Even purified enzyme preparations are often heterogeneous. For example, preparations of aspartate aminotransferase or cytochrome oxidase can consist of several different forms of the enzyme. For this reason we consider how different the kinetics of the reactions catalysed by a mixture of forms of an enzyme must be to provide some indication of the characteristics of the species present. Based on the standard Michaelis-Menten model, we show that if the Michaelis constants (Km) of two isoforms differ by a factor of at least 20 the steady-state kinetics can be used to characterise the mixture. However, even if heterogeneity is reflected in the kinetic data, the proportions of the different forms of the enzyme cannot be estimated from the kinetic data alone. Consequently, the heterogeneity of enzyme preparations is rarely reflected in measurements of their steady-state kinetics unless the species present have significantly different kinetic properties. This has two implications: (1) it is difficult, but not impossible, to detect molecular heterogeneity using kinetic data and (2) even when it is possible, a considerable quantity of high quality data is required.
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.
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.
Gums; composed of polysaccharides, carbohydrates, proteins, and minerals, are high molecular weight hydrophilic compounds with several biological applications. This study describes the nutritional and toxic elements content, chemical composition, synthesis of silver nanoparticles (G-AgNPs), and pharmacological and catalytic properties of Prunus armeniaca (apricot), Prunus domestica (plums), Prunus persica (peaches), Acacia modesta (phulai), Acacia arabica (kikar), and Salmalia malabarica (silk cotton tree) gums. The elemental contents were analyzed by inductively coupled plasma-optical emission spectroscopy (ICP-OES) and ICP-mass spectrometry (ICP-MS). NMR spectroscopy was used for the identification of class of compounds in the mixture, their functional groups were determined through FTIR techniques, and plasmon resonance and size of G-AgNPs through UV-Vis spectroscopic technique and transmission electron microscopy (TEM). From the results, nutritional elements were present at appreciable concentrations, whereas toxic elements showed content below the maximum permissible ranges. Using the elemental data, linear discriminant and principal component analyses classified the gums to 99.9% variability index. Furthermore, G-AgNPs exhibited significant antioxidant, antibacterial, and redox catalytic potential. Hence, the subject G-AgNPs could have promising nutritional, therapeutic and environmental remediation applications.
In this study, the photocatalytic degradation of batik wastewater in the presence of zinc oxide (ZnO) as photocatalyst was
investigated. The effect of various operating parameters, such as pH of batik wastewater, catalyst dosage and aeration
on the photocatalytic degradation process, was examined. The mineralization of batik wastewater was also evaluated
through chemical oxygen demand analysis. The decolorization of batik wastewater was enhanced at acidic conditions
(pH3) which was 88.2% after 10 h irradiated under solar light, meanwhile its mineralization was 286 mg/L after 12 h
irradiation time. The data obtained for photocatalytic degradation of batik wastewater was well fitted with the LangmuirHinshelwood
kinetic model. It can be concluded that batik wastewater could be decolorized and mineralized under solar
light irradiation with presence of ZnO.
A hybrid biofuel cell, a zinc-air cell employing laccase as the oxygen reduction catalyst is investigated. A simple cell design is employed; a membraneless single chamber and a freely suspended laccase in the buffer electrolyte. The cell is characterised based on its open-circuit voltage, power density profile and galvanostatic discharge at 0.5 mA. The activity of laccase as an oxidoreductase is substantiated from the cell discharge profiles. The use of air electrode in the cell design enhanced the energy output by 14%. The zinc-air biofuel cell registered an open-circuit voltage of 1.2 V and is capable to deliver a maximum power density of 1.1 mWcm-2 at 0.4 V. Despite its simple design features, the power output is comparable to that of biocatalytic cell utilising a much more complex system design.
Catalytic co-pyrolysis (CCP) of spent coffee ground (SCG) and cellulose over HZSM-5 and HY was characterized thermogravimetrically, and a catalytic pyrolysis of two samples was conducted using a tandem micro reactor that directly connected with gas chromatography-mass spectrometry. To access the more fundamental investigations on CCP, the effects of the zeolite pore structure, reaction temperature, in-situ/ex-situ reaction mode, catalyst to feedstock ratio, and the SCG and cellulose mixing ratio were experimentally evaluated. The temperature showing the highest thermal degradation rate of cellulose with SCG slightly delayed due to the interactions during the thermolysis of two samples. HZSM-5 in reference to HY produced more aromatic hydrocarbons from CCP. With respect to the reaction temperature, the formation of aromatic hydrocarbons increased with the pyrolytic temperature. Moreover, the in-situ/ex-situ reaction mode, catalyst/feedstock, and cellulose/SCG ratio were optimized to improve the aromatic hydrocarbon yield.
