Titanium dioxide photocatalyst was synthesised by microemulsions method under controlled hydrolysis of titanium butoxide, Ti(O(CH2)3)CH3. The synthesised TiO2 photocatalyst was compared with Sigma-commercial TiO2 by carrying out the investigation on its properties using scanning electron microscopy (SEM), x-ray diffraction (XRD) analysis and thermal gravimetric analysis (TGA). The photocatalytic activities for both photocatalysts were studied for atrazine photodegradation.
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.
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.
Finding a proper transition structure for the peptide bond formation process can lead one to a better understanding of the role of ribosome in catalyzing this reaction. Using computer simulations, we performed the potential energy surface scan on the ester bond dissociation of P-site aminoacyl-tRNA and the peptide bond formation of P-site and A-site amino acids. The full fragments of initiator tRNA(i)(met) and elongator tRNA(phe) are attached to both cognate and non-cognate amino acids as the P-site substrate. The A-site amino acid for all four calculations is methionine. We used ONIOM calculations to reduce the computational cost. Our study illustrates the reduced rate of peptide bond formation for misacylated tRNA(i)(met) in the absence of ribosomal bases. The misacylated elongator tRNA(phe), however, did not show any difference in its PES compared with that for the phe-tRNA(phe). This demonstrates the structural specification of initiator tRNA(i)(met) for the amino acids side chain.
The current demands of sustainable green methodologies have increased the use of enzymatic technology in industrial processes. Employment of enzyme as biocatalysts offers the benefits of mild reaction conditions, biodegradability and catalytic efficiency. The harsh conditions of industrial processes, however, increase propensity of enzyme destabilization, shortening their industrial lifespan. Consequently, the technology of enzyme immobilization provides an effective means to circumvent these concerns by enhancing enzyme catalytic properties and also simplify downstream processing and improve operational stability. There are several techniques used to immobilize the enzymes onto supports which range from reversible physical adsorption and ionic linkages, to the irreversible stable covalent bonds. Such techniques produce immobilized enzymes of varying stability due to changes in the surface microenvironment and degree of multipoint attachment. Hence, it is mandatory to obtain information about the structure of the enzyme protein following interaction with the support surface as well as interactions of the enzymes with other proteins. Characterization technologies at the nanoscale level to study enzymes immobilized on surfaces are crucial to obtain valuable qualitative and quantitative information, including morphological visualization of the immobilized enzymes. These technologies are pertinent to assess efficacy of an immobilization technique and development of future enzyme immobilization strategies.
Methoxylation is a relevant technological process applied in the production of high-value α-pinene derivatives. This report investigates the use of potassium alum [KAl(SO4)2 · 12H2O] as a catalyst in the methoxylation of α-pinene. In this study, the methoxylation reaction was optimized for the highest conversion of α-pinene and selectivity, assessed for the factors, catalyst loading (0.5; 1.0; and 1.5 g), volume ratio of α-pinene: methanol (1:4, 1:7, 1:10), reaction temperature (50, 55, 60 and 65 °C), and reaction time (72, 144, 216, 288, 360 min). The highest selectivity of KAl(SO4)2∙12H2O in the methoxylation of α-pinene was achieved under an optimal condition of 1 g of catalyst loading, volume ratio of 1:10, as well as the reaction temperature and incubation time of 65 °C and 6 h, respectively. GC-MS results revealed the yields of the methoxylated products from the 98.2% conversion of α-pinene, to be 59.6%, 8.9%, and 7.1% for α-terpinyl methyl ether (TME), fenchyl methyl ether (FME), bornyl methyl ether (BME), respectively. It was apparent that a lower KAl(SO4)2∙12H2O loading (0.5-1.5 g) was more economical for the methoxylation reaction. The findings seen here indicated the suitability of the KAl(SO4)2 · 12H2O to catalyze the methoxylation of α-pinene to produce an commercially important ethers.
A combination between the nanostructured photocatalyst and cellulose-based materials promotes a new functionality of cellulose towards the development of new bio-hybrid materials for various applications especially in water treatment and renewable energy. The excellent compatibility and association between nanostructured photocatalyst and cellulose-based materials was induced by bio-combability and high hydrophilicity of the cellulose components. The electron rich hydroxyl group of celluloses helps to promote superior interaction with photocatalyst. The formation of bio-hybrid nanostructured are attaining huge interest nowadays due to the synergistic properties of individual cellulose-based material and photocatalyst nanoparticles. Therefore, in this review we introduce some cellulose-based material and discusses its compatibility with nanostructured photocatalyst in terms of physical and chemical properties. In addition, we gather information and evidence on the fabrication techniques of cellulose-based hybrid nanostructured photocatalyst and its recent application in the field of water treatment and renewable energy.
