ZnS and CdS nanoparticles were prepared by a simple microwave irradiation method under mild conditions. The obtained nanoparticles were characterized by XRD, TEM and EDX. The results indicated that high purity of nanosized ZnS and CdS was successfully obtained with cubic and hexagonal crystalline structures, respectively. The band gap energies of ZnS and CdS nanoparticles were estimated using UV-visible absorption spectra to be about 4.22 and 2.64 eV, respectively. Photocatalytic degradation of methylene blue was carried out using physical mixtures of ZnS and CdS nanoparticles under a 500-W halogen lamp of visible light irradiation. The residual concentration of methylene blue solution was monitored using UV-visible absorption spectrometry. From the study of the variation in composition of ZnS:CdS, a composition of 1:4 (by weight) was found to be very efficient for degradation of methylene blue. In this case the degradation efficiency of the photocatalyst nanoparticles after 6 h irradiation time was about 73% with a reaction rate of 3.61 × 10-3 min-1. Higher degradation efficiency and reaction rate were achieved by increasing the amount of photocatalyst and initial pH of the solution.
Finding a proper transition structure for the peptide bond formation process can lead to a better understanding of the role of the ribosome in catalyzing this reaction. A potential energy surface scan was performed on the ester bond dissociation of the P-site aminoacyl-tRNA and the peptide bond formation of P-site and A-site amino acids. The full fragment of initiator tRNAi met attached to both cognate (met) and non-cognate (ala) amino acids as the P-site substrate and the methionine as the A-site amino acid was used in this study. Due to the large size of tRNA, ONIOM calculations were used to reduce the computational cost. This study illustrated that the rate of peptide bond formation was reduced for misacylated tRNA without the presence of ribosomal bases. This demonstrated that there were indeed specific structural interactions involving the amino acid side chain within the tRNAi met.
Xylitol is a high value sugar alcohol with anticariogenic properties that is used as an ideal sweetener for diabetic patients. Industrially, xylitol is manufactured by catalytic reduction of pure xylose, which has
some disadvantages. The fermentation process has been studied as an alternative, but its viability is dependent on the optimization of several variables. This fermentation process on an industrial-scale is not feasible due to decreased productivity. Compared to the fermentation process, enzymatic method is expected to make a substantial increase in productivity. Enzymatic xylitol production from xylose exist in lignocellulosics is an attractive and promising alternative method to the chemical process. The enzymatic method might be able to overcome the disadvantages of the chemical process. This article reviews the literature on the processes for xylitol production and identifies further ways for improved xylitol production to compete with the current chemical process.
The current research investigates synthesis of methyl esters by transesterification of waste cooking oil in a heterogeneous system, using barium meliorated construction site waste marble as solid base catalyst. The pretreated catalyst was calcined at 830 °C for 4h prior to its activity test to obtained solid oxide characterized by scanning electron microscopy/energy dispersive spectroscopy, BET surface area and pore size measurement. It was found that the as prepared catalyst has large pores which contributed to its high activity in transesterification reaction. The methyl ester yield of 88% was obtained when the methanol/oil molar ratio was 9:1, reaction temperature at 65 °C, reaction time 3h and catalyst/oil mass ratio of 3.0 wt.%. The catalyst can be reused over three cycles, offer low operating conditions, reduce energy consumption and waste generation in the production of biodiesel.
Palm empty fruit bunch ash (EFB-ash) was used as a natural catalyst, rich in potassium to enhance the CO2 gasification reactivity of palm shell char (PS-char). Various EFB-ash loadings (ranging from 0 to 12.5wt.%) were implemented to improve the reactivity of PS-char during CO2 gasification studies using thermogravimetric analysis. The achieved results explored that the highest gasification reactivity was devoted to 10% EFB-ash loaded char. The SEM-EDS and XRD analyses further confirmed the successful loading of EFB-ash on PS-char which contributed to promoting the gasification reactivity of char. Random pore model was applied to determine the kinetic parameters in catalytic gasification of char at various temperatures of 800-900°C. The dependence of char reaction rate on gasification temperature resulted in a straight line in Arrhenius-type plot, from which the activation energy of 158.75kJ/mol was obtained for the catalytic char gasification.
