported photocatalyst was separated under permanent magnetic field with a mass recovery ≈ 98% for further reuse.
Engkabang fat esters were produced via alcoholysis reaction between Engkabang fat and oleyl alcohol, catalyzed by Lipozyme RM IM. The reaction was carried out in a 500 ml Stirred tank reactor using heptane and hexane as solvents. Response surface methodology (RSM) based on a four-factor-five-level Central composite design (CCD) was applied to evaluate the effects of synthesis parameters, namely temperature, substrate molar ratio (oleyl alcohol: Engkabang fat), enzyme amount and impeller speed. The optimum yields of 96.2% and 91.4% were obtained for heptane and hexane at the optimum temperature of 53.9°C, impeller speeds of 309.5 and 309.0 rpm, enzyme amounts of 4.82 and 5.65 g and substrate molar ratios of 2.94 and 3.39:1, respectively. The actual yields obtained compared well with the predicted values of 100.0% and 91.5%, respectively. Meanwhile, the properties of the esters show that they are suitable to be used as ingredient for cosmetic applications.
Photocatalytic degradation of p-cresol was carried out using ZnO under UV irradiation. The amount of photocatalyst, concentration of p-cresol and pH were studied as variables. The residual concentration and mineralization of p-cresol was monitored using a UV-visible spectrophotometer and total organic carbon (TOC) analyzer, respectively. The intermediates were detected by ultra high pressure liquid chromatography (UPLC). The highest photodegradation of p-cresol was observed at 2.5 g/L of ZnO and 100 ppm of p-cresol. P-cresol photocatalytic degradation was favorable in the pH range of 6-9. The detected intermediates were 4-hydroxy-benzaldehyde and 4-methyl-1,2-benzodiol. TOC studies show that 93% of total organic carbon was removed from solution during irradiation time. Reusability shows no significant reduction in photocatalytic performance in photodegrading p-cresol.
A hybrid biofuel cell, a zinc-air cell employing laccase as the oxygen reduction catalyst is investigated. A simple cell design is employed; a membraneless single chamber and a freely suspended laccase in the buffer electrolyte. The cell is characterised based on its open-circuit voltage, power density profile and galvanostatic discharge at 0.5 mA. The activity of laccase as an oxidoreductase is substantiated from the cell discharge profiles. The use of air electrode in the cell design enhanced the energy output by 14%. The zinc-air biofuel cell registered an open-circuit voltage of 1.2 V and is capable to deliver a maximum power density of 1.1 mWcm-2 at 0.4 V. Despite its simple design features, the power output is comparable to that of biocatalytic cell utilising a much more complex system design.
In this study, an artificial neural network (ANN) trained by backpropagation algorithm, Levenberg-Marquadart, was applied to predict the yield of enzymatic synthesis of dioctyl adipate. Immobilized Candida antarctica lipase B was used as a biocatalyst for the reaction. Temperature, time, amount of enzyme, and substrate molar ratio were the four input variables. After evaluating various ANN configurations, the best network was composed of seven hidden nodes using a hyperbolic tangent sigmoid transfer function. The correlation coefficient (R2) and mean absolute error (MAE) values between the actual and predicted responses were determined as 0.9998 and 0.0966 for training set and 0.9241 and 1.9439 for validating dataset. A simulation test with a testing dataset showed that the MAE was low and R2 was close to 1. These results imply the good generalization of the developed model and its capability to predict the reaction yield. Comparison of the performance of radial basis network with the developed models showed that radial basis function was more accurate but its performance was poor when tested with unseen data. In further part of the study, the feedforward backpropagation model was used for prediction of the ester yield within the given range of the main parameters.
The fuel crisis and environmental concerns, mainly due to global warming, have led researchers to consider the importance of biofuels such as biodiesel. Vegetable oils, which are too viscous to be used directly in engines, are converted into their corresponding methyl or ethyl esters by a process called transesterification. With the recent debates on "food versus fuel," non-edible oils, such as Jatropha curcas, are emerging as one of the main contenders for biodiesel production. Much research is still needed to explore and realize the full potential of a green fuel from J. curcas. Upcoming projects and plantations of Jatropha in countries such as India, Malaysia, and Indonesia suggest a promising future for this plant as a potential biodiesel feedstock. Many of the drawbacks associated with chemical catalysts can be overcome by using lipases for enzymatic transesterification. The high cost of lipases can be overcome, to a certain extent, by immobilization techniques. This article reviews the importance of the J. curcas plant and describes existing research conducted on Jatropha biodiesel production. The article highlights areas where further research is required and relevance of designing an immobilized lipase for biodiesel production is discussed.