The current work aimed to investigate the degradation of the triclocarban (TCC) in aqueous solution using a modified zeolite/TiO2 composite (MZTC) synthesized by applying the electrochemical anodization (ECA). The synthesis process was conducted at different voltages (10, 40, and 60) V in 1 h and using electrophoresis deposition (EPD) in doping zeolite. The MZTC was covered with the array ordered, smooth and optimum elongated nanotubes with 5.1 μm of the length, 120.3 nm of the inner diameter 14.5 nm of the wall thickness with pure titanium and crystalline titania as determined by FESEM/EDS, and XRD. The kinetic study by following Langmuir-Hinshelwood(L-H) model and pseudo first order, the significant constant rate was obtained at pH 11 which was 0.079 ppm/min, 0.75 cm2 of MZTC catalyst loading size achieved 0.076 ppm/min and 5 ppm of TCC initial concentration reached 0.162 ppm/min. The high-performance liquid chromatography (HPLC) analysis for mechanism study of TCC photocatalytic degradation revealed eleven intermediate products after the whole process of photocatalysis. In regard of toxicology assessment by the bacteria which is Photobacterium phosphoreum, the obtained concentration of TCC at minute 60 was less satisfied with remained 0.36 ppm of TCC was detected indicates that the concentration was above allowable level. Where the allowable level of TCC in stream is 0.1 ppm.
Powdered-photocatalysis of organic wastewater is widely investigated, unfortunately not industrially implemented due to its high energy requirement. Interestingly, such issue may be alleviated via the elimination of mechanical stirring required. Core-shell ZnO-based photocatalysts were developed herein, subsequently demonstrated efficient photocatalytic activities in the absence of mechanical stirring. Results show that the developed SiO2-cored ZnO photocatalyst are highly crystalline, while significantly smaller than coreless, pure ZnO due to the multi-point crystallization prompted. Additionally, it is also inherited with considerable buoyancy ability from SiO2-core in the absence of mechanical stirring, concurrently rendered with UV-active properties due to its ZnO-shell. Experimentally, 55% of particles of ZnO_0.0025 (0.0025 mol of ZnO-deposition) were found stably suspended for 60 min in liquid substrate, as opposed to the instant-settling of pure ZnO particles. In term of photocatalytic activity, ZnO_0.01 manifested the best methylene blue (MB) degradation with 150 mL/min of O2-bubbling. 67.63% of MB was degraded with photocatalyst loading of 0.2 g/L after 120 min UV-irradiation, simultaneously recorded the highest pseudo-first order reaction constant of 9.636 × 10-3 min-1. As summary, the auto-suspending photocatalysis conceptualized in current study offers a high possibility in reducing energy requirement for photo-treatment of wastewater, hence advocating its industrialization potential in near future.
Nanostructured photocatalysts commonly offered opportunities to solve issues scrutinized with the environmental challenges caused by steep population growth and rapid urbanization. This photocatalyst is a controllable characteristic, which can provide humans with a clean and sustainable ecosystem. Over the last decades, one of the current thriving research focuses on visible-light-driven CeO2-based photocatalysts due to their superior characteristics, including unique fluorite-type structure, rigid framework, and facile reducing oxidizing properties of cerium's tetravalent (Ce4+) and trivalent (Ce3+) valence states. Notwithstanding, owing to its inherent wide energy gap, the solar energy utilization efficiency is low, which limits its application in wastewater treatment. Numerous modifications of CeO2 have been employed to enhance photodegradation performances, such as metals and non-metals doping, adding support materials, and coupling with another semiconductor. Besides, all these doping will form a different heterojunction and show a different way of electron-hole migration. Compared to conventional heterojunction, advanced heterojunction types such as p-n heterojunction, Z-scheme, Schottky junction, and surface plasmon resonance effect exhibit superior performance for degradation owing to their excellent charge carrier separation, and the reaction occurs at a relatively higher redox potential. This review attends to providing deep insights on heterojunction mechanisms and the latest progress on photodegradation of various contaminants in wastewater using CeO2-based photocatalysts. Hence, making the CeO2 photocatalyst more foresee and promising to further development and research.
