ZSM-5 zeolite was synthesized by sourcing silica from wheat husk ash and was converted into its protonated form following careful, conventionally accepted ion-exchange method and calcinations. The H-ZSM-5 zeolite (Si/Al ratio = 30) prepared was appropriately characterized by XRD, FT-IR, SEM, TEM, TG-DTA, CV, and so forth, and evaluated as recyclable catalyst in selective organic transformations including three- and four-component reactions. The catalytic activity of the zeolite sample supposedly relates to increased density of the accessible acid sites.
Cu50Ni50 nanoparticles were synthesized using a modified polyol method and deposited on samarium-doped ceria, SDC, and yttria-stabilized zirconia, YSZ, supports to form reverse water-gas shift, RWGS, catalysts. The best CO yields, obtained with the Cu50Ni50/SDC catalyst, were about 90% of the equilibrium CO yields. In contrast CO yields using Pt/SDC catalysts were equal to equilibrium CO yields at 700°C. Catalyst selectivity to CO was 100% at hydrogen partial pressures equal to CO2 partial pressures, 1 kPa, and decreased as methane was formed when the hydrogen partial pressure was 2 kPa or greater. The reaction results were explained using a combination of Eley-Rideal and Langmuir-Hinshelwood mechanisms that involved adsorption on the metal surface and the concentration of oxygen vacancies in the support. Finally the Cu50Ni50/SDC catalyst was found to be thermally stable for 48 hours at 600/700°C.
A carbonate mineral, dolomite, was used as a heterogeneous catalyst to produce methyl-esters from soybean oil. The samples were analyzed by XRF, TGA, XRD, TPD-CO 2 , and SEM. The calcination of dolomite at 800°C/1 h resulted in a highly active mixed metal oxides. In addition, the influence of the reaction variables such as the temperature, catalyst amount, and methanol/soybean oil molar ratio in methyl-ester production was optimized by the application of a central composite design in conjunction with the response surface methodology (RSM). The XRF analysis is carried out after the reuses procedure which shows that the deactivation process is mainly due to the selective calcium leaching. Overall, the calcined dolomite exhibited high catalytic activity at moderate operating conditions for biodiesel production.
Supported titanium dioxide (TiO2) was investigated for the photodegradation of the insecticide fenamiphos in water. The photocatalyst was immobilised on borosilicate glass plates and the kinetics of degradation were studied in a stirred tank reactor under UV irradiation. Two types of TiO2, for example, Millennium PC500 (100% anatase) and Degussa P25 (80% anatase, 20% rutile), were used. Their activities have been based on the rates of insecticide disappearance. Experiments were investigated to evaluate the effect of pH and initial concentrations of fenamiphos as well as catalyst doses on the photocatalytic degradation of fenamiphos. Kinetic parameters were experimentally determined and an apparent first-order kinetic was observed. For photolysis process of fenamiphos, two photoproducts were identified and characterized using high performance liquid chromatography/mass spectrometry (HPLC/MS). The plausible mechanism of photolysis involved is the oxidation of sulfonamide group. In presence of photocatalyst TiO2, photodegradation was observed. Under identical conditions, Degussa P25 shows higher photocatalytic activity in regard to PC500 Millennium and complete degradation was observed after 180 min.
A new approach has been demonstrated for the synthesis of solid ammonium sulphate attached to silica rice husk ash. The 3-(aminopropyl)triethoxysilane was immobilized onto silica at room temperature to functionalize the silica with ammine end groups (–NH2). The amine group was sulphated with sulphuric acid to produce a novel micro-rod-like shaped acidic catalyst (as seen with TEM) designated RHNH3SO4H (RH = rice husk). The TGA analysis shows that the catalyst is stable at temperatures below 200°C. The acidity measurement of the catalyst indicates that it has Brønsted acid sites. Cellulose extracted from waste of rice husk and cellulose extracted from office paper were hydrolysed to glucose in 6 h, and the glucose was hydrolysed afterwards to other products within 13 h. The catalyst is reusable many times without a significant loss of catalytic activity.