Visible-light driven photocatalyst bismuth vanadate (BiVO4) photocatalyst was synthesized by the polyol route using ethylene glycol. The precipitate was washed, dried and calcined at 450 degrees C for 3 hr. The sample was characterized by X-ray diffractometry (XRD), field emission scanning electron microscopy (FE-SEM), zeta potential, surface area (BET method) and band gap energy via diffuse reflectance spectroscopy (DRS). The synthesized BiVO4 has a monoclinic phase with a surface area of 4.3 m2/g and a band gap energy of 2.46 eV. A majority of the particles were in the range of 90-130 nm as obtained from the particle size distribution histrogram. The efficiency of the sample as a visible-light driven photocatalyst was examined by photodegrading Methylene Blue (MB). The effects of some operational photodegradation parameters such as mass loading, initial dye concentration and pH were also examined. Experimental design methodology was applied by response surface modeling and optimization of the removal of MB. The multivariate experimental design was employed to develop a quadratic model as a functional relationship between the percentage removal of MB and three experimental factors (BiVO4 loading, MB initial concentration and pH). The percentage removal of MB approached 67.21% under optimized conditions. In addition, a satisfactory goodness-of-fit was achieved between the,predictive and the experimental results.
The ambient sonocatalytic degradation of congo red, methyl orange, and methylene blue by titanium dioxide (TiO(2)) catalyst at initial concentrations between 10 and 50mg/L, catalyst loadings between 1.0 and 3.0mg/L and hydrogen peroxide (H(2)O(2)) concentrations up to 600 mg/L is reported. A 20 kHz ultrasonic processor at 50 W was used to accelerate the reaction. The catalysts were exposed to heat treatments between 400 and 1000 degrees C for up to 4h to induce phase change. Sonocatalysts with small amount of rutile phase showed better sonocatalytic activity but excessive rutile phase should be avoided. TiO(2) heated to 800 degrees C for 2h showed the highest sonocatalytic activity and the degradation of dyes was influenced by their chemical structures, chemical phases and characteristics of the catalysts. Congo red exhibited the highest degradation rate, attributed to multiple labile azo bonds to cause highest reactivity with the free radicals generated. An initial concentration of 10mg/L, 1.5 g/L of catalyst loading and 450 ppm of H(2)O(2) gave the best congo red removal efficiency of above 80% in 180 min. Rate coefficients for the sonocatalytic process was successfully established and the reused catalyst showed an activity drop by merely 10%.
The paper reports on the performance of chromium or/and copper supported on H-ZSM-5(Si/Al = 240) modified with silicon tetrachloride (Cr1.5/SiCl4-Z, Cu1.5/SiCl4-Z and Cr1.0Cu0.5/SiCl4-Z) as catalysts in the combustion of chlorinated VOCs (Cl-VOCs). A reactor operated at a gas hourly space velocity (GHSV) of 32,000 h(-1), a temperature between 100 and 500 degrees C with 2500 ppm of dichloromethane (DCM), trichloromethane (TCM) and trichloroethylene (TCE) is used for activity studies. The deactivation study is conducted at a GHSV of 3800 h(-1), at 400 degrees C for up to 12 h with a feed concentration of 35,000 ppm. Treatment with silicon tetrachloride improves the chemical resistance of H-ZSM-5 against hydrogen chloride. TCM is more reactive compared to DCM but it produces more by-products due to its high chlorine content. The stabilization of TCE is attributed to resonance effects. Water vapor increases the carbon dioxide yield through its role as hydrolysis agent forming reactive carbocations and acting as hydrogen-supplying agent to suppress chlorine-transfer reactions. The deactivation of Cr1.0Cu0.5/SiCl4-Z is mainly due to the chlorination of its metal species, especially with higher Cl/H feed. Coking is limited, particularly with DCM and TCM. In accordance with the Mars-van Krevelen model, the weakening of overall metal reducibility due to chlorination leads to a loss of catalytic activity.
Industrial wastewaters contain hazardous contaminants that pollute the environment and cause socioeconomic problems, thus demanding the employment of effective remediation procedures such as photocatalysis. Zinc oxide (ZnO) nanomaterials have emerged to be a promising photocatalyst for the removal of pollutants in wastewater owing to their excellent and attractive characteristics. The dynamic tunable features of ZnO allow a wide range of functionalization for enhanced photocatalytic efficiency. The current review summarizes the recent advances in the fabrication, modification, and industrial application of ZnO photocatalyst based on the analysis of the latest studies, including the following aspects: (1) overview on the properties, structures, and features of ZnO, (2) employment of dopants, heterojunction, and immobilization techniques for improved photodegradation performance, (3) applicability of suspended and immobilized photocatalytic systems, (4) application of ZnO hybrids for the removal of various types of hazardous pollutants from different wastewater sources in industries, and (5) potential of bio-inspired ZnO hybrid nanomaterials for photocatalytic applications using renewable and biodegradable resources for greener photocatalytic technologies. In addition, the knowledge gap in this field of work is also highlighted.