An active heterogeneous Al2O3 modified MgZnO (MgZnAlO) catalyst was prepared and the catalytic activity was investigated for the transesterification of different vegetable oils (refined palm oil, waste cooking palm oil, palm kernel oil and coconut oil) with methanol to produce biodiesel. The catalyst was characterized by using X-ray diffraction, Fourier transform infrared spectra, thermo gravimetric and differential thermal analysis to ascertain its versatility. Effects of important reaction parameters such as methanol to oil molar ratio, catalyst dosage, reaction temperature and reaction time on oil conversion were examined. Within the range of studied variability, the suitable transesterification conditions (methanol/oil ratio 16:1, catalyst loading 3.32 wt.%, reaction time 6h, temperature 182°C), the oil conversion of 98% could be achieved with reference to coconut oil in a single stage. The catalyst can be easily recovered and reused for five cycles without significant deactivation.
The effects of organic solvents and their binary mixture in the glucose functionalization of bacterial poly-3-hydroxyalkanoates catalyzed by Lecitase™ Ultra were studied. Equal volume binary mixture of DMSO and chloroform with moderate polarity was more effective for the enzyme catalyzed synthesis of the carbohydrate polymer at ≈38.2 (±0.8)% reactant conversion as compared to the mono-phasic and other binary solvents studied. The apparent reaction rate constant as a function of medium water activity (aw) was observed to increase with increasing solvent polarity, with optimum aw of 0.2, 0.4 and 0.7 (±0.1) observed in hydrophilic DMSO, binary mixture DMSO:isooctane and hydrophobic isooctane, respectively. Molecular sieve loading between 13 to 15gL(-1) (±0.2) and reaction temperature between 40 to 50°C were found optimal. Functionalized PHA polymer showed potential characteristics and biodegradability.
Porous ZnO nanostructures have become the subject of research interest--due to their special structures with high surface to volume ratio that may produce peculiar properties for use in optoelectronics, sensing and catalysis applications. A microwave-assisted hydrothermal method has been used for effecting the formation of porous nanostructure of metaloxide materials, such as CoO and SnO2, in solution. Here, by adopting the unique performance of a microwave-assisted-hydrothermal method, we realized the formation of highly porous ZnO nanostructures directly on the substrate surface, instead of in solution. The effects of the ambient reaction conditions and the microwave power on the structural growth of the ZnO nanostructures were studied in detail. Two different ambient reaction conditions, namely refluxed and isolated in autoclave systems, were used in this work. Porous ZnO (PZO) nanostructures with networked-nanoflakes morphology is the typical result for this approach. It was found that the morphology of the ZnO nanostructures was strongly depended on the ambient conditions of the reaction; the isolated-autoclave system may produce reasonably high porous ZnO that is constituted by vertically oriented grainy-flakes structures, whereas the refluxed system produced solid vertically-oriented flake structures. The microwave power did not influence the structural growth of the ZnO. It was also found that both the ambient reaction conditions and the microwave power used influenced the crystallographic orientation of the PZO. For instance, PZO with dominant (002) Bragg plane could be obtained by using refluxed system, whereas PZO with dominant (101) plane could be realized if using isolated system. For the case of microwave power, the crystallographic orientation of PZO prepared using both systems changed from dominant (002) to (101) planes if the power was increased. The mechanism for the formation of porous ZnO nanostructures using the present approach is proposed. The ZnO nanostructures prepared using the present method should find an extensive use in currently existing application due to its property of reasonably high porosity.
Utilization of macroalgae biomass for bioethanol production appears as an alternative source to lignocellulosic materials. In this study, for the first time, Amberlyst (TM)-15 was explored as a potential catalyst to hydrolyze carbohydrates from Eucheuma cottonii extract to simple reducing sugar prior to fermentation process. Several important hydrolysis parameters were studied for process optimization including catalyst loading (2-5%, w/v), reaction temperature (110-130°C), reaction time (0-2.5 h) and biomass loading (5.5-15.5%, w/v). Optimum sugar yield of 39.7% was attained based on the following optimum conditions: reaction temperature at 120°C, catalyst loading of 4% (w/v), 12.5% (w/v) of biomass concentration and reaction time of 1.5h. Fermentation of the hydrolysate using Saccharomyces cerevisiae produced 0.33 g/g of bioethanol yield with an efficiency of 65%. The strategy of combining heterogeneous-catalyzed hydrolysis and fermentation with S. cerevisiae could be a feasible strategy to produce bioethanol from macroalgae biomass.
A new effective RF tar thermocatalytic treatment process with low energy intensive has been proposed to remove tar from biomass gasification. Toluene and naphthalene as biomass tar model compounds were removed via both thermal and catalytic treatment over a wide temperature range from 850 °C to 1200 °C and 450 °C to 900 °C, respectively at residence time of 0-0.7 s. Thermal characteristics of the new technique are also described in this paper. This study clearly clarified that toluene was much easier to be removed than naphthalene. Soot was found as the final product of thermal treatment of the tar model and completely removed during catalytic treatment. Radical reactions generated by RF non-thermal effect improve the tar removal. The study showed that Y-zeolite has better catalytic activity compared to dolomite on toluene and naphthalene removal due to its acidic nature and large surface area, even at lower reaction temperature of about 550 °C.