A facile, clean, economical, efficient, and green process was developed for the preparation of Z-aldoximes at room temperature under solvent-free condition using emeraldine base form of polyaniline as novel catalyst. In this methodology, PANI base absorbed the by-product of HCl (polluting chemical) from hydroxylamine hydrochloride and converted to polyaniline-hydrochloride salt (PANI-HCl salt). This PANI-HCl salt could be easily recovered and used in new attempts without any purification in many areas such as catalyst, electrical and electronics applications meant for conducting polymers. As far as our knowledge is concerned, emeraldine base as catalyst in organic synthesis for the first time.
Biodiesel from sunflower oil using lipase chemically immobilized on silk-cocoon matrix in a packed-bed bioreactor was investigated. The immobilization was demonstrated by field-emission scanning electron microscopy and activity study. The lipase loading was 738.74 U (~0.01 g lipase powder)/g-lipase-immobilized matrix. TheKm(Michaelis-Menten constant) of the free and the immobilized lipase was 451.26 μM and 257.26 μM, respectively. LowKmvalue of the immobilized lipase is attributed to the hydrophobic nature of the matrix that facilitated the substrate diffusion to the enzyme surface. The biodiesel yield of 81.62% was obtained at 48 hours reaction time, 6 : 1 methanol : oil ratio (v/v), and 30°C. The immobilized lipase showed high operational stability at 30°C. The substrate conversion was only marginally decreased till third cycle (each of 48 hours duration) of the reaction since less than even 5% of the original activity was decreased in each of the second and third cycle. The findings demonstrated the potential of the silk-cocoon as lipase immobilization matrix for industrial production of biodiesel.
The potential of oxidation pretreated Hastelloy tube as a hydrocarbon steam reforming catalyst was assessed using tetradecane, toluene, and naphthalene as model compounds. Surface characterization showed that Fe 2 O 3 , Cr 2 O 3 , MoO 3 , and NiO were formed on the surface of the alloy after oxidation at 1000°C for 2 hours. Catalytic evaluation showed good activity and stability with tetradecane while lower activity with increased rate of carbon formation was observed with naphthalene.
Ordered mesoporous materials are promising catalyst supports due to their uniform pore size distribution, high specific surface area and pore volume, tunable pore sizes, and long-range ordering of the pore packing. The evaporation-induced self-assembly (EISA) process was applied to synthesize mesoporous mixed oxides, which consist of cobalt ions highly dispersed in an alumina matrix. The characterization of the mesoporous mixed cobalt-aluminum oxides with cobalt loadings in the range from 5 to 15 wt% and calcination temperatures of 673, 973, and 1073 K indicates that Co 2+ is homogeneously distributed in the mesoporous alumina matrix. As a function of the Co loading, different phases are present comprising poorly crystalline alumina and mixed cobalt aluminum oxides of the spinel type. The mixed cobalt-aluminum oxides were applied as catalysts in CO oxidation and turned out to be highly active.
This paper purports to review catalysis, particularly the organocatalysis and its origin, key trends, challenges, examples, scope, and importance. The definition of organocatalyst corresponds to a low molecular weight organic molecule which in stoichiometric amounts catalyzes a chemical reaction. In this review, the use of the termheterogenized organocatalystwill be exclusively confined to a catalytic system containing an organic molecule immobilized onto some sort of support material and is responsible for accelerating a chemical reaction. Firstly, a brief description of the field is provided putting it in a green and sustainable perspective of chemistry. Next, research findings on the use of organocatalysts on various inorganic supports including nano(porous)materials, nanoparticles, silica, and zeolite/zeolitic materials are scrutinized in brief. Then future scope, research directions, and academic and industrial applications will be outlined. A succinct account will summarize some of the research and developments in the field. This review tries to bring many outstanding researches together and shows the vitality of the organocatalysis through several aspects.
Polyaniline salt containing 1-hydroxyethane-1,1-diphosphonic acid with nanosphere morphology in semicrystalline powder form was successfully synthesized by interfacial polymerization pathway and demonstrated as polymer based acid catalyzed in the synthesis of 1,4-dihydropyridines and polyhydroquinoline derivatives. This catalyst promotes the reaction under solvent free condition in excellent yield in 10 min with recyclability. The advantages of this methodology are the easy synthesis of polymer containing acid group catalyst in powder form having easily handlable, efficient, versatile, and reusable nature.