The synthesis of high quality graphene via economic way is highly desirable for practical applications. In this study, graphene flake was successfully synthesized on Cu/MgO catalyst derived from recovered Cu via etching in ammonium persulfate solution. Recovered Cu acted as efficient active metal in Cu/MgO catalyst with good crystal structure and composition according to XRD and XRF results. FESEM, EDX, HRTEM, Raman spectroscopy and SAED analysis were carried out on the synthesized graphene. The formation of single, bilayer and few layer of graphene from Cu/MgO catalyst derived from recovered Cu was feasible.
The global economy is threatened by the depletion of fossil resources and fluctuations in fossil fuel prices, and thus it is necessary to exploit sustainable energy sources. Carbon-neutral fuels including bio-oil obtained from biomass pyrolysis can act as alternatives to fossil fuels. Co-pyrolysis of lignocellulosic biomass and plastic is efficient to upgrade the quality of bio-oil because plastic facilitates deoxygenation. However, catalysts are required to produce bio-oil that is suitable for potential use as transportation fuel. This review presents an overview of recent advances in catalytic co-pyrolysis of biomass and plastic from the perspective of chemistry, catalyst, and feedstock pretreatment. Additionally, this review introduces not only recent research results of acid catalysts for catalytic co-pyrolysis, but also recent approaches that utilize base catalysts. Future research directions are suggested for commercially feasible co-pyrolysis process.
: Hydrogen (H2) is a clean energy carrier which can help to solve environmental issues with the depletion of fossil fuels. Sodium borohydride (NaBH4) is a promising candidate material for solid state hydrogen storage due to its huge hydrogen storage capacity and nontoxicity. However, the hydrolysis of NaBH4 usually requires expensive noble metal catalysts for a high H2 generation rate (HGR). Here, we synthesized high-aspect ratio copper nanowires (CuNWs) using a hydrothermal method and used them as the catalyst for the hydrolysis of NaBH4 to produce H2. The catalytic H2 generation demonstrated that 0.1 ng of CuNWs could achieve the highest volume of H2 gas in 240 min. The as-prepared CuNWs exhibited remarkable catalytic performance: the HGR of this study (2.7 × 1010 mL min-1 g-1) is ~3.27 × 107 times higher than a previous study on a Cu-based catalyst. Furthermore, a low activation energy (Ea) of 42.48 kJ mol-1 was calculated. Next, the retreated CuNWs showed an outstanding and stable performance for five consecutive cycles. Moreover, consistent catalytic activity was observed when the same CuNWs strip was used for four consecutive weeks. Based on the results obtained, we have shown that CuNWs can be a plausible candidate for the replacement of a costly catalyst for H2 generation.
In this study, solid coconut waste and CaO/PVA was used as raw material and catalyst respectively to produce biodiesel through in situ transesterification. Both, raw material and catalyst were packed in a packed bed reactor. The reaction was fixed for 3 h and the mixing was kept constant at 350 rpm. The highest biodiesel yield of 95% was obtained at reaction temperature of 61 °C with catalyst loading (CaO/PVA) of 2.29 wt% and methanol to solid ratio of 12:1. CaO-waste derived catalyst has been successfully proven to be utilized as heterogeneous base catalyst for the production of biodiesel from solid coconut waste.
Nanostructured photocatalysts commonly offered opportunities to solve issues scrutinized with the environmental challenges caused by steep population growth and rapid urbanization. This photocatalyst is a controllable characteristic, which can provide humans with a clean and sustainable ecosystem. Over the last decades, one of the current thriving research focuses on visible-light-driven CeO2-based photocatalysts due to their superior characteristics, including unique fluorite-type structure, rigid framework, and facile reducing oxidizing properties of cerium's tetravalent (Ce4+) and trivalent (Ce3+) valence states. Notwithstanding, owing to its inherent wide energy gap, the solar energy utilization efficiency is low, which limits its application in wastewater treatment. Numerous modifications of CeO2 have been employed to enhance photodegradation performances, such as metals and non-metals doping, adding support materials, and coupling with another semiconductor. Besides, all these doping will form a different heterojunction and show a different way of electron-hole migration. Compared to conventional heterojunction, advanced heterojunction types such as p-n heterojunction, Z-scheme, Schottky junction, and surface plasmon resonance effect exhibit superior performance for degradation owing to their excellent charge carrier separation, and the reaction occurs at a relatively higher redox potential. This review attends to providing deep insights on heterojunction mechanisms and the latest progress on photodegradation of various contaminants in wastewater using CeO2-based photocatalysts. Hence, making the CeO2 photocatalyst more foresee and promising to further development and research.
Recently, hetero junction materials (p-n-p and n-p-n) have been developed for uplifting the visible light activity to destroy the harmful pollutants in wastewater. This manuscript presents a vivid description of novel n-p-n junction materials namely CeO2-PPy-ZnO. This novel n-p-n junction was applied as the photocatalyst in drifting the mobility of charge carriers and hence obtaining the better photocatalytic activity when compared with p-n and pure system. Such catalyst's syntheses were successful via the copolymerization method. The structural, morphological and optical characterization techniques were applied to identify the physio-chemical properties of the prepared materials. Additionally, the superior performance of this n-p-n nanostructured material was demonstrated in the destruction of micro organic (chlorophenol) toxic wastes under visible light. The accomplished ability of the prepared catalysts (up to 92% degradation of chlorophenol after 180 min of irradiation) and their profound degradation mechanism was explained in detail.
