The textile industry consumes a large volume of organic dyes and water. These organic dyes, which remained in the effluents, are usually persistent and difficult to degrade by conventional wastewater treatment techniques. If the wastewater is not treated properly and is discharged into water system, it will cause environmental pollution and risk to living organisms. To mitigate these impacts, the photo-driven catalysis process using semiconductor materials emerges as a promising approach. The semiconductor photocatalysts are able to remove the organic effluent through their mineralization and decolorization abilities. Besides the commonly used titanium dioxide (TiO2), manganese dioxide (MnO2) is a potential photocatalyst for wastewater treatment. MnO2 has a narrow bandgap energy of 1~2 eV. Thus, it possesses high possibility to be driven by visible light and infrared light for dye degradation. This paper reviews the MnO2-based photocatalysts in various aspects, including its fundamental and photocatalytic mechanisms, recent progress in the synthesis of MnO2 nanostructures in particle forms and on supporting systems, and regeneration of photocatalysts for repeated use. In addition, the effect of various factors that could affect the photocatalytic performance of MnO2 nanostructures are discussed, followed by the future prospects of the development of this semiconductor photocatalysts towards commercialization.
Sequentially precipitated Mg-promoted nickel-silica catalysts with ageing performed under various ultrasonic intensities were employed to study the catalyst performance in the partial hydrogenation of sunflower oil. Results from various characterisation studies showed that increasing ultrasonic intensity caused a higher degree of hydroxycarbonate erosion and suppressed the formation of Ni silicates and silica support, which improved Ni dispersion, BET surface area and catalyst reducibility. Growth of silica clusters on the catalyst aggregates were observed in the absence of ultrasonication, which explained the higher silica and nickel silicate content on the outer surface of the catalyst particle. Application of ultrasound also altered the electron density of the Ni species, which led to higher activity and enhanced product selectivity for sonicated catalysts. The catalyst synthesised with ultrasonic intensity of 20.78 Wcm-2 achieved 22.6% increase in hydrogenation activity, along with 28.5% decrease in trans-C18:1 yield at IV = 70, thus supporting the feasibility of such technique.
A unidirectional flow solar photocatalytic fuel cell (PFC) was successfully developed for the first time to offer alternative for electricity generation and simultaneous wastewater treatment. This study was focused on the synthesis of α-, δ- and β-MnO2 by wet chemical hydrothermal method for application as the cathodic catalyst in PFC. The crystallographic evolution was performed by varying the ratios of KMnO4 to MnSO4. The mechanism of the PFC with the MnO2/C as cathode was also discussed. Results showed that the catalytic activity of MnO2/C cathode was mainly predominated by their crystallographic structures which included Mn-O bond strength and tunnel size, following order of α- > δ- > β-MnO2/C. Interestingly, it was discovered that the specific surface areas (SBET) of different crystal phases did not give an impact on the PFC performance. However, the Pmax could be significantly influenced by the micropore surface area (Smicro) in the comparison among α-MnO2. Furthermore, the morphological transformation carried out by altering the hydrothermal duration demonstrated that the nanowire α-M3(24 h)/C with 1:1 ratio of KMnO4 and MnSO4 yielded excellent PFC performance with a Pmax of 2.8680 μW cm-2 and the lowest Rint of 700 Ω.
This paper remarks the general correlations of the shape and crystallinity of titanium dioxide (TiO₂) support on gold deposition and carbon monoxide (CO) oxidation. It was found that due to the larger rutile TiO₂ particles and thus the pore volume, the deposited gold particles tended to agglomerate, resulting in smaller catalyst surface area and limited gold loading, whilst anatase TiO₂ enabled better gold deposition. Those properties directly related to gold particle size and thus the number of low coordinated atoms play dominant roles in enhancing CO oxidation activity. Gold deposited on anatase spheroidal TiO₂ at photo-deposition wavelength of 410 nm for 5 min resulted in the highest CO oxidation activity of 0.0617 mmol CO/s.gAu (89.5% conversion) due to the comparatively highest catalyst surface area (114.4 m²/g), smallest gold particle size (2.8 nm), highest gold loading (7.2%), and highest Au⁰ content (68 mg/g catalyst). CO oxidation activity was also found to be directly proportional to the Au⁰ content. Based on diffuse reflectance infrared Fourier transform spectroscopy, we postulate that anatase TiO₂-supported Au undergoes rapid direct oxidation whilst CO oxidation on rutile TiO₂-supported Au could be inhibited by co-adsorption of oxygen.
Recently, the discharge of flue gas has become a global issue due to the rapid development in industrial and anthropogenic activities. Various dry and wet treatment approaches including conventional and hybrid hybrid wet scrubbing have been employing to combat against these toxic exhaust emissions. However, certain issues i.e., large energy consumption, generation of secondary pollutants, low regeneration of scrubbing liquid and high efficieny are hindering their practical applications on industrial level. Despite this, the hybrid wet scrubbing technique (advanced oxidation, ionic-liquids and solid engineered interface hybrid materials based techniques) is gaining great attention because of its low installation costs, simultaneous removal of multi-air pollutants and low energy requirements. However, the lack of understanding about the basic principles and fundamental requirements are great hurdles for its commercial scale application, which is aim of this review article. This review article highlights the recent developments, minimization of GHG, sustainable improvements for the regeneration of used catalyst via green and electron rich donors. It explains, various hybrid wet scrubbing techniques can perform well under mild condition with possible improvements such as development of stable, heterogeneous catalysts, fast and in-situ regeneration for large scale applications. Finally, it discussed recovery of resources i.e., N2O, NH3 and N2, the key challenges about several competitive side products and loss of catalytic activity over time to treat toxic gases via feasible solutions by hybrid wet scrubbing techniques.
The performance of Cu/TiO2/FA composite, a hybrid adsorbent-photocatalyst consisting of copper-doped titania particles supported on fly ash, was optimized, under visible light irradiation, for the removal of the model dye pollutant methyl orange (MO) by using a response surface methodology and Box-Behnken experimental design. Three independent variables were considered for the optimization study: catalyst/solvent dosage (0.5 - 2.0 g/L), irradiation time (30-120 min), and the initial concentration (5- 25 ppm) of the dye. A 99.91% rate of removal was achieved using 2 g/L dosage, 5 ppm initial concentration, and 100 min of irradiation time as the optimal operating conditions. The recorded trends support the hypothesis of a combined and synergic adsorption-photocatalytic degradation process which fully exploits the "capture and destroy" approach for pollutant removal.
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.
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 first enantioselective synthesis of (-)-conolutinine was achieved in 10 steps. The synthesis featured a catalytic asymmetric bromocyclization of tryptamine to forge the tricycle intermediate. Hydration of an alkene catalyzed by Co(acac)2 was also employed as a key step to diastereoselectively introduce the tertiary alcohol moiety. The absolute configuration of (-)-conolutinine was established to be (2S,5aS,8aS,13aR) based on this asymmetric total synthesis.
Quasi-homogeneous ligand-protected gold nanoclusters (Au NCs) with atomic precision and well-defined structure offer great opportunity for exploring the catalytic nature of nanogold catalysts at a molecular level. Herein, using real-time electrospray ionization mass spectrometry (ESI-MS), we have successfully identified the desorption and re-adsorption of p-mercaptobenzoic acid (p-MBA) ligands from Au25(p-MBA)18 NC catalysts during the hydrogenation of 4-nitrophenol in solution. This ligand dynamic (desorption and re-adsorption) would initiate structural transformation of Au25(p-MBA)18 NC catalysts during the reaction, forming a mixture of smaller Au NCs (Au23(p-MBA)16 as the major species) at the beginning of catalytic reaction, which could further be transformed into larger Au NCs (Au26(p-MBA)19 as the major species). The adsorption of hydrides (from NaBH4) is identified as the determining factor that could induce the ligand dynamic and structural transformation of NC catalysts. This study provides fundamental insights into the catalytic nature of Au NCs, including catalytic mechanism, active species and stability of Au NC catalysts during a catalytic reaction.
In this research, biomass from oil palm empty fruit bunch was used as the carbon precursor and sulfonated by 4-benzenediazonium sulfonate (4-BDS) to produce solid acid catalyst. The as-synthesized catalysts were characterized and the performances were tested in esterification of palm fatty acid distillate (PFAD) for biodiesel production. Scanning Electron Microscopy (SEM) showed that clear porous and rough carbon surface was successfully developed after calcination which favored the attachment of sulfonic groups. Thermogravimetric Analysis (TGA) result showed that the catalyst was thermally stable up to 600 °C. Fourier Transform Infrared Spectroscopy (FTIR) proved that SO and SO3H sulfonic groups were successfully attached to the carbon catalyst. From the catalytic activity tests, the results showed that the catalyst which was calcined at 200 °C and sulfonated with 15:1 sulfanilic acid to AC ratio was the optimum catalyst as it provided the highest biodiesel yield. Further investigation showed that the reaction time of 7 h and 20 wt.% of catalyst loading were reported as optimum esterification conditions which provided the highest biodiesel yield at 98.1 %.
5-Hydroxymethylfurfural (HMF) has been identified as a promising biomass-derived platform chemical. In this study, one pot production of HMF was studied in ionic liquid (IL) under probe sonication technique. Compared with the conventional heating technique, the use of probe ultrasonic irradiation reduced the reaction time from hours to minutes. Glucose, cellulose and local bamboo, treated with ultrasonic, produced HMF in the yields of 43%, 31% and 13% respectively, within less than 10min. The influence of various parameters such as acoustic power, reaction time, catalysts and glucose loading were studied. About 40% HMF yield at glucose conversion above 90% could be obtained with 2% of catalyst in 3min. Negligible amount of soluble by-product was detected, and humin formation could be controlled by adjusting the different process parameters. Upon extraction of HMF, the mixture of ionic liquid and catalyst could be reused and exhibited no significant reduction of HMF yield over five successive runs. The purity of regenerated [C4C1im]Cl and HMF was confirmed by NMR spectroscopy, indicating neither changes in the chemical structure nor presence of any major contaminants during the conversion under ultrasonic treatment. 13C NMR suggests that [C4C1im]Cl/CrCl3 catalyses mutarotation of α-glucopyranose to β-glucopyranose leading to isomerization and finally conversion to HMF. The experimental results demonstrate that the use of probe sonication technique for conversion to HMF provides a positive process benefit.
The solubility limitations of phenolic acids in many lipidic environments are now greatly improved by their enzymatic esterification in ionic liquids (ILs). Herein, four different ILs were tested for the esterification of dihydrocaffeic acid with hexanol and the best IL was selected for the synthesis of four other n-alkyl esters with different chain-lengths. The effect of alkyl chain length on the anti-oxidative properties of the resulted purified esters was investigated using β-carotene bleaching (BCB) and free radical scavenging method DPPH and compared with butylated hydroxytoluene (BHT) as reference compound. All four esters (methyl, hexyl, dodecyl and octadecyl dihydrocaffeates) exhibited relatively strong radical scavenging abilities. The scavenging activity of the test compounds was in the following order: methyl ester>hexyl ester⩾dodecyl ester>octadecyl ester>BHT while the order for the BCB anti-oxidative activity was; BHT>octadecyl ester>dodecyl ester>hexyl ester>methyl ester.
Oligostilbenoids are polyphenols that are widely distributed in nature with multifaceted biological activities. To achieve biomimetic synthesis of unnatural derivatives, we subjected three resveratrol analogues to oligomerization by means of one-electron oxidants. Upon varying the metal oxidant (AgOAc, CuBr(2), FeCl(3)6 H(2)O, FeCl(3)6 H(2)O/NaI, PbO(2), VOF(3)), the solvent (over the whole range of polarities), and the oxygenated substitution pattern of the starting material, stilbenoid oligomers with totally different carbon skeletons were obtained. Here we propose to explain the determinism of the type of skeleton produced with the aid of hard and soft acid/base concepts in conjunction with the solvating properties of the solvents and the preferred alignment by the effect of pi stacking.
The synthesis of kojic acid derivative (KAD) from kojic and palmitic acid (C16:0) in the presence of immobilized lipase from Rhizomucor miehei (commercially known as Lipozyme RMIM), was studied using a shake flask system. Kojic acid is a polyfunctional heterocycles that acts as a source of nucleophile in this reaction allowing the formation of a lipophilic KAD. In this study, the source of biocatalyst, Lipozyme RMIM, was derived from the lipase of Rhizomucor miehei immobilized on weak anion exchange macro-porous Duolite ES 562 by the adsorption technique. The effects of solvents, enzyme loading, reaction temperature, and substrate molar ratio on the reaction rate were investigated. In one-factor-at-a-time (OFAT) experiments, a high reaction rate (30.6 × 10-3 M·min-1) of KAD synthesis was recorded using acetone, enzyme loading of 1.25% (w/v), reaction time of 12 h, temperature of 50 °C and substrate molar ratio of 5:1. Thereafter, a yield of KAD synthesis was optimized via the response surface methodology (RSM) whereby the optimized molar ratio (fatty acid: kojic acid), enzyme loading, reaction temperature and reaction time were 6.74, 1.97% (w/v), 45.9 °C, and 20 h respectively, giving a high yield of KAD (64.47%). This condition was reevaluated in a 0.5 L stirred tank reactor (STR) where the agitation effects of two impellers; Rushton turbine (RT) and pitch-blade turbine (PBT), were investigated. In the STR, a very high yield of KAD synthesis (84.12%) was achieved using RT at 250 rpm, which was higher than the shake flask, thus indicating better mixing quality in STR. In a rheological study, a pseudoplastic behavior of KAD mixture was proposed for potential application in lotion formulation.
Conjugated linoleic acid (CLA)-rich triacylglycerols (TAG) have received significant attention owing to their health promoting properties. In this study, CLA-rich TAG were successfully synthesized by an immobilized mutant lipase (MAS1-H108A)-catalyzed esterification of CLA-rich fatty acids and glycerol under vacuum. MAS1-H108A was first immobilized onto ECR1030 resin. Results showed that the lipase/support ratio of 41 mg/g was suitable for the immobilization and the thermostability of immobilized MAS1-H108A was greatly enhanced. Subsequently, the immobilized MAS1-H108A was employed for the synthesis of CLA-rich TAG and 95.21% TAG with 69.19% CLA was obtained under the optimized conditions. The TAG content (95.21%) obtained by immobilized MAS1-H108A is the reported highest value thus far, which was significantly higher than that (9.26%) obtained by Novozym 435 under the same conditions. Although the TAG content comparable to the results obtained in this study could also be obtained by Novozym 435, the used enzyme amount is approximately 5-fold of the immobilized MAS1-H108A. Additionally, the immobilized MAS1-H108A exhibited excellent recyclability during esterification retaining 95.11% of its initial activity after 10 batches. Overall, such immobilized mutant lipase with superior esterification activity and recyclability has the potential to be used in oils and fats industry.
LML-type structured lipids are one type of medium- and long-chain triacylglycerols. LML was synthesized using immobilized Talaromyces thermophilus lipase (TTL)-catalyzed interesterification of tricaprylin and ethyl linoleate. The resin AB-8 was chosen, and the lipase/support ratio was determined to be 60 mg/g. Subsequently, the immobilized TTL with strict sn-1,3 regiospecificity was applied to synthesize LML. Under the optimized conditions (60 °C, reaction time 6 h, enzyme loading of 6% of the total weight of substrates, substrate of molar ratio of ethyl linoleate to tricaprylin of 6:1), Triacylglycerols with two long- and one medium-chain FAs (DL-TAG) content as high as 52.86 mol% was obtained. Scale-up reaction further verified the industrial potential of the established process. The final product contained 85.24 mol% DL-TAG of which 97 mol% was LML after purification. The final product obtained with the high LML content would have substantial potential to be used as functional oils.
Recycling waste cooking vegetable oils by reclaiming and using these oils as biodiesel feedstocks is one of the promising solutions to address global energy demands. However, producing these biodiesels poses a significant challenge because of their poor physicochemical properties due the high free fatty acid content and impurities present in the feedstock, which will reduce the biodiesel yields. Hence, this study implemented the following strategy in order to address this issue: (1) 70 vol% of waste cooking vegetable oil blended with 30 vol% of Calophyllum inophyllum oil named as WC70CI30 used to alter its properties, (2) a three-stage process (degumming, esterification, and transesterification) was conducted which reduces the free fatty acid content and presence of impurities, and (3) the transesterification process parameters (methanol/oil ratio, reaction temperature, reaction time, and catalyst concentration) were optimized using response surface methodology in order to increase the biodiesel conversion yield. The results show that the WC70CI30 biodiesel has favourable physicochemical properties, good cold flow properties, and high oxidation stability (22.4 h), which fulfil the fuel specifications stated in the ASTM D6751 and EN 14214 standards. It found that the WC70CI30 biodiesel has great potential as a diesel substitute without the need for antioxidants and pour point depressants.
The continuous growth of population and the steady improvement of people's living standards have accelerated the generation of massive food waste. Untreated food waste has great potential to harm the environment and human health due to bad odor release, bacterial leaching, and virus transmission. However, the application of traditional disposal techniques like composting, landfilling, animal feeding, and anaerobic digestion are difficult to ease the environmental burdens because of problems such as large land occupation, virus transmission, hazardous gas emissions, and poor efficiency. Pyrolysis is a practical and promising route to reduce the environmental burden by converting food waste into bioenergy. This paper aims to analyze the characteristics of food waste, introduce the production of biofuels from conventional and advanced pyrolysis of food waste, and provide a basis for scientific disposal and sustainable management of food waste. The review shows that co-pyrolysis and catalytic pyrolysis significantly impact the pyrolysis process and product characteristics. The addition of tire waste promotes the synthesis of hydrocarbons and inhibits the formation of oxygenated compounds efficiently. The application of calcium oxide (CaO) exhibits good performance in the increment of bio-oil yield and hydrocarbon content. Based on this literature review, pyrolysis can be considered as the optimal technique for dealing with food waste and producing valuable products.
Demand for diesel continues to increase due to rapid population growth, which could contribute to fossil fuel exhaustion. Biodiesel has been widely developed as a replacement for conventional diesel to resolve the issue. Biodiesel production from waste cooking oil (WCO) was carried out via the transesterification process using two types of bentonite catalysts, which are raw bentonite and NaOH/bentonite. By using the impregnation method, the NaOH/bentonite catalyst was synthesized at 60°C for 12 hours. The transesterification was conducted with 0.5wt% of catalyst, at 15:1 (methanol- to-oil), for 2 hours at different reaction temperatures. The characterization of both raw bentonite and NaOH/bentonite was done using X-ray Diffraction (XRD) and Brunauer, Emmett, Teller (BET) surface characterization. A high yield of FAMEs (72%) was found to be obtained in continuous stirring at 55ºC for 2 hours and 15:1 methanol/oil molar ratio with 0.5wt.% (0.15g) of NaOH/bentonite catalyst.