The reactivity and selectivity of Fenton system (Fe 2+ /H 2 O 2 ) were improved with N-hydroxyphthalimide (NHPI) as cocatalyst. The oxidation process of benzyl alcohol to benzaldehyde has been studied. The reaction catalyzed by this new Fe 2+ /H 2 O 2 /NHPI system can be well performed under room temperature without adding any organic solvent. Besides, this catalyst system is effective for the oxidation of different alcohols.
The visible-light-driven semiconductor photocatalysts are the current research focus techniques used to decompose organic pollutants/compounds. The photodegradation efficiency of organic compounds by photocatalyst is expected to be better compared to UV-light-driven semiconductor photocatalysts technique since the major components of our solar energy are visible light (~44%). However, as most of the previous research work has been carried out using semiconductor photocatalysts in the form of powder, extra steps and costs are needed to remove this powder from the slurry to prevent secondary pollution. In this research work, we will explain our fabrication technique of V2O5 nanoflakes by growing radially on PET fibers. By utilizing the flexibility and high surface area of polymeric fibers as novel substrate for the growth of V2O5 nanoflakes, the Rhodamine B (RhB) could be degraded under visible light irradiation. The photodegradation of RhB solution by V2O5 nanoflakes followed the 1st order kinetic with a constant rate of 0.0065 min−1. The success of this research work indicates that V2O5 nanoflakes grown on PET fibre could be possibly used as organic waste water purifier under continuous flow condition. A photodegradation mechanism of V2O5 nanostructures to degrade RhB dye is proposed based on the energy diagram.
The lamellar perovskite K0,8Ti0,8Nb1,2O5 was prepared by solid state reaction, and its protonic form was used in a sequence of intercalation steps with n-butylamine, cetyltrimethylammonium bromide (CTABr), and tetraethyl orthosilicate (TEOS). After calcination, a high surface area, mesoporous SiO2-pillared titanoniobate, was obtained. The samples were characterized by XRD, EDX, TG-DTG, N2 adsorption isotherms, and NH3-TPD. The pillarization procedure affected the textural properties, the amount, and strength distribution of acid sites. The influence of the pillarization procedure on the catalytic properties of the lamellar titanoniobates was investigated on ethanol dehydration. High ethanol conversions and ethylene yields (>90%) were obtained in the presence of the SiO2-pillared titanoniobate catalyst, at 350–450°C.
Unsupported and supported iron oxide catalysts were prepared by incipient wetness impregnation method and studied in the water-gas shift reaction (WGSR) in the temperature range 350–450°C. The techniques of characterization employed were BET, X-ray diffraction, acid-base measurements by microcalorimetry and in situ diffuse reflectance infrared Fourier transform spectroscopy. MgO, TiO 2 , or SiO 2 was added in order to (i) obtain a catalyst exempt of chromium oxide and (ii) study the effect of their acid-base properties on catalytic activity of Fe 2 O 3 . X-ray diffraction studies, and calorimetric and diffuse reflectance infrared Fourier transform measurements reveal a complete change in the physicochemical properties of the iron oxide catalyst after MgO addition due to the formation of the spinel oxide phase. These results could indicate that the MgFe 2 O 4 phase stabilizes the reduced iron phase, preventing its sintering under realistic WGSR conditions (high H 2 O partial pressures).
Hydrotalcite, also known as aluminum-magnesium layered double hydroxide (LDH) or anionic clay, is a synthetic compound that was broadly investigated in the past decade due to its many potential applications. In this work, we present an environmentally benign process for the transesterification (methanolysis) of neem oil to fatty acid methyl esters (FAME) using Zn-Mg-Al hydrotalcites as solid base catalysts in a heterogeneous manner. The catalysts were characterized by XRD, FT-IR, TPD-CO 2 , and the BET surface area analysis. It is well-known that the catalytic performance of hydrotalcite is dramatically increased through the incorporation of Zn into the surface of Mg-Al hydrotalcite material. The optimized parameters, 10 : 1 methanol/oil molar ratio with 7.5 g catalysts reacted under stirring speed 450 rpm at 65°C for 4 h reaction, gave a maximum ester conversion of 90.5% for the sample with Zn-Mg-Al ratio of 3 : 3 : 1.