The combination of exceptional functionalities offered by 3D graphene-based macrostructures (GBMs) has attracted tremendous interest. 2D graphene nanosheets have a high chemical stability, high surface area and customizable porosity, which was extensively researched for a variety of applications including CO2 adsorption, water treatment, batteries, sensors, catalysis, etc. Recently, 3D GBMs have been successfully achieved through few approaches, including direct and non-direct self-assembly methods. In this review, the possible routes used to prepare both 2D graphene and interconnected 3D GBMs are described and analyzed regarding the involved chemistry of each 2D/3D graphene system. Improvement of the accessible surface of 3D GBMs where the interface exchanges are occurring is of great importance. A better control of the chemical mechanisms involved in the self-assembly mechanism itself at the nanometer scale is certainly the key for a future research breakthrough regarding 3D GBMs.
Herein we reported the effect of doping and addition of surfactant on SnO2 nanostructures for enhanced photocatalytic activity. Pristine SnO2, Zn-SnO2 and SDS-(Zn-SnO2) was prepared via simple co-precipitation method and the product was annealed at 600 °C to obtain a clear phase. The structural, optical, vibrational, morphological characteristics of the synthesized SnO2, Zn-SnO2 and SDS-(Zn-SnO2) product were investigated. SnO2, Zn-SnO2 and SDS-(Zn-SnO2) possess crystallite size of 20 nm, 19 nm and 18 nm correspondingly with tetragonal structure and high purity. The metal oxygen vibrations were present in FT-IR spectra. The obtained bandgap energies of SnO2, Zn-SnO2 and SDS-(Zn-SnO2) were 3.58 eV, 3.51 eV and 2.81 eV due to the effect of dopant and surfactant. This narrowing of bandgap helped in the photocatalytic activity. The morphology of the pristine sample showed poor growth of nanostructures with high level of agglomeration which was effectively reduced for other two samples. Product photocatalytic action was tested beneath visible light of 300 W. SDS-(Zn-SnO2) nanostructure efficiency showed 90% degradation of RhB dye which is 2.5 times higher than pristine sample. Narrow bandgap, crystallite size, better growth of nanostructures paved the way for SDS-(Zn-SnO2) to degrade the toxic pollutant. The superior performance and individuality of SDS-(Zn-SnO2) will makes it a potential competitor on reducing toxic pollutants from wastewater in future research.
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.
Selected Brønsted acidic ionic liquids were tested as homogeneous catalysts for the dehydration of methanol to dimethyl ether. Ionic liquids incorporating an alkanesulfonic acid as a part of the cation, a complex acidic anion, [A(2)H](-), or both, proved to be good catalysts for this process, providing high conversions and selectivities. Homogeneous catalysis in the liquid state represents a novel approach to dimethyl ether synthesis.
Biocatalytic reaction is a type of reaction which uses enzyme or whole-cell as a (bio)-catalyst to achieve a desired conversion, under controlled conditions in a bioreactor. Temperature produces opposed effects on enzyme activity and stability, and is therefore a key variable in any biocatalytic processes. An exothermic biocatalytic reaction, in a continuous-stirred-tank reactor (CSTR), was analyzed where dynamic equations (non-linear differential equations) could be derived from the Michaelis-Menten and Arrhenius equations, by performing mass and energy balances on the reactor. In this work, the effects of the different parameters such as dilution rate, proportional control constant and dimensionless total enzyme concentration, on the stability of the system, were studied. The stability of the reaction could be analyzed, based on the ODE (ordinary differential equation), solved using the numerical technique in MATLAB® and the analytical investigation using Mathematica.® The numerical analysis can be carried out by considering the hase-plane behaviour and bifurcation diagrams of the dynamic equations, while the analytical analysis using Mathematica® can be undertaken by evaluating the eigenvalues of the system. In order to model the operational stability of biocatalysts, modulation factors need to be considered so that a proper design of bioreactors can be done. Temperature, as a key variable in such bioprocess systems, can be conveniently optimized through the use of appropriate models.
Indoles are amongst the most important class of heteroaromatics in organic chemistry, being commonly found in biologically active natural products and therapeutically useful compounds. The synthesis of indoles is therefore important and several methods for their synthesis that make use of silver(I) catalysts and reagents have been developed in recent years. This Focus Review contains, to the best of our knowledge, a comprehensive coverage of silver-mediated indole forming reactions since the first reaction of this type was reported in 2004.
