Xylitol is a high-value low-calorie sweetener used as sugar substitute in food and pharmaceutical industry. Xylitol phosphate dehydrogenase (XPDH) catalyses the conversion of d-xylulose 5-phosphate (XU5P) and d-ribulose 5-phosphate (RU5P) to xylitol and ribitol respectively in the presence of nicotinamide adenine dinucleotide hydride (NADH). Although these enzymes have been shown to produce xylitol and ribitol, there is an incomplete understanding of the mechanism of the catalytic events of these reactions and the detailed mechanism has yet to be elucidated. The main goal of this work is to analyse the conformational changes of XPDH-bound ligands such as zinc, NADH, XU5P, and RU5P to elucidate the key amino acids involved in the substrate binding. In silico modelling, comparative molecular dynamics simulations, interaction analysis and conformational study were carried out on three XPDH enzymes of the Medium-chain dehydrogenase (MDR) family in order to elucidate the atomistic details of conformational transition, especially on the open and closed state of XPDH. The analysis also revealed the possible mechanism of substrate specificity that are responsible in the catalyse hydride transfer are the residues His58 and Ser39 which would act as the proton donor for reduction of XU5P and RU5P respectively. The structural comparison and MD simulations displayed a significant difference in the conformational dynamics of the catalytic and coenzyme loops between Apo and XPDH-complexes and highlight the contribution of newly found triad residues. This study would assist future mutagenesis study and enzyme modification work to increase the catalysis efficiency of xylitol production in the industry.
Over the past decades, research efforts are being devoted into utilizing the biomass waste as a major source of green energy to maintain the economic, environmental, and social sustainability. Specifically, there is an emerging consensus on the significance of glycerol (an underutilised waste from biodiesel industry) as a cheap, non-toxic, and renewable source for valuable chemicals synthesis. There are numerous methods enacted to convert this glycerol waste to tartronic acid, mesoxalic acid, glyceraldehyde, dihydroxyacetone, oxalic acid and so on. Among these, the green electro-oxidation technique is one of the techniques that possesses potential for industrial application due to advantages such as non-toxicity process, fast response, and lower energy consumption. The current review covers the general understanding on commonly used techniques for alcohol (C1 & C2) conversion, with a specific insight on glycerol (C3) electro-oxidation (GOR). Since catalysts are the backbone of chemical reaction, they are responsible for the overall economy prospect of any processes. To this end, a comprehensive review on catalysts, which include noble metals, non-noble metals, and non-metals anchored over various supports are incorporated in this review. Moreover, a fundamental insight into the development of future electrocatalysts for glycerol oxidation along with products analysis is also presented.
Porous ZnO nanostructures have become the subject of research interest--due to their special structures with high surface to volume ratio that may produce peculiar properties for use in optoelectronics, sensing and catalysis applications. A microwave-assisted hydrothermal method has been used for effecting the formation of porous nanostructure of metaloxide materials, such as CoO and SnO2, in solution. Here, by adopting the unique performance of a microwave-assisted-hydrothermal method, we realized the formation of highly porous ZnO nanostructures directly on the substrate surface, instead of in solution. The effects of the ambient reaction conditions and the microwave power on the structural growth of the ZnO nanostructures were studied in detail. Two different ambient reaction conditions, namely refluxed and isolated in autoclave systems, were used in this work. Porous ZnO (PZO) nanostructures with networked-nanoflakes morphology is the typical result for this approach. It was found that the morphology of the ZnO nanostructures was strongly depended on the ambient conditions of the reaction; the isolated-autoclave system may produce reasonably high porous ZnO that is constituted by vertically oriented grainy-flakes structures, whereas the refluxed system produced solid vertically-oriented flake structures. The microwave power did not influence the structural growth of the ZnO. It was also found that both the ambient reaction conditions and the microwave power used influenced the crystallographic orientation of the PZO. For instance, PZO with dominant (002) Bragg plane could be obtained by using refluxed system, whereas PZO with dominant (101) plane could be realized if using isolated system. For the case of microwave power, the crystallographic orientation of PZO prepared using both systems changed from dominant (002) to (101) planes if the power was increased. The mechanism for the formation of porous ZnO nanostructures using the present approach is proposed. The ZnO nanostructures prepared using the present method should find an extensive use in currently existing application due to its property of reasonably high porosity.