A review of the pyrolysis process of used tyre as a method of producing an alternative energy source is presented in this paper. The study reports the characteristics of used tyre materials and methods of recycling, types and principles of pyrolysis, the pyrolysis products and their composition, effects of process parameters, and kinetic models applied to pyrolysis. From publications, the proximate analysis of tyre rubber shows that it is composed of about 28.6 wt.% fixed carbon, 62 wt.% volatile material, 8.5 wt.% ash, and 0.9 wt.% moisture. Elemental analysis reveals that tyre rubber has an estimated value of 82 wt.% of C, 8 wt.% of H, 0.4 wt.% of N, 1.3 wt.% of S, 2.4 wt.% of O, and 5.9 wt.% of ash. Thermogravimetry analysis confirms that the pyrolysis of used tyre at atmospheric pressure commences at 250°C and completes at 550°C. The three primary products obtained from used tyre pyrolysis are solid residue (around 36 wt.%), liquid fraction or biocrude (around 55 wt.%), and gas fraction (around 9 wt.%). Although there is variation in the value of kinetic parameters obtained by different authors from the kinetic modeling of used tyre, the process is generally accepted as a first order reaction based on Arrhenius theory.
Photocatalysis using semiconductor oxides was being investigated extensively for the degradation of dyes in effluent water. This paper reports our findings on visible light induced photocatalytic degradation of azo dye, methyl red mediated nitrogen and manganese codoped nano-titanium dioxide (N/Mn-TiO2). The codoped samples with varying weight percentages were synthesized by sol-gel method and characterized by various analytical techniques. The X-ray diffraction data showed that the synthesized samples were in anatase phase with 2θ at 25.3°. UV-visible diffuse reflectance spectral analysis revealed that the presence of dopants in TiO2 caused a significant absorption shift towards visible region and their presence was confirmed by X-ray photoelectron spectral data. The release of hydroxyl radical (major active species in photocatalytic degradation) by the photocatalyst in aqueous solution under visible light irradiation was quantitatively investigated by the photoluminiscent technique (PL). The effect of various experimental parameters like dopant concentration, pH, catalyst dosage, and initial dye concentrations was investigated and optimum conditions were established. The extent of mineralization of methyl red was studied by chemical oxygen demand (COD) assays and the results showed complete mineralization of the dye.
In this work, MCM-41, magnetite (MAG), and a composite of magnetite and MCM-41 (MCM-MAG) were synthesized by a simple route for the production of active systems in the decomposition of organic waste. The materials were characterized by N 2 adsorption/desorption, X-ray diffraction analysis (XRD), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM). Our results indicated that the decolorization kinetics of the dyes were in the order of MCM-MAG > MCM-41 > magnetite. Mineralization of the dyes was monitored by total organic carbon (TOC) decrease. The dye solutions could be completely decolorized and effectively mineralized, with an average overall TOC removal 43% for a Fenton-like reaction time of 180 min. The degradation activity of the MCM-MAG was stable during four consecutive experiments, confirming their stability and reusability of the composite. The great advantage of this composite is that it may be easily magnetically recovered and reused.
A series of Au/CoO x -TiO 2 with various Co/Ti ratios prepared. CoO x /TiO 2 was prepared by incipient wetness impregnation with aqueous solution of cobalt nitrate. Au catalysts were prepared by deposition-precipitation (DP) method at pH 7 and 338 K. The catalysts were characterized by inductively coupled plasma-mass spectrometry, temperature programming reduction, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The reaction was carried out in a fixed bed reactor with a feed containing 1% CO in air at weight hourly space velocities of 120,000 mL/h g and 180,000 mL/h g. High gold dispersion and narrow particle size distribution were obtained by DP method. The addition of CoO x into Au/TiO 2 enhanced the activity of CO oxidation significantly. Au/5% CoO x -TiO 2 had the highest catalyst among all the catalysts. CoO x was mainly in the form of nanosize Co 3 O 4 which could stabilize the Au nanoparticles. CoO x donated partial electrons to Au. The interactions among Au, CoO x , and TiO 2 account for the high catalytic activity for CO oxidation.