The synthesis of fatty acid ethyl esters (FAEEs) by a two-step in situ (reactive) esterification/transesterification from Jatropha curcas L. (JCL) seeds using microwave system has been investigated. Free fatty acid was reduced from 14% to less than 1% in the first step using H2SO4 as acid catalyst after 35 min of microwave irradiation heating. The organic phase in the first step was subjected to a second reaction by adding 5 N KOH in ethanol as the basic catalyst. Response surface methodology (RSM) based on central composite design (CCD) was utilized to design the experiments and analyze the influence of process variables (particles seed size, time of irradiation, agitation speed and catalyst loading) on conversion of triglycerides (TGs) in the second step. The highest triglycerides conversion to fatty acid ethyl esters (FAEEs) was 97.29% at the optimum conditions:<0.5mm seed size, 12.21 min irradiation time, 8.15 ml KOH catalyst loading and 331.52 rpm agitation speed in the 110 W microwave power system.
Four different lipases were compared for ultrasound-mediated synthesis of the biodegradable copolymer poly-4-hydroxybutyrate-co-6-hydroxyhexanoate. The copolymerization was carried out in chloroform. Of the enzymes tested, Novozym 435 exhibited the highest copolymerization rate, in fact the reaction rate was observed to increase with about 26-fold from 30 to 50°C (7.9×10(-3)Ms(-1)), sonic power intensity of 2.6×10(3)Wm(-2) and dissipated energy of 130.4Jml(-1). Copolymerization rates with the Candida antarctica lipase A, Candida rugosa lipase, and Lecitase Ultra™ were lower at 2.4×10(-4), 1.3×10(-4) and 3.5×10(-4)Ms(-1), respectively. The catalytic efficiency depended on the enzyme. The efficiency ranged from 4.15×10(-3)s(-1)M(-1) for Novozym 435-1.48×10(-3)s(-1)M(-1) for C. rugosa lipase. Depending on the enzyme and sonication intensity, the monomer conversion ranged from 8.2% to 48.5%. The sonication power, time and temperature were found to affect the rate of copolymerization. Increasing sonication power intensity from 1.9×10(3) to 4.5×10(3)Wm(-2) resulted in an increased in acoustic pressure (P(a)) from 3.7×10(8) to 5.7×10(8)Nm(-2) almost 2.4-3.7 times greater than the acoustic pressure (1.5×10(8)Nm(-2)) that is required to cause cavitation in water. A corresponding acoustic particle acceleration (a) of 9.6×10(3)-1.5×10(4)ms(-2) was calculated i.e. approximately 984-1500 times greater than under the action of gravity.
The production of lignin from empty fruit bunch (EFB) has been carried out using liquefaction method with 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid (IL), in presence of sulfuric acid (H2SO4) as a catalyst. Response surface methodology (RSM) based on a factorial Central Composite Design (CCD) was employed to identify the optimum condition for lignin yield. The result indicated that the second order model was adequate for all the independent variables on the response with R(2)=0.8609. The optimum temperature, time, ionic liquid to EFB ratio, and catalyst concentration were 150.5 °C, 151 min, 3:1 wt/wt and 4.73 wt%, respectively for lignin yield=26.6%. The presence of lignin liquefied product was confirmed by UV-Vis and FTIR analysis. It was also demonstrated lignin extraction from lignocellulosic using recycled IL gave sufficient performance.
Selecting a proper support in the catalyst system plays an important role in hydrogen production via ethanol steam reforming. In this study, sol gel made alumina supports prepared for nickel (Ni) catalysts were calcined at different temperatures. A series of (Ni/AlS.G.) catalysts were synthesized by an impregnation procedure. The influence of varying the calcination temperature of the sol gel made supports on catalyst activity was tested in ethanol reforming reaction. The characteristics of the sol gel alumina supports and Ni catalysts were affected by the calcination temperature of the supports. The structure of the sol gel made alumina supports was transformed in the order of γ → (γ + θ) → θ-alumina as the calcination temperature of the supports increased from 600 °C to 1000 °C. Both hydrogen yield and ethanol conversion presented a volcano-shaped behavior with maximum values of 4.3 mol/mol ethanol fed and 99.5%, respectively. The optimum values were exhibited over Ni/AlS.G800 (Ni catalyst supported on sol gel made alumina calcined at 800 °C). The high performance of the Ni/AlS.G800 catalyst may be attributed to the strong interaction of Ni species and sol gel made alumina which lead to high nickel dispersion and small particle size.