In this study, carbon-silica based acid catalysts derived from rice husks (RH) were successfully synthesised using microwave (MW) technology. The results showed that MW sulphonation produced Sulphur (S) content of 17.2-18.5 times higher than in raw RH. Fourier-transform Infrared Spectroscopy (FTIR) showed peak at 1035 cm-1 which corresponded to O˭S˭O stretching of sulphonic (-SO3H) group. XRD showed sulfonated RH catalysts (SRHCs) have amorphous structure, and through SEM, broadening of the RH voids and also formation of pores is observed. RH600 had the highest surface area of 14.52 m2/g. SRHCs showed high catalytic activity for esterification of oleic acid with methanol with RH600 had the highest initial formation rate (6.33 mmolL-1min-1) and yield (97%). The reusability of the catalyst showed gradually dropped yield of product for every recycle, which might be due to leaching of -SO3H. Finally, esterification of oil recovered from palm oil mill effluent (POME) with methanol achieved a conversion of 87.3% free fatty acids (FFA) into fatty acid methyl esters (FAME).
New solid acid catalyst consisting of zirconium sulfate (ZS) supported on a pure-HMS hexagonal mesoporous material (HMS) have been prepared and characterized. This heterogeneous catalyst is able to make a contribution to the field of acid catalyst involving bulky organic molecules. XRD analysis shows that ZS is intact after impregnated on HMS surface and formed finely dispersed species. No ZS crystal phase was developed even at ZS loadings as high as 40 wt %. The occurrence of chemical interaction between ZS and HMS was observed by XPS analysis. Further, XRF results demonstrated that there is no leaching of ZS elements after impregnation. This study shows that ZS can be impregnated on HMS and would be a promising solid acid catalyst for acid-type reactions espcially invovling bulky organic molecuels.
Since the discovery of carbon nanotubes (CNTs) in 1991, a fundamental question still remained on how to control morphologically the synthesis of CNTs. This task has always been a challenge. In this paper, we report the results that we have published previously with the aim of sharing the possible controlled synthesis approach via this novel production method. Findings demonstrated that various CNTs could be synthesized by using specially developed supported catalysts from the catalytic decomposition of methane. These synthesized CNTs include carbon nanofibres, single-walled and multi-walled CNTs, Y-junction CNTs and CNTs with special morphologies. It was also revealed that catalyst composition and reaction parameters played an important role in controlling the morphology and type of CNTs formed. The synthesis of CNTs with various morphologies is important because this can enrich the nanostructures of the carbon family. This finding also provides useful data for better understanding of the parameters that govern the growth mechanism of CNTs which may be required in the near future for enhanced controlled synthesis of CNTs.
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.
Dry reforming of methane (DRM) is one of the more promising methods for syngas (synthetic gas) production and co-utilization of methane and carbon dioxide, which are the main greenhouse gases. Magnesium is commonly applied in a Ni-based catalyst in DRM to improve catalyst performance and inhibit carbon deposition. The aim of this review is to gain better insight into recent developments on the use of Mg as a support or promoter for DRM catalysts. Its high basicity and high thermal stability make Mg suitable for introduction into the highly endothermic reaction of DRM. The introduction of Mg as a support or promoter for Ni-based catalysts allows for good metal dispersion on the catalyst surface, which consequently facilitates high catalytic activity and low catalyst deactivation. The mechanism of DRM and carbon formation and reduction are reviewed. This work further explores how different constraints, such as the synthesis method, metal loading, pretreatment, and operating conditions, influence the dry reforming reactions and product yields. In this review, different strategies for enhancing catalytic activity and the effect of metal dispersion on Mg-containing oxide catalysts are highlighted.