Hydrothermal carbonization (HTC) provides alternatives technique to produce a nanosize activated carbon from biomass with a high surface area. Herein, this study we prepared empty fruit bunch-based activated carbon (EFBHAC) using HTC technique. The activated carbon was then functionalized with K2CO3 and Cu(NO3)2 to produce bifunctional nano-catalyst for simultaneous esterification-transesterification of waste cooking oil (WCO). The physicochemical properties were performed i.e. N2 sorptions analysis, TPD-CO2/NH3, FESEM, EDX, FTIR and XRD analysis. The results revealed that produced EFBHAC possessed a BET surface area of 4056.17 m2 g-1, with pore volume of 0.827 cm3 g-1 and 5.42 nm of pore diameter resulting from hydrolysis, dehydration decarboxylation, aromatization and re-condensation during HTC process. Impregnation of EFBHAC with K2CO3 and Cu(NO3)2 granted a high amount of basicity and acidity of 9.21 mmol g-1 and 31.41 mmol g-1, respectively, accountable to high biodiesel yield of 97.1%, produced at the optimum condition of 5 wt% of catalyst loading, 12:1 of methanol to oil molar ratio at 70 °C for 2 h. More than 80% of biodiesel was produced after the 5th cycle depicted the good reusability. The transformations from WCO to biodiesel was confirmed via 1H NMR, FTIR and TGA analysis. Fuel properties revealed kinematic viscosity of 3.3 mm2 s-1, cetane number of 51, flash point of 160.5 °C, cloud and pour point of 11 °C and -3 °C, respectively. These results show the excellent potential of waste materials to prepare bifunctional nano-catalysts to produce higher biodiesel yield which has potential to be commercialized.
A detailed study on the surface properties of oleic acid-stabilized PtNi nanoparticles supported on silica is reported. The oleic acid-stabilized PtNi nanoparticles were synthesized using NaBH4 as the reducing agent at various temperatures and oleic acid concentrations, prior to incorporation onto the silica support. X-ray diffraction studies of the unsupported oleic acid-stabilized PtNi particles revealed that the PtNi existed as alloys. Upon incorporation onto silica support, surface properties of the catalysts were investigated using H2-temperature reduction (H2-TPR), H2-temperature desorption (H2-TPD) and H2-chemisorption techniques. It was found that for the bimetallic catalysts, no oxides or very little oxidation occurred. Furthermore, these catalysts exhibited both Pt and Ni active sites on its surface though the availability of Ni active sites was dominant. A comparison of the surface properties of these materials with those prepared without oleic acid in our previous work [N. H. H. Abu Bakar et al., J. Catal. 265, 63 (2009)] and how they affect the hydrogenation of benzene is also discussed.
Titania and ceria incorporated rice husk silica based catalyst was synthesized via sol-gel method using CTAB and glycerol as surface directing agents at room temperature and labeled as RHS-50Ti10Ce. The catalyst was used to study the adsorption and photodegradation of methylene blue (MB) under UV irradiation. The powder XRD pattern of RHS-50Ti10Ce was much broader (2θ=25-30°) than that of the parent RHS (2θ=22°). The catalyst exhibited type IV isotherm with H3 hysteresis loop, and the TEM images showed partially ordered pore arrangements. The TGA-DTG thermograms confirmed the complete removal of the templates after calcination at 500°C. RHS-50Ti10Ce exhibited excellent adsorption capability with more than 99% removal of MB from a 40 mg L(-1) solution in just 15 min. It also decolorized an 80 mg L(-1) MB solution under UV irradiation in 210 min, which was comparable with the commercialized pure anatase TiO2.
Iron and 4-(methylamino)benzoic acid have been successfully incorporated into silica extracted from rice husk. The silica/Fe/amine complex, RH-Fe(5% amine), showed a ca. 24% increase in specific surface area compared to RH-Fe. This increase was attributed to the templated formation of regular pores. The XRD showed the RH-Fe(5% amine) to be amorphous. The Friedel-Crafts benzylation reaction with toluene using RH-Fe(5% amine) showed a drastic reduction in the di-substituted products to ca. 1.0%.
Silica supported iron catalyst was prepared from rice husk ash (RHA) via the sol-gel technique using an aqueous solution of iron(III) salt in 3.0 M HNO3. The sample was dried at 110 degrees C and labeled as RHA-Fe. A sample of RHA-Fe was calcined at 700 degrees C for 5 h and labeled as RHA-Fe700. X-ray diffraction spectrogram showed that both RHA-Fe and RHA-Fe700 were amorphous. The SEM/EDX results showed that the metal was present as agglomerates and the Fe ions were not homogeneously distributed in RHA-Fe but RHA-Fe700 was shown to be homogeneous. The specific surface areas for RHA-Fe and RHA-Fe700 were determined by BET nitrogen adsorption studies and found to be 87.4 and 55.8 m(2) g(-1), respectively. Both catalysts showed high activity in the reaction between toluene and benzyl chloride. The mono-substituted benzyltoluene was the major product and both catalysts yielded more than 92% of the product. The GC showed that both the ortho- and para-substituted monoisomers were present in about equal quantities. The minor products consisting of 16 di-substituted isomers were also observed in the GC-MS spectra of both catalytic products. The catalyst was found to be reusable without loss of activity and with no leaching of the metal.