The optical properties of a ZnO photocatalyst were enhanced with various dopant concentrations of Fe(3+). Doped ZnO nanoparticles were synthesized via a sol-gel method without the use of capping agents or surfactants and was then characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultraviolet-visible (UV-Vis) spectroscopy. The results showed that ZnO has a wurtzite, hexagonal structure and that the Fe(3+) ions were well incorporated into the ZnO crystal lattice. As the Fe(3+) concentration increased from 0.25 wt.% to 1 wt.%, the crystal size decreased in comparison with the undoped ZnO. The spectral absorption shifts of the visible light region (red shift) and the band gap decreases for each Fe-ZnO sample were investigated. The photocatalytic activities of the ZnO and Fe-ZnO samples were evaluated based on the degradation of 2-chlorophenol in aqueous solution under solar radiation. The samples with a small concentration of Fe(3+) ions showed enhanced photocatalytic activity with an optimal maximum performance at 0.5 wt.%. The results indicated that toxicity removal of 2-chlorophenol at same line of degradation efficiency. Small crystallite size and low band gap were attributed to high activities of Fe-ZnO samples under various concentrations of Fe(3+) ions compared to undoped ZnO.
A novel samarium-doped spherical-like ZnO hierarchical nanostructure (Sm/ZnO) was synthesized via a facile and surfactant-free chemical solution route. The as-synthesized products were characterized by X-ray diffraction, Brunauer-Emmett-Teller surface area analysis, field emission scanning electron microscopy together with an energy dispersion X-ray spectrum analysis, transmission electron microscopy, UV-visible diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The results revealed that Sm ion was successfully doped into ZnO. It was also observed that the Sm doping increased the visible light absorption ability of Sm/ZnO and a red shift for Sm/ZnO appeared when compared to pure ZnO. The photocatalytic studies revealed that the Sm/ZnO exhibited excellent photocatalytic degradation of 2,4-dichlorophenol (2,4-DCP) compared with the pure ZnO and commercial TiO2 under visible light irradiation. The photocatalytic enhancement of Sm/ZnO products was attributed to their high charge separation efficiency and ·OH generation ability as evidenced by the photoluminescence spectra. The photocatalytic investigation also showed that various parameters exerted their individual influence on the degradation rate of 2,4-DCP. By using a certain of radical scavengers, ·OH was determined to play a pivotal role for the 2,4-DCP degradation. Moreover, the Sm/ZnO could be easily separated and reused, indicating great potential for practical applications in environmental cleanup.
The utilization of carbon dioxide for the production of valuable chemicals via catalysts is one of the efficient ways to mitigate the greenhouse gases in the atmosphere. It is known that the carbon dioxide conversion and product yields are still low even if the reaction is operated at high pressure and temperature. The carbon dioxide utilization and conversion provides many challenges in exploring new concepts and opportunities for development of unique catalysts for the purpose of activating the carbon dioxide molecules. In this paper, the role of carbon-based nanocatalysts in the hydrogenation of carbon dioxide and direct synthesis of dimethyl carbonate from carbon dioxide and methanol are reviewed. The current catalytic results obtained with different carbon-based nanocatalysts systems are presented and how these materials contribute to the carbon dioxide conversion is explained. In addition, different strategies and preparation methods of nanometallic catalysts on various carbon supports are described to optimize the dispersion of metal nanoparticles and catalytic activity.
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.
This study investigates the influence of alkali (Na, K), alkaline earth (Ca, Mg) and transition (Fe) metal nitrates on CO2 gasification reactivity of pistachio nut shell (PNS) char. The preliminary gasification experiments were performed in thermogravimetric analyzer (TGA) and the results showed considerable improvement in carbon conversion; Na-char>Ca-char>Fe-char>K-char>Mg-char>raw char. Based on TGA studies, NaNO3 (with loadings of 3-7 wt%) was selected as the superior catalyst for further gasification studies in bench-scale reactor; the highest reactivity was devoted to 5 wt% Na loaded char. The data acquired for gasification rate of catalyzed char were fitted with several kinetic models, among which, random pore model was adopted as the best model. Based on obtained gasification rate constant and using the Arrhenius plot, activation energy of 5 wt% Na loaded char was calculated as 151.46 kJ/mol which was 53 kJ/mol lower than that of un-catalyzed char.
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.