The world faces the challenge to produce ultra-low sulfur diesel with low-cost technology. Therefore, this research emphasised on production of low sulfur fuel utilising nanoparticle catalyst under mild condition. A small amount of cobalt oxide (10-30 wt%) was introduced into the Fe/Al2O3 catalyst through the wet impregnation method. Cobalt modification induces a positive effect on the performance of the iron catalyst. Hence, the insertion of cobalt species into Fe/Al2O3 led to the formation of lattice fringes in all directions which resulted in the formation of Co3O4 and Fe3O4 species. The optimised catalyst, Co/Fe-Al2O3, calcined at 400 °C with a dopant ratio of 10:90 indicating the highest desulfurisation activity by removing 96% of thiophene, 100% of dibenzothiophene (DBT) and 92% of 4,6-dimethyl dibenzothiophene (4,6-DMDBT). Based on the density functional theory (DFT) on Co/Fe-Al2O3, two pathways with the overall energy of -40.78 eV were suggested for the complete oxidation of DBT.
The influence of pre-slaughter electrical stunning techniques and slaughter without stunning on bleeding efficiency and shelf life of chevon during a 14 d postmortem aging were assessed. Thirty two Boer crossbred bucks were randomly assigned to four slaughtering techniques viz slaughter without stunning (SWS), low frequency head-only electrical stunning (LFHO; 1 A for 3 s at a frequency of 50 Hz), low frequency head-to-back electrical stunning (LFHB; 1 A for 3 s at a frequency of 50 Hz) and high frequency head-to-back electrical stunning (HFHB; 1 A for 3 s at a frequency of 850 Hz). The SWS, LFHO and HFHB goats had higher (p<0.05) blood loss and lower residual hemoglobin in muscle compared to LFHB. The LFHB meat had higher (p<0.05) TBARS value than other treatments on d 7 and 14 d postmortem. Slaughtering methods had no effect on protein oxidation. Higher bacterial counts were observed in LFHB meat compared to those from SWS, LFHO and HFHB after 3 d postmortem. Results indicate that the low bleed-out in LFHB lowered the lipid oxidative stability and microbiological quality of chevon during aging.
The presence of phenolic compounds in the aquatic environment has posed severe risks due to their toxicity. Among the phenolic families, nitro- and alkyl-phenolic compounds have been categorized as precedence contaminants by the United States Environmental Protection Agency (US EPA). Therefore, efficient treatment methods for wastewater containing nitro- and alkyl-phenolic compounds are urgently needed. Due to the advantages of creating reactive species and generating efficient degradation of hazardous contaminants in wastewater, advanced oxidation processes (AOPs) are well-known in the field of treating toxic contaminants. In this review paper, the recent directions in AOPs, catalysts, mechanisms, and kinetics of AOPs are comprehensively reviewed. Furthermore, the conclusion summarizes the research findings, future prospects, and opportunities for this study. The main direction of AOPs lies on the optimization of catalyst and operating parameters, with industrial applications remain as the main challenge. This review article is expected to present a summary and in-depth understanding of AOPs development; and thus, inspiring scientists to accelerate the evolution of AOPs in industrial applications.
Global demand for epoxidized vegetable oil has been steadily growing. Epoxidized vegetable oils are typically produced using a two-pot synthesis process in which the oxidation and epoxidation reactions are carried out sequentially. This two-pot synthesis method, however, has a major drawback in industrialscale production, particularly when it comes to operational and process safety issues. A laboratory-scale one-pot synthesis method was attempted in this study with the aim to safely synthesize epoxidized Moringa Oleifera oil (eMOo) by avoiding the occurrence of undesired exothermic runaway reaction. The oil extracted from Moringa Oleifera oil seed kernel (MOo) was used as a starting component due to its high degree of unsaturation and also because the Moringa Oleifera plant can be freely grown in any soil conditions. Two parallel oxidation and epoxidation reactions were carried out simultaneously in this one-pot synthesis method to produce eMOo. The effect of five different mole ratios of MOo, acetic acid and hydrogen peroxide (1:1:1, 1:1:2, 1:1.5:2, 1:1.75:2 and 1:2:2, respectively) on reaction mechanism was investigated at the controlled temperature range of 43 - 55°C and reaction time of 0 - 120 min. The physicochemical properties of MOo as well as the oxirane oxygen content (OOC) of the resulting eMOo were characterized. In addition, GC-MS and FTIR analysis were performed to verify the molecular composition of MOo and also to identify the epoxy group of the resulting eMOo respectively. Among the five different mole ratios studied, the 1:1.5:2 mole ratio has the highest unsaturation conversion of 79.57% and OOC of 4.12%.
Natural soil minerals often contain numerous impurities, resulting in comparatively lower catalytic activity. Tropical soils are viewed as poor from soil organic matter, cations, and anions, which are considered the main impurities in the soil that are restricted to utilizing natural minerals as a catalyst. In this regard, the dissolved iron and hematite crystals that presented naturally in tropical soil were evaluated to activate oxidants and degrade pyrene. The optimum results obtained in this study were 73 %, and the rate constant was 0.0553 h-1 under experimental conditions [pyrene] = 300 mg/50 g, pH = 7, T = 55 °C, airflow = 260 mL/min, [Persulfate (PS)] = 1.0 g/L, and humic acid (HA) ( % w/w) = 0.5 %. The soil characterization analysis after the remediation process showed an increase in moieties and cracks of the soil aggregate, and a decline in the iron and aluminium contents. The scavengers test revealed that both SO4•- and O2•- were responsible for the pyrene degradation, while HO• had a minor role in the degradation process. In addition, the monitoring of by-products, degradation pathways, and toxicity assessment were also investigated. This system is considered an efficient, green method, and could provide a step forward to develop low-cost soil remediation for full-scale implementation.
The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications.
This paper reports a rapid and in-situ electrochemical polymerization method for the fabrication of polypyrrole nanoparticles incorporated reduced graphene oxide (rGO@PPy) nanocomposites on a ITO conducting glass and its application as a counter electrode for platinum-free dye-sensitized solar cell (DSSC). The scanning electron microscopic images show the uniform distribution of PPy nanoparticles with diameter ranges between 20 and 30 nm on the rGO sheets. The electrochemical studies reveal that the rGO@PPy has smaller charge transfer resistance and similar electrocatalytic activity as that of the standard Pt counter electrode for the I₃(-)/I(-) redox reaction. The overall solar to electrical energy conversion efficiency of the DSSC with the rGO@PPy counter electrode is 2.21%, which is merely equal to the efficiency of DSSC with sputtered Pt counter electrode (2.19%). The excellent photovoltaic performance, rapid and simple fabrication method and low-cost of the rGO@PPy can be potentially exploited as a alternative counter electrode to the expensive Pt in DSSCs.
The recent developments of nanostructured WO3 thin films synthesized through the electrochemical route of electrochemical anodization and cathodic electrodeposition for the application in photoelectrochemical (PEC) water splitting are reviewed. The key fundamental reaction mechanisms of electrochemical anodization and cathodic electrodeposition methods for synthesizing nanostructured WO3 thin films are explained. In addition, the effects of metal oxide precursors, electrode substrates, applied potentials and current densities, and annealing temperatures on size, composition, and thickness of the electrochemically synthesized nanostructured WO3 thin films are elucidated in detail. Finally, a summary is given for the general evaluation practices used to calculate the energy conversion efficiency of nanostructured WO3 thin films and a recommendation is provided to standardize the presentation of research results in the field to allow for easy comparison of reported PEC efficiencies in the near future.
The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C). A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a V max for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent K m for NADH was 0.79 mM. At 5 mM NADH, the apparent V max and apparent K m values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (k cat/K m ) of the Mo-reducing enzyme was 5.47 M(-1) s(-1). The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction.
Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO.
The aim of this study was to investigate the effect of atmospheric frying followed by drainage under vacuum on the stability of oil, compared to similar frying with drainage at atmospheric pressure. Changes in the oil were assessed by the free fatty acid (FFA) content, p-anisidine value (AnV), colour, viscosity, fatty acid profile and concentration of tocols. The rate of FFA formation in the case of vacuum drainage was found to be about half that of atmospheric drainage. Oil deterioration by oxidation and polymerisation was also reduced by the use of vacuum drainage. The AnV of the oil after vacuum drainage was lower by about 12%, the total colour difference was improved by 14% and viscosity was slightly reduced after 5 days of frying, compared to the values for oil that had been drained at atmospheric pressure. There was a reduction in the loss of polyunsaturated fatty acids in the case of vacuum drainage after 5 days of frying but differences in retention of tocols were only evident in the first two days of frying.
Terpenes and terpenoids are among the key impact substances in the food and fragrance industries. Equipped with pharmacological properties and applications as ideal precursors for the biotechnological production of natural aroma chemicals, interests in these compounds have been escalating. Hence, the syntheses of new derivatives that can show improved properties are often called for. Stereoselective biotransformation offers several benefits to increase the rate of production, in terms of both the percentage yield and its enantiomeric excesses. Baker's yeast (Saccharomyces cerevisiae) is broadly used as a whole cell stereospecific reduction biocatalyst, due to its capability in reducing carbonyls and carbon-carbon double bonds, which also extends its functionality as a versatile biocatalyst in terpenoid biotransformation. This review provides some insights on the development and prospects in the reductive biotransformation of monoterpenoids and sesquiterpenoids using S. cerevisiae, with an overview of strategies to overcome the common challenges in large-scale implementation.
Sonophotocatalysis involves the use of a combination of ultrasonic sound waves, ultraviolet radiation and a semiconductor photocatalyst to enhance a chemical reaction by the formation of free radicals in aqueous systems. Researchers have used sonophotocatalysis in a variety of investigations i.e. from water decontamination to direct pollutant degradation. This degradation process provides an excellent opportunity to reduce reaction time and the amount of reagents used without the need for extreme physical conditions. Given its advantages, the sonophotocatalysis process has a futuristic application from an engineering and fundamental aspect in commercial applications. A detailed search of published reports was done and analyzed in this paper with respect to sonication, photocatalysis and advanced oxidation processes.
Selective Non-Catalytic Reduction (SNCR) of nitric oxide has been studied experimentally by injecting aqueous urea solution with and without additive in a pilot-scale diesel fired tunnel furnace at 3.4% excess oxygen level and with low ppm of baseline NO(x) ranging from 65 to 75 ppm within the investigated temperature range. The tests have been carried out using commercial grade urea as NO(x) reducing agent and commercial grade sodium carbonate as additive. The furnace simulated the small-scale combustion systems, where the operating temperatures are usually in the range of about 973 to 1323 K and NO(x) emission level remains below 100 ppm. With 5% plain urea solution, at Normalized Stoichiometric Ratio (NSR) of 4 as much as 54% reduction was achieved at 1128 K, whilst in the additive case the NO(x) reduction was improved to as much as 69% at 1093 K. Apart from this improvement, in the additive case, the effective temperature window as well as peak temperature of NO(x) reduction shifted towards lower temperatures. The result is quite significant, especially for this investigated level of baseline NO(x). The ammonia slip measurements showed that in both cases the slip was below 16 ppm at NSR of 4 and optimum temperature of NO(x) reduction. Finally, the investigations demonstrated that urea based SNCR is quite applicable to small-scale combustion applications and commercial grade sodium carbonate is a potential additive.
This paper presents the preparation of in situ electrodeposited rGO/MnO2 nanocomposite as a binder-free electrode for supercapacitor application. The work describes and evaluates the performance of prepared electrode via green and facile electrodeposition technique of in situ rGO/MnO2-glucose carbon nanocomposites. The carbon content in the composite electrode increased after GO and D (+) glucose solution has been added in the deposition electrolyte. This study found that a suitable concentration of D (+) glucose in the deposition electrolyte can slow down the nucleation process of MnO2 particles and lead to uniform and ultrathin nanoflakes structure. The optimize electrode exhibited low transfer resistance and resulted on excellent electrochemical performance in three electrolyte systems viz. Na2SO4, KOH and KOH/K3Fe(CN)6 redox electrolytes. The optimum energy density and power density were 1851 Whkg(-1) and 68 kWkg(-1) at current density of 20 Ag(-1) in mixed KOH/K3Fe(CN)6 electrolyte.
A combination of persulfate and hydrogen peroxide (S2O8(2-)/H2O2) was used to oxidizelandfill leachate. The reaction was performed under varying S2O8(2-)/H2O2 ratio (g/g), S2O8(2-)/H2O2 dosages (g/g), pH, and reaction time (minutes), so as to determine the optimum operational conditions. Results indicated that under optimum operational conditions (i.e. 120 min of oxidation using a S2O8(2-)/H2O2 ratio of 1 g/1.47 g at a persulfate and hydrogen peroxide dosage of 5.88 g/50 ml and8.63 g/50 ml respectively, at pH 11) removal of 81% COD and 83% NH3-N was achieved. In addition, the biodegradability (BOD5/COD ratio) of the leachate was improved from 0.09 to 0.17. The results obtained from the combined use of (S2O8(2-)/H2O2) were compared with those obtained with sodium persulfate only, hydrogen peroxide only and sodium persulfate followed by hydrogen peroxide. The combined method (S2O8(2-)/H2O2) achieved higher removal efficiencies for COD and NH3-N compared with the other methods using a single oxidizing agent. Additionally, the study has proved that the combination of S2O8(2-)/H2O2 is more efficient than the sequential use of sodium persulfate followed by hydrogen peroxide in advanced oxidation processes aiming at treatingstabilizedlandfill leachate.
Geometric isomerization can expand the scope of biological activities of natural products. The observed chemical diversity among the pseurotin-type fungal secondary metabolites is in part generated by a trans to cis isomerization of an olefin. In vitro characterizations of pseurotin biosynthetic enzymes revealed that the glutathione S-transferase PsoE requires participation of the bifunctional C-methyltransferase/epoxidase PsoF to complete the trans to cis isomerization of the pathway intermediate presynerazol. The crystal structure of the PsoE/glutathione/presynerazol complex indicated stereospecific glutathione-presynerazol conjugate formation is the principal function of PsoE. Moreover, PsoF was identified to have an additional, unexpected oxidative isomerase activity, thus making it a trifunctional enzyme which is key to the complexity generation in pseurotin biosynthesis. Through the study, we identified a novel mechanism of accomplishing a seemingly simple trans to cis isomerization reaction.
In mangrove ecosystems, litter fall accumulates as refractory organic carbon on the sediment surface and creates anoxic sediment layers. Fiddler crabs, through their burrowing activity, translocate oxygen into the anoxic layers and promote aerobic respiration, iron reduction and nitrification. In this study, the effects of four species of fiddler crabs (Uca triangularis, Uca rosea, Uca forcipata and Uca paradussumieri) on organic content, water content, porosity, redox potential and solid phase iron pools of mangrove sediments were investigated. In each crab's habitat, six cores down to 30 cm depth were taken from burrowed and non-burrowed sampling plots. Redox potential and oxidized iron pools were highest in surface sediment, while porosity, water and organic content were higher in deeper sediment. Reduced iron (Fe (II)) and redox potential were significantly different between burrowed and non-burrowed plots. Crab burrows extend the oxidized surface layer down to 4 cm depth and through the oxidation effect, reduce the organic content of sediments. The effects of burrows varied between the four species based on their shore location. The oxidation effect of burrows enhance the decomposition rate and stimulate iron reduction, which are processes that are expected to play an important role in biogeochemical properties of mangrove sediments.
To overcome the critical limitations of liquid-electrolyte-based dye-sensitized solar cells, quasi-solid-state electrolytes have been explored as a means of addressing long-term device stability, albeit with comparatively low ionic conductivities and device performances. Although metal oxide additives have been shown to augment ionic conductivity, their propensity to aggregate into large crystalline particles upon high-heat annealing hinders their full potential in quasi-solid-state electrolytes. In this work, sonochemical processing has been successfully applied to generate fine Co3O4 nanoparticles that are highly dispersible in a PAN:P(VP-co-VAc) polymer-blended gel electrolyte, even after calcination. An optimized nanocomposite gel polymer electrolyte containing 3 wt % sonicated Co3O4 nanoparticles (PVVA-3) delivers the highest ionic conductivity (4.62 × 10-3 S cm-1) of the series. This property is accompanied by a 51% enhancement in the apparent diffusion coefficient of triiodide versus both unmodified and unsonicated electrolyte samples. The dye-sensitized solar cell based on PVVA-3 displays a power conversion efficiency of 6.46% under AM1.5 G, 100 mW cm-2. By identifying the optimal loading of sonochemically processed nanoparticles, we are able to generate a homogenous extended particle network that effectively mobilizes redox-active species through a highly amorphous host matrix. This effect is manifested in a selective 51% enhancement in photocurrent density (JSC = 16.2 mA cm-2) and a lowered barrier to N719 dye regeneration (RCT = 193 Ω) versus an unmodified solar cell. To the best of our knowledge, this work represents the highest known efficiency to date for dye-sensitized solar cells based on a sonicated Co3O4-modified gel polymer electrolyte. Sonochemical processing, when applied in this manner, has the potential to make meaningful contributions toward the ongoing mission to achieve the widespread exploitation of stable and low-cost dye-sensitized solar cells.
An upsurge in sustainable energy demands has ultimately made supercapattery one of the important choice for energy storage, owing to highly advantageous energy density and long life span. In this work, novel strontium based mixed phased nanostructures were synthesized by using probe sonicator with sonication power 500 W at frequency of 20 kHz. The synthesized material was subsequently calcined at different temperature ranging from 200 to 800 °C. Structural and morphological analysis of the synthesized materials reveals the formation of mixed particle and rod like nanostructures with multiple crystal phases of strontium oxides and carbonates. Crystallinity, grain size and morphology of grown nanomaterials significantly improved with the increase of calcination temperature due to sufficient particle growth and low agglomeration. The electrochemical performance analysis confirms the redox activeness of the Sr-based electrode materials. Material calcined at 600 °C show high specific capacitance of 350 F g-1 and specific capacity of 175 C g-1 at current density of 0.3 A g-1 due to less particle agglomeration, good charge transfer and more contribution of electrochemical active sites for redox reactions. In addition, the developed supercapattery of Sr-based nanomaterials//activated carbon demonstrated high performance with maximum energy density of 21.8 Wh kg-1 and an excellent power density of 2400 W kg-1 for the lower and higher current densities. Furthermore, the supercapattery retain 87% of its capacity after continuous 3000 charge/discharge cycles. The device characteristics were further investigated by analyzing the capacitive and diffusion controlled contributions. The versatile strategy of developing mixed phased nanomaterials pave the way to synthesize other transition metal based nanomaterials with superior electrochemical performance for hybrid energy storage devices.