In this study, nano-sized ITO supported Pt-Pd bimetallic catalyst was synthesized for the degradation of methyl parathion pesticide, a common extremely toxic contaminant in aqueous solution. On the characterization with different techniques, a beautiful scenario of honeycomb architecture composed of ultra-small nanoneedles or fine hairs was found. Average size of nanocatalyst also confirmed which was in the range of 3-5 nm. High percent degradation (94%) was obtained in 30 s using 1.5 × 10- 1 mg of synthesized nanocatalyst, 0.5 mM NaBH4, and 110 W microwave radiations power. Recyclability of nanocatalyst was efficient till 4th cycle observed during study of reusability. The supported Pt-Pd bimetallic nanocatalyst on ITO displayed many advantages over conventional methods for degradation of methyl parathion pesticide, such as high percent degradation, short reaction time, small amount of nanocatalyst, and multitime reusability. Graphical abstract Schematic illustration of reaction for degradation of methyl parathion.
Gums; composed of polysaccharides, carbohydrates, proteins, and minerals, are high molecular weight hydrophilic compounds with several biological applications. This study describes the nutritional and toxic elements content, chemical composition, synthesis of silver nanoparticles (G-AgNPs), and pharmacological and catalytic properties of Prunus armeniaca (apricot), Prunus domestica (plums), Prunus persica (peaches), Acacia modesta (phulai), Acacia arabica (kikar), and Salmalia malabarica (silk cotton tree) gums. The elemental contents were analyzed by inductively coupled plasma-optical emission spectroscopy (ICP-OES) and ICP-mass spectrometry (ICP-MS). NMR spectroscopy was used for the identification of class of compounds in the mixture, their functional groups were determined through FTIR techniques, and plasmon resonance and size of G-AgNPs through UV-Vis spectroscopic technique and transmission electron microscopy (TEM). From the results, nutritional elements were present at appreciable concentrations, whereas toxic elements showed content below the maximum permissible ranges. Using the elemental data, linear discriminant and principal component analyses classified the gums to 99.9% variability index. Furthermore, G-AgNPs exhibited significant antioxidant, antibacterial, and redox catalytic potential. Hence, the subject G-AgNPs could have promising nutritional, therapeutic and environmental remediation applications.
In this study, a novel method for the production of biodiesel under mild conditions using fine particles of sodium methoxide formed in dimethyl carbonate (DMC) is proposed. Biodiesel is generally produced from vegetable oils by the transesterification of triglycerides with methanol. However, this reaction produces glycerol as a byproduct, and raw materials are not effectively utilized. Transesterification with DMC has recently been studied because glycerol is not formed in the process. Although solid-state sodium methoxide has been reported to be inactive for this reaction, the catalytic activity dramatically increased with the preparation of fine catalyst powders by crystallization. The transesterification of canola oil with DMC was studied using this catalyst for the preparation of biodiesel. A conversion greater than 96% was obtained at 65°C for 2h with a 3:1M ratio of DMC and oil and 2.0 wt% catalyst.
Bifunctional heterogeneous catalysts have a great potential to overcome the shortcomings of homogeneous and enzymatic catalysts and simplify the biodiesel production processes using low-grade, high-free-fatty-acid feedstock. In this study, we developed ZrO2-based bifunctional heterogeneous catalysts for simultaneous esterification and transesterification of microalgae to biodiesel. To avoid the disadvantage of the low surface area of ZrO2, the catalysts were prepared via a surfactant-assisted sol-gel method, followed by hydrothermal treatments. The response surface methodology central composite design was employed to investigate various factors, like the surfactant/Zr molar ratio, pH, aging time, and temperature on the ZrO2 surface area. The data were statistically analyzed to predict the optimal combination of factors, and further experiments were conducted for verification. Bi2O3 was supported on ZrO2 via the incipient wetness impregnation method. The catalysts were characterized by a variety of techniques, which disclosed that the surfactant-assisted ZrO2 nanoparticles possess higher surface area, better acid-base properties, and well-formed pore structures than bare ZrO2. The highest yield of fatty acid methyl esters (73.21%) was achieved using Bi2O3/ZrO2(CTAB), and the catalytic activity of the developed catalysts was linearly correlated with the total densities of the acidic and basic sites. The mechanism of the simultaneous reactions was also discussed.