Immobilized Candida antarctica lipase B-catalyzed esterification of xylitol and two fatty acids (capric and caproic acid) were studied in a solvent-free system. The Taguchi orthogonal array method based on three-level-four-variables with nine experiments was applied for the analysis and optimization of the reaction parameters including time, substrate molar ratio, amount of enzyme, and amount of molecular sieve. The obtained conversion was higher in the esterification of xylitol and capric acid with longer chain length. The optimum conditions derived via the Taguchi approach for the synthesis of xylitol caprate and xylitol caproate were reaction time, 29 and 18h; substrate molar ratio, 0.3 and 1.0; enzyme amount, 0.20 and 0.05g, and molecular sieve amount of 0.03g, respectively. The good correlation between the predicted conversions (74.18% and 61.23%) and the actual values (74.05% and 60.5%) shows that the model derived from the Taguchi orthogonal array can be used for optimization and better understanding of the effect of reaction parameters on the enzymatic synthesis of xylitol esters in a solvent-free system.
For the synthesis of a highly active TiO2-chitosan nanocomposite, pH plays a crucial role towards controlling its morphology, size, crystallinity, thermal stability, and surface adsorption properties. The presence of chitosan (CS) biopolymer facilitates greater sustainability to the photoexcited electrons and holes on the catalysts' surface. The variation of synthesis pH from 2 to 5 resulted in different physico-chemical and photocatalytic properties, whereby a pH of 3 resulted in TiO2-chitosan nanocomposite with the highest photocatalytic degradation (above 99 %) of methylene orange (MO) dye. This was attributed to the efficient surface absorption properties, high crystallinity, and the presence of reactive surfaces of -NH2 and -OH groups, which enhances the adsorption-photodegradation effect. The larger surface oxygen vacancies coupled with reduced electron-hole recombination further enhanced the photocatalytic activity. It is undeniable that the pH during synthesis is critical towards the development of the properties of the TiO2-chitosan nanocomposite for the enhancement of photocatalytic activity.
The primary aim of this study is to develop an economical, stable, and effective heterogeneous catalyst for wastewater remediation via the Fenton oxidation process. For this purpose, Fe3O4-montmorillonite alginate (FeMA) composite beads were synthesized by entrapping Fe3O4-montmorillonite in calcium alginate beads. The performance of the catalysts was evaluated via the Fenton degradation of ofloxacin (OFL), an antibiotic that is frequently detected in water bodies. The physiochemical properties of the FeMA composite beads were characterized using X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscope/energy dispersive X-ray (FESEM/EDX), Brunauer-Emmett-Teller (BET) analysis, Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). FeMA composite beads were found to have a higher surface area, higher porosity, and better thermal stability compared to pristine alginate beads. The composite beads were subsequently used for Fenton degradation of ofloxacin (OFL) in an aqueous solution. The effects of Fe3O4-montmorillonite loading on alginate, FeMA composite beads dosage, initial solution pH, initial OFL concentration, different oxidants, H2O2 dosage, reaction temperature, and inorganic salts on Fenton degradation of OFL in aqueous solution was investigated. The results revealed that the percentage of OFL degradation reached about 80 % under optimized conditions, while the total organic carbon (TOC) removal reached about 53 %. The entrapment of Fe3O4-montmorillonite in alginate beads results in less iron ions leaching compared to previous observation, and the efficiency remains constant over the five cycles investigated. The kinetics of the Fenton degradation process are best fitted to the pseudo-first-order kinetic model. It is therefore believed that FeMA composite beads can be a promising material for wastewater remediation via the Fenton oxidation process.
In the present study, 4-methylpyridin-2-amine was reacted with 3-bromothiophene-2-carbaldehyde and the Schiff base (E)-1-(3-bromothiophen-2-yl)-N-(4-methylpyridin-2-yl)methanimine was obtained in a 79% yield. Coupling of the Schiff base with aryl/het-aryl boronic acids under Suzuki coupling reaction conditions, using Pd(PPh3)4 as catalyst, yielded products with the hydrolysis of the imine linkages (5a-5k, 6a-6h) in good to moderate yields. To gain mechanistic insight into the transition metal-catalyzed hydrolysis of the compounds, density functional theory (DFT) calculations were performed. The theoretical calculations strongly supported the experiment and provided an insight into the transition metal-catalyzed hydrolysis of imines.
Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption.