Palm olein (POL) was modified by enzymatic interesterification with different degrees of acyl migration in a solvent-free packed bed reactor. The fatty acid and acylglycerol composition, isomer content, thermodynamic behavior, and relationship between crystal polymorphism, solid fat content (SFC), crystal microstructure, and texture before and after modification were studied. We found that the increase in sn-2 saturation interesterification was not only due to the generated tripalmitin (PPP) but also caused by acyl migration, and the SFC profiles were changed accordingly. The emergence of high melting point acylglycerols was an important factor accelerating the crystallization rate, further shortening the crystallization induction time, leading to the formation of large crystal spherulites, thereby reducing the hardness. The transformation from the β' to the β form occurred during post-hardening during storage. The isomer content also affected the physicochemical properties of the modified POL.
In this study, nickel-loaded perovskite oxides catalysts were synthesized via the impregnation of 10%Ni on XTiO3 (X = Ce, Sr, La, Ba, Ca, and Fe) supports and employed in the catalytic steam gasification of swine manure to produce H2-rich syngas for the first time. The synthesized catalysts were characterized using BET, H2-TPR, XRD, HR-TEM, and EDX analysis. Briefly, using perovskite supports resulted in the production of ultrafine catalyst nanoparticles with a uniform dispersion of Ni particles. According to the catalytic activity test, the gas yield showed the increment as 10% Ni/LaTiO3 < 10% Ni/FeTiO3 < 10% Ni/CeTiO3 < 10% Ni/BaTiO3 < 10% Ni/SrTiO3 < 10% Ni/CaTiO3. Meanwhile, zero coke formation was achieved due to the oxygen mobility of prepared catalysts. Also, the increase in the H2 production for the applied catalysts was in the sequence as 10% Ni/CeTiO3 < 10% Ni/FeTiO3 < 10% Ni/LaTiO3 < 10% Ni/BaTiO3 < 10% Ni/SrTiO3 < 10% Ni/CaTiO3. The maximum H2 selectivity (∼48 vol%) obtained by10% Ni/CaTiO3 was probably due to the synergistic effect of Ni and Ti on enhancing the water-gas shift reaction, and Ca on creating the maximum oxygen mobility compared to other alkaline earth metals doped at the A place of perovskite. Overall, this study provides a suitable solution for enhanced H2 production through steam gasification of swine manure along with suggesting the appropriate supports to prevent Ni deactivation by lowering coke formation at the same time.
In this study, the photocatalytic degradation of toxic pollutant (2-chlorophenol) in the presence of ZnO nanoparticles (ZnO NPs) was investigated under solar radiation. The three main factors, namely pH of solution, solar intensity and calcination temperature, were selected in order to examine their effects on the efficiency of the degradation process. The response surface methodology (RSM) technique based on D-optimal design was applied to optimise the process. ANOVA analysis showed that solar intensity and calcination temperature were the two significant factors for degradation efficiency. The optimum conditions in the model were solar intensity at 19.8 W/m(2), calcination temperature at 404 °C and pH of 6.0. The maximum degradation efficiency was predicted to be 90.5% which was in good agreement with the actual experimental value of 93.5%. The fit of the D-optimal design correlated very well with the experimental results with higher values of R (2) and R (2)adj correlation coefficients of 0.9847 and 0.9676, respectively. The intermediate mechanism behaviour of the 2-chlorophenol degradation process was determined by gas chromatography-mass spectrometry (GC-MS). The results confirmed that 2-chlorophenol was converted to acetic acid, a non-toxic compound.
This study investigated the coagulation performance of titanium tetrachloride (TiCl4) for leachate treatment and preparation of titanium oxide (TiO2) from generated sludge through calcination process at different temperatures and times. TiCl4 with chitosan as coagulant aid employed to perform coagulation process on Alor Ponhsu Landfill leachate. Further calcination process was done to synthesize TiO2 from produced sludge for photocatalytic applications. The studied factors included pH, TiCl4 dosage, and chitosan dosage. The results indicated that maximum reduction in suspended solids was 92.02% at pH 4, 1200 mg/L TiCl4, and 250 mg/L chitosan addition, and maximum reduction in chemical oxygen demand was 71.92% at experimental condition of 1200 mg/L TiCl4 and 500 mg/L chitosan with pH 10. The maximum and minimum band gaps of prepared TiO2 achieved at 3.35 eV and 2.75 eV, respectively. Morphology and phase analysis of prepared TiO2 characterized using scanning electron microscope (SEM) and X-ray diffraction (XRD). The XRD spectrums showed the anatase phase at lower calcination temperature and the rutile phase at elevated temperature. The photocatalysis activity of produced TiO2 investigated under UV irradiation and showed almost fast degradation similar to commercial TiO2. The results indicated that TiO2 powder was successfully prepared from generated sludge from TiCl4 coagulation for photocatalytic applications.
The novel phosphonium-based ionic liquid (IL), triphenyl methyl phosphonium tosylate ([TPMP][Tos]), has been synthesized and applied as a phase transfer catalyst (PTC) in the ultrasound-assisted oxidative desulfurization (UAODS). Oxidation of model fuel (MF) containing dibenzothiophene (DBT) was carried out using an equimolar mixture of H2O2-CH3COOH as an oxidant at 40-70 °C in the presence of IL. The sulfur compound is converted into polar sulfone, and the maximum desulfurization efficiency was examined. The effect of process parameters such as reaction temperature, reaction time, molar ratio of oxidant to sulfur (n(O/S)), and the mass ratio of ionic liquid to model fuel (m(IL/MF)) was studied, and the conditions for maximizing the DBT conversion rate were found. Maximum conversion (> 99%) was obtained at a temperature of 70 °C with m(IL/MF) of 0.8. The oxidation reactivity of various sulfur compounds was studied at different time intervals. To verify the effect of ionic liquid and ultrasound irradiation, extractive desulfurization (EDS), oxidative desulfurization (ODS), and UAODS in the presence of IL were carried out. The experimental results show that the UAODS process gives the highest desulfurization efficiency. A kinetic study was performed to estimate the rate constant and the order of oxidation reaction.
Graphitic carbon nitride (g-C3N4) has been regarded as a promising visible light-driven photocatalyst ascribable to its tailorable structures, thermal stability and chemical inertness. Enhanced photocatalytic activity is achievable by the construction of homojunction nanocomposites to reduce the undesired recombination of photogenerated charge carriers. In the present work, a novel g-C3N4/g-C3N4 metal-free homojunction photocatalyst was synthesized via hydrothermal polymerization. The g-C3N4/g-C3N4 derived from urea and thiourea demonstrated admirable photocatalytic activity towards rhodamine B (RhB) degradation upon irradiation of an 18 W LED light. The viability of the photoreaction with a low-powered excitation source highlighted the economic and environmental benefits of the process. The optimal g-C3N4/g-C3N4 homojunction photocatalyst exhibited a 2- and 1.8-fold increase in efficiency in relative to pristine g-C3N4 derived from urea and thiourea respectively. The enhanced photocatalytic performance is credited to the improved interfacial transfer and separation of electron-hole pairs across the homojunction interface. Furthermore, an excellent photochemical stability and durability is displayed by g-C3N4/g-C3N4 after three consecutive cycles. In addition, a plausible photocatalytic mechanism was proposed based on various scavenging tests. Overall, experimental results generated from this study is expected to intrigue novel research inspirations in developing metal-free homojunction photocatalysts to be feasible for large-scale wastewater treatment without compromising economically. Graphical abstract.
In this work, sand/zinc oxide (ZnO)/titanium dioxide (TiO2)-based photocatalysts were hybridized with graphene oxide (GO) and GO_multi-walled carbon nanotubes (MWCNTs) hybrid solution. The novel hybrid was then used in photocatalysis to degrade dye contamination. The nanocomposite photocatalyst was initially fabricated by growing ZnO nanorods (NRs) via sol-gel immersion followed by synthesizing TiO2 NRs for different times (5 and 20 h) using a hydrothermal method on sand as a substrate. Prior to the hybridization, the initial GO was synthesized using electrochemical exfoliation and further mixed with 1 wt% MWCNTs to form GO_MWCNTs hybrid solution. The synthesized GO and GO_MWCNTs hybrid solution were then incorporated onto sand/ZnO/TiO2 nanocomposite-based photocatalysts through immersion. Various sand/ZnO/TiO2-based photocatalysts were then tested for methylene blue (MB) dye degradation within 3 days. On the basis of UV-Vis measurement, the highest MB degradation was achieved by using sand/ZnO NRs/TiO2 NRs (5 h)/GO_MWCNTs (92.60%). The high surface area and high electrical conductivity of GO_MWCNTs prolonged the lifetime of electron/hole separation and thus enhanced the photocatalytic performance.
Oxidation of o-xylene was performed using alkaline battery-based catalyst doped with platinum to investigate the properties and activities. O-xylene was selected as the model of volatile organic compound (VOC) in this work. Physicochemical properties of the selected catalysts were characterized by FE/TEM (field emission transmission electron microscopy), BET (Brunauer-Emmett-Teller) analysis, XRD (X-ray powder diffraction), SEM/EDX (scanning electron microscopy/energy dispersive X-ray spectroscopy), and H2-TPR (hydrogen temperature programmed reduction). Major elements of the spent alkaline battery-based catalyst treated with sulfuric acid solution [SAB (400) catalyst] were manganese, zinc, iron, oxygen, carbon, chlorine, aluminum, sodium, silicon, and potassium. Increasing the doping amount of platinum on SAB (400) catalyst from 0.1 to 1 wt% increased particle size of platinum and lowered the temperature of TPR (TTP) for SAB (400) catalyst. Better redox properties were achieved with an increase in the o-xylene conversion according to the doping amount of platinum. When GHSV (gas hourly space velocity) was 40,000 h-1, o-xylene was oxidized completely over SAB (400) catalyst and 1.0 wt% Pt/SAB(400) catalyst at temperatures of 400 °C and 280 °C, respectively.
Herein, we report a detailed study on creating heterojunction between graphitic carbon nitride (g-C3N4) and bismuth phosphate (BiPO4), enhancing the unpaired free electron mobility. This leads to an accelerated photocatalysis of 2,4-dichlorophenols (2,4-DCPs) under sunlight irradiation. The heterojunction formation was efficaciously conducted via a modest thermal deposition technique. The function of g-C3N4 plays a significant role in generating free electrons under sunlight irradiation. Together, the generated electrons at the g-C3N4 conduction band (CB) are transferred and trapped by the BiPO4 to form active superoxide anion radicals (•O2-). These active radicals will be accountable for the photodegradation of 2,4-DCPs. The synthesized composite characteristics were methodically examined through several chemical and physical studies. Due to the inimitable features of both g-C3N4 and BiPO4, its heterojunction formation, 2.5wt% BiPO4/g-C3N4 achieved complete 2,4-DCP removal (100%) in 90 min under sunlight irradiation. This is due to the presence of g-C3N4 that enhanced electron mobility through the formation of heterojunctions that lengthens the electron-hole pairs' lifetime and maximizes the entire solar spectrum absorption to generate active electrons at the g-C3N4 conduction band. Thus, this formation significantly draws the attention for future environmental remediation, especially in enhancing the entire solar spectrum's harvesting.
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.
In the present work, we prepared MgO-La2O3-mixed-metal oxides (MMO) as efficient photocatalysts for degradation of organic pollutants. First, a series of MgAl-%La-CO3-layered double hydroxide (LDH) precursors with different contents of La (5, 10, and 20 wt%) were synthesized by the co-precipitation process and then calcined at 600 °C. The prepared materials were characterized by XRD, SEM-EDX, FTIR, TGA, ICP, and UV-vis diffuse reflectance spectroscopy. XRD indicated that MgO, La2O3, and MgAl2O4 phases were found to coexist in the calcined materials. Also, XRD confirms the orthorhombic-tetragonal phases of MgO-La2O3. The samples exhibited a small band gap of 3.0-3.22 eV based on DRS. The photocatalytic activity of the catalysts was assessed for the degradation of two dyes, namely, tartrazine (TZ) and patent blue (PB) as model organic pollutants in aqueous mediums under UV-visible light. Detailed photocatalytic tests that focused on the impacts of dopant amount of La, catalyst dose, initial pH of the solution, irradiation time, dye concentration, and reuse were carried out and discussed in this research. The experimental findings reveal that the highest photocatalytic activity was achieved with the MgO-La2O3-10% MMO with photocatalysts with a degradation efficiency of 97.4% and 93.87% for TZ and PB, respectively, within 150 min of irradiation. The addition of La to the sample was responsible for its highest photocatalytic activity. Response surface methodology (RSM) and gradient boosting regressor (GBR), as artificial intelligence techniques, were employed to assess individual and interactive influences of initial dye concentration, catalyst dose, initial pH, and irradiation time on the degradation performance. The GBR technique predicts the degradation efficiency results with R2 = 0.98 for both TZ and PB. Moreover, ANOVA analysis employing CCD-RSM reveals a high agreement between the quadratic model predictions and the experimental results for TZ and PB (R2 = 0.9327 and Adj-R2 = 0.8699, R2 = 0.9574 and Adj-R2 = 0.8704, respectively). Optimization outcomes indicated that maximum degradation efficiency was attained under the following optimum conditions: catalyst dose 0.3 g/L, initial dye concentration 20 mg/L, pH 4, and reaction time 150 min. On the whole, this study confirms that the proposed artificial intelligence (AI) techniques constituted reliable and robust computer techniques for monitoring and modeling the photodegradation of organic pollutants from aqueous mediums by MgO-La2O3-MMO heterostructure catalysts.
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.
Photocatalysis utilizing semiconductors offer a cost-effective and promising solution for the removal of pollutants. MXene and perovskites, which possess desirable properties such as a suitable bandgap, stability, and affordability, have emerged as a highly promising material for photocatalytic activity. However, the efficiency of MXene and perovskites is limited by their fast recombination rates and inadequate light harvesting abilities. Nonetheless, several additional modifications have been shown to enhance their performance, thereby warranting further exploration. This study delves into the fundamental principles of reactive species for MXene-perovskites. Various methods of modification of MXene-perovskite-based photocatalysts, including Schottky junction, Z-scheme and S-scheme are analyzed with regard to their operation, differences, identification techniques and reusability. The assemblance of heterojunctions is demonstrated to enhance photocatalytic activity while also suppressing charge carrier recombination. Furthermore, the separation of photocatalysts through magnetic-based methods is also investigated. Consequently, MXene-perovskite-based photocatalysts are seen as an exciting emerging technology that necessitates further research and development.
The catalytic activity of low-dimensional electrocatalysts is highly dependent on their local atomic structures, particularly those less-coordinated sites found at edges and corners; therefore, a direct probe of the electrocatalytic current at specified local sites with true nanoscopic resolution has become critically important. Despite the growing availability of operando imaging tools, to date it has not been possible to measure the electrocatalytic activities from individual material edges and directly correlate those with the local structural defects. Herein, we show the possibility of using feedback and generation/collection modes of operation of the scanning electrochemical microscope (SECM) to independently image the topography and local electrocatalytic activity with 15-nm spatial resolution. We employed this operando microscopy technique to map out the oxygen evolution activity of a semi-2D nickel oxide nanosheet. The improved resolution and sensitivity enables us to distinguish the higher activities of the materials' edges from that of the fully coordinated surfaces in operando The combination of spatially resolved electrochemical information with state-of-the-art electron tomography, that unravels the 3D complexity of the edges, and ab initio calculations allows us to reveal the intricate coordination dependent activity along individual edges of the semi-2D material that is not achievable by other methods. The comparison of the simulated line scans to the experimental data suggests that the catalytic current density at the nanosheet edge is ∼200 times higher than that at the NiO basal plane.
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.
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.
CO2 gasification of oil palm shell (OPS) char to produce CO through the Boudouard reaction (C + CO2 ↔ 2CO) was investigated under microwave irradiation. A microwave heating system was developed to carry out the CO2 gasification in a packed bed of OPS char. The influence of char particle size, temperature and gas flow rate on CO2 conversion and CO evolution was considered. It was attempted to improve the reactivity of OPS char in gasification reaction through incorporation of Fe catalyst into the char skeleton. Very promising results were achieved in our experiments, where a CO2 conversion of 99% could be maintained during 60 min microwave-induced gasification of iron-catalyzed char. When similar gasification experiments were performed in conventional electric furnace, the superior performance of microwave over thermal driven reaction was elucidated. The activation energies of 36.0, 74.2 and 247.2 kJ/mol were obtained for catalytic and non-catalytic microwave and thermal heating, respectively.
A series of tripeptide organocatalysts containing a secondary amine group and two amino acids with polar side chain units were developed and evaluated in the direct asymmetric intermolecular aldol reaction of 4-nitrobenzaldehyde and cyclohexanone. The effectiveness of short polar peptides as asymmetric catalysts in aldol reactions to attain high yields of enantio- and diastereoselective isomers were investigated. In a comparison, glutamic acid and histidine produced higher % ee and yields when they were applied as the second amino acid in short trimeric peptides. These short polar peptides were found to be efficient organocatalysts for the asymmetric aldol addition reaction in aqueous media.
Nanoporous materials such as Mobil composite material number 41 (MCM-41) are attractive for applications such as catalysis, adsorption, supports, and carriers. Green synthesis of MCM-41 is particularly appealing because the chemical reagents are useful and valuable. We report on the eco-friendly synthesis of MCM-41 nanoporous materials via multi-cycle approach by re-using the non-reacted reagents in supernatant as mother liquor after separating the solid product. This approach was achieved via minimal requirement of chemical compensation where additional fresh reactants were added into the mother liquor followed by pH adjustment after each cycle of synthesis. The solid product of each successive batch was collected and characterized while the non-reacted reagents in supernatant can be recovered and re-used to produce subsequent cycle of MCM-41. The multi-cycle synthesis is demonstrated up to three times in this research. This approach suggests a low cost and eco-friendly synthesis of nanoporous material since less waste is discarded after the product has been collected, and in addition, product yield can be maintained at the high level.