The present study reported for the first time covalent immobilization of protocatechuate 3,4-dioxygenase (3,4-POD) onto functionalized multi-walled carbon nanotubes (F-MWCNT) for degrading the toxic 3,4-dihydroxybenzoic acid (3,4-DHBA) pollutant in water. The F-MWCNTs had a maximum 3,4-POD loading of 1060 μg/mg. Immobilized 3,4 POD had 44% of relative structural changes to its free configurations. Nevertheless, >90% of relative activity and about 50% of catalytic efficiency were retained to the free enzyme. Immobilized 3,4-POD demonstrated higher alkaline stability and thermostability than the free 3,4-POD. The free and immobilized 3,4-POD lost 82% and 66% of relative activities, respectively after 180 min of incubations at 90 °C. Excellent shelf-life was observed for the immobilized 3,4-POD with residual activity of 56% compared with 41% and 39% of the free 3,4-POD at 4 °C and 25 °C over 30 days storage. Immobilized 3,4-POD showed >60% of catalytic activity retention even after ten-cycle uses, defraying the expenses of free 3,4-POD productions for long term uses. Finally, the immobilized 3,4-POD removed 71% of 3,4-DHBA from water in <4 h, paving its future application for water purification with reduced costs and time.
In the present work, two-dimensional bismuth oxybromide (BiOBr) was synthesized and coupled with co-catalyst molybdenum disulphide (MoS2) via a simple hydrothermal process. The photoactivity of the resulting hybrid photocatalyst (MoS2/BiOBr) was evaluated under the irradiation of 15 W energy-saving light bulb at ambient condition using Reactive Black 5 (RB5) as model dye solution. The photo-degradation of RB5 by BiOBr loaded with 0.2 wt% MoS2 (MoBi-2) exhibited more than 1.4 and 5.0 folds of enhancement over pristine BiOBr and titanium dioxide (Degussa, P25), respectively. The increased photocatalytic performance was a result of an efficient migration of excited electrons from BiOBr to MoS2, prolonging the electron-hole pairs recombination rate. A possible charge transfer diagram of this hybrid composite photocatalyst, and the reaction mechanism for the photodegradation of RB5 were proposed.
Chemical interesterification of rubber seed oil has been investigated for four different designed orifice devices in a pilot scale hydrodynamic cavitation (HC) system. Upstream pressure within 1-3.5bar induced cavities to intensify the process. An optimal orifice plate geometry was considered as plate with 1mm dia hole having 21 holes at 3bar inlet pressure. The optimisation results of interesterification were revealed by response surface methodology; methyl acetate to oil molar ratio of 14:1, catalyst amount of 0.75wt.% and reaction time of 20min at 50°C. HC is compared to mechanical stirring (MS) at optimised values. The reaction rate constant and the frequency factor of HC were 3.4-fold shorter and 3.2-fold higher than MS. The interesterified product was characterised by following EN 14214 and ASTM D 6751 international standards.
Although a promising technique, phytoextraction has yet to see significant commercialization. Major limitations include metal uptake rates and subsequent processing costs. However, it has been shown that liquid-culture-grown Arabidopsis can take up and store palladium as nanoparticles. The processed plant biomass has catalytic activity comparable to that of commercially available catalysts, creating a product of higher value than extracted bulk metal. We demonstrate that the minimum level of palladium in Arabidopsis dried tissues for catalytic activity comparable to commercially available 3% palladium-on-carbon catalysts was achieved from dried plant biomass containing between 12 and 18 g·kg-1 Pd. To advance this technology, species suitable for in-the-field application: mustard, miscanthus, and 16 willow species and cultivars, were tested. These species were able to grow, and take up, palladium from both synthetic and mine-sourced tailings. Although levels of palladium accumulation in field-suitable species are below that required for commercially available 3% palladium-on-carbon catalysts, this study both sets the target, and is a step toward, the development of field-suitable species that concentrate catalytically active levels of palladium. Life cycle assessment on the phytomining approaches described here indicates that the use of plants to accumulate palladium for industrial applications has the potential to decrease the overall environmental impacts associated with extracting palladium using present-day mining processes.
Fibrous silica-titania (FST) catalysts were synthesized by microemulsion followed by silica seed-crystal crystallization methods under various molar ratios of toluene to water (T/W). The catalysts were characterized by XRD, UV-DRS, FESEM, TEM, AFM, N2 adsorption-desorption, FTIR, and ESR. The results revealed that altering the T/W ratio affected the growth of the silica and titania and led to different size, fiber density, silica-titania structure, and number of hydroxyl groups, as well as oxygen vacancies in the FSTs, which altered their behavior toward subsequent application. Photodegradation of ibuprofen (IBP) are in the following order: FST(6:1) (90%) > FST(5:1) (84%) > FST(7:1) (79%) > commercial TiO2 (67%). A kinetics study using Langmuir-Hinshelwood model illustrated that the photodegradation followed the pseudo-first-order and adsorption was the rate-limiting step. Optimization by response surface methodology (RSM) showed that the pH, initial concentration, and catalyst dosage were the remarkable parameters in photodegradation of IBP. The FST (6:1) maintained its photocatalytic activities for up to five cycles reaction without serious catalyst deactivation, and was also able to degrade other endocrine-disrupting chemicals, indicating its potential use for the treatment of those chemicals in wastewater.
Photocatalytic degradation is among the promising technology for removal of various dyes and organic contaminants from environment owing to its excellent catalytic activity, low energy utilization, and low cost. As one of potential photocatalysts, Fe2O3 has emerged as an important material for degradation of numerous dyes and organic contaminants caused by its tolerable band gap, wide harvesting of visible light, good stability and recyclability. The present review thoroughly summarized the classification, synthesis route of Fe2O3 with different morphologies, and several modifications of Fe2O3 for improved photocatalytic performance. These include the incorporation with supporting materials, formation of heterojunction with other semiconductor photocatalysts, as well as the fabrication of Z-scheme. Explicitly, the other photocatalytic applications of Fe2O3, including for removal of heavy metals, reduction of CO2, evolution of H2, and N2 fixation are also deliberately discussed to further highlight the huge potential of this catalyst. Moreover, the prospects and future challenges are also comprised to expose the unscrutinized criteria of Fe2O3 photocatalyst. This review aims to contribute a knowledge transfer for providing more information on the potential of Fe2O3 photocatalyst. In the meantime, it might give an idea for utilization of this photocatalyst in other environmental remediation application.
Recovery of chemicals and fuels from unrecyclable waste plastics at high temperatures (>800 °C) has received much research attention. Thermodynamic equilibrium calculation suggests that it is possible to perform the low-temperature steam reforming of polystyrene. In this study, we synthesized a Ni-Fe bimetallic catalyst for the low-temperature (500 °C) steam reforming of polystyrene. XRD characterization showed that Ni-Fe alloy was formed in the catalyst. Compared to conventional Ni catalysts, the Ni-Fe bimetallic catalysts can significantly increase the H2/CO ratio in the produced gas with high gas production yield. The online gas analysis revealed that H2, CO, and CO2 were formed in the same temperature range. H2 and CO were formed simultaneously through steam reforming reactions, and CO2 was formed through water-gas shift reaction. New morphologies of carbon deposition on the catalyst surface were found, suggesting that wax could be condensed on the catalyst surface at a low temperature.
Lipase-catalyzed production of palm esters was performed via alcoholysis of palm oil and oleyl alcohol in solvent and solvent-free systems using a 2 L stirred tank reactor (STR). Two immobilized lipases were tested and Lipozyme RM IM exhibited superior performance in both reaction systems. Reusability studies of the enzymes in a solvent-free system also demonstrated the high stability of Lipozyme RM IM as shown by its ability to yield more than 70% palm esters with up to 19 cycles of reusing the same enzymes. Modification of the enzyme washing process improved the stability of Lipozyme TL IM in a solvent system as demonstrated by maintaining 65% yield after 5 times of repeated enzyme use. The scale up process for both lipases was conducted in the presence of solvents by using the impeller tip speed approach. Lipozyme RM IM-catalyzed reaction in a 15 L STR produced 85.7% yield and there was a significant drop to 60.7% in the 300 L STR, whereas Lipozyme TL IM had a lower yield (65%) when the reaction volume was increased to 15 L. The low yields could be due to the accumulation of enzymes at the bottom of the vessel. Purification of palm esters via solvent-solvent extraction revealed that more than 90% of oleyl alcohol was extracted after the third extraction cycle at 150 rpm impeller speed with reduced palm esters: ethanol ratio (v/v) from 1:4 to 1:3.
A synergistic effect of the activated limestone-based catalyst (LBC) and microwave irradiation on the transesterification of waste cooking oil (WCO) was screened using a two-level factorial design and response surface methodology. The catalyst was prepared using a wet-impregnation method and was characterised for its surface element, surface morphology, surface area and porosity. The reaction was performed in a purpose-built continuous microwave assisted reactor (CMAR), while the conversion and yield of biodiesel were measured using a gas chromatography. The results showed that the catalyst loading, methanol to oil molar ratio and the reaction time significantly affect the WCO conversion. The optimum conversion of oil to biodiesel up to 96.65% was achieved at catalyst loading of 5.47 wt%, methanol to oil molar ratio of 12.21:1 and the reaction time of 55.26 min. The application of CMAR in this work reduced the transesterification time by about 77% compared to the reaction time needed for a conventional reactor. The biodiesel produced in this work met the specification of American Society for Testing and Materials (ASTM D6751). Engine test results shows the biodiesel has a lower NOx and particulate matters emissions compared to petrodiesel.
Fast pyrolysis is a potential technology for converting lignocellulosic biomass into bio-oil. Nevertheless, the high amounts of acid, oxygenated compounds, and water content diminish the energy density of the bio-oil and cause it to be unsuitable for direct usage. Catalytic fast pyrolysis (CFP) is able to improve bio-oil properties so that downstream upgrading processes can be economically feasible. Here, calcium oxide (CaO), magnesium oxide (MgO), and zinc oxide (ZnO) were employed due to their potential in enhancing bio-oil properties. The results showed that overall, all three catalysts positively impacted the empty fruit bunch fibre-derived bio-oil properties. Among the catalysts, CaO showed the most favorable effects in terms of reducing the acidity of the bio-oil and anhydrosugar. Thermal stability of bio-oils produced in the presence of CaO was studied as well.
Interest in biodiesel research has escalated over the years due to dwindling fossil fuel reserves. The implementation of a carbon-based solid acid catalyst in biodiesel production eradicates the separation problems associated with homogeneous catalysis. However, its application in the glycerol-free interesterification process for biodiesel production is still rarely being studied in the literature. In this study, novel environmentally benign catalysts were prepared from oil palm empty fruit bunch (OPEFB) derived activated carbon (AC) which is sustainable and low cost via direct sulfonation using concentrated sulfuric acid. The effects of synthesizing variables such as carbonization and sulfonation temperatures with different holding times towards the fatty acid methyl ester (FAME) yield in interesterification reaction with oleic acid and methyl acetate were investigated in detail. It was found that the optimum carbonization temperature and duration together with sulfonation temperature and duration were 600 °C, 3 h, 100 °C and 6 h, respectively. The catalyst possessed an amorphous structure with a high total acid density of 9.0 mmol NaOH g-1 due to the well-developed porous framework structure of the carbon support. Under these optimum conditions, the OPEFB derived solid acid catalyst recorded an excellent catalytic activity of 50.5% methyl oleate yield at 100 °C after 8 h with 50:1 methyl acetate to oleic acid molar ratio and 10 wt% catalyst dosage. The heterogeneous acid catalyst derived from OPEFB had shown promising properties that made them highly suitable for cost-effective and environmental-friendly glycerol-free biodiesel production.
Flower-like titanium dioxide (TiO2) nanostructures are successfully synthesized using a hybrid sol-gel and a simple hydrothermal method. The sample was characterized using various techniques to study their physicochemical properties and was tested as a photocatalyst for methyl orange degradation and as an antibacterial material. Raman spectrum and X-ray diffraction (XRD) pattern show that the phase structure of the synthesized TiO2 is anatase with 80-100 nm in diameter and 150-200 nm in length of flower-like nanostructures as proved by field emission scanning electron microscope (FESEM). The energy-dispersive X-ray spectroscopy (EDS) analysis of flower-like anatase TiO2 nanostructure found that only titanium and oxygen elements are present in the sample. The anatase phase was confirmed further by a high-resolution transmission electron microscope (HRTEM) and selected area electron diffraction (SAED) pattern analysis. The Brunauer-Emmett-Teller (BET) result shows that the sample had a large surface area (108.24 m2/g) and large band gap energy (3.26 eV) due to their nanosize. X-ray photoelectron spectroscopy (XPS) analysis revealed the formation of Ti4+ and Ti3+ species which could prevent the recombination of the photogenerated electron, thus increased the electron transportation and photocatalytic activity of flower-like anatase TiO2 nanostructure to degrade the methyl orange (83.03%) in a short time (60 minutes). These properties also support the good performance of flower-like titanium dioxide (TiO2) nanostructure as an antibacterial material which is comparable with penicillin which is 13.00 ± 0.02 mm inhibition zone against Staphylococcus aureus.