Industrial wastewaters contain hazardous contaminants that pollute the environment and cause socioeconomic problems, thus demanding the employment of effective remediation procedures such as photocatalysis. Zinc oxide (ZnO) nanomaterials have emerged to be a promising photocatalyst for the removal of pollutants in wastewater owing to their excellent and attractive characteristics. The dynamic tunable features of ZnO allow a wide range of functionalization for enhanced photocatalytic efficiency. The current review summarizes the recent advances in the fabrication, modification, and industrial application of ZnO photocatalyst based on the analysis of the latest studies, including the following aspects: (1) overview on the properties, structures, and features of ZnO, (2) employment of dopants, heterojunction, and immobilization techniques for improved photodegradation performance, (3) applicability of suspended and immobilized photocatalytic systems, (4) application of ZnO hybrids for the removal of various types of hazardous pollutants from different wastewater sources in industries, and (5) potential of bio-inspired ZnO hybrid nanomaterials for photocatalytic applications using renewable and biodegradable resources for greener photocatalytic technologies. In addition, the knowledge gap in this field of work is also highlighted.
The present work investigates the proficiency of green silver oxide nanocatalyst synthesised from Monotheca buxifolia (Falc.) Dcne. leaves extract, and their application for biodiesel synthesis from novel Prunus bokhariensis seed oil (non-edible). The seed oil content of 55% and FFA content of 0.80 mg KOH/g were reported. Several analytical tools (EDX, FT-IR, SEM and XRD) were used to characterise the Ag2O nanocatalyst. Maximum (89%) FAME yield of the PBSOB (Prunus bokhariensis seed oil biodiesel) was achieved at ambient transesterification conditions i.e. 3.5 wt% nanocatalyst loading, 2.5 h reaction time, 130 °C of reaction temperature and 12:1 alcohol to oil ratio. The synthesised PBSOB was additionally characterised by analytical methods like, GC-MS and FT-IR. The different aspects of fuel were identified i.e. flash point (84 °C), kinematic viscosity (4.01 cSt @ 40 °C), sulphur content (0.0003 wt %), density (0.853 kg/L) and acid number (0.167 mg KOH/g). All the above properties were verified and agreed well with biodiesel international standards (European Union (14214), China GB/T (20828) and ASTM (6751, 951). In general, Prunus bokhariensis seed oil and Ag2O nanocatalyst seem to be remarkably active, cheap and stable candidates for the biodiesel industry in future.
The present work demonstrates the coupling of titanium dioxide, TiO2 nanoparticles (TNP) with N-doped, Bi-doped, and N-Bi co-doped rice husk-derived carbon dots (CDs) via a facile dispersion method, forming respective photocatalyst composites of CDs/TNP, N-CDs/TNP, Bi-CDs/TNP and N-Bi-CDs/TNP. Characterization analyzes verified the successful incorporation of respective CDs samples into TNP, forming photocatalyst composite with narrowed band gap and quenched photoluminescence intensity. Photocatalytic activity of TNP and the respective composites was investigated for photodegradation of diclofenac (DCF) under both simulated sunlight and natural sunlight irradiation. The as-prepared N-Bi-CDs/TNP composite showed the best photocatalytic performance among all composites, able to completely degrade 5 ppm of DCF within 60 min and 180 min under both types of visible light irradiation, respectively. The N-Bi-CDs/TNP composite also showed a TOC removal efficiency up to 87.63%. N-Bi-CDs, worked as photosensitizer and electron reservoir, contributed to the outstanding photocatalytic activity of N-Bi-CDs/TNP, whereby the recombination was prolonged and light absorption was shifted towards the visible light region. Furthermore, the composite of N-Bi-CDs/TNP also demonstrated good stability and reusability over repeated degradation cycles. The photodegradation of DCF resulted into several intermediates, which were identified from LC-MS analysis. The present work could provide an insight on the application of heteroatoms doped and co-doped carbon dots in semiconductor oxide as high performance photocatalysts.
The fatty acid methyl ester (FAME) production from dairy effluent scum as a sustainable energy source using CaO obtained from organic ash over titanium dioxide nanoparticles (TNPs) as the transesterification nano-catalyst has been studied. The physical and chemical properties of the synthesized catalysts were characterized, and the effect of different experimental factors on the biodiesel yield was studied. It was revealed that the CaO-TiO2 nano-catalyst displayed bifunctional properties, has both basic and acid phases, and leads to various effects on the catalyst activity in the transesterification process. These bifunctional properties are critical for achieving simultaneous transesterification of dairy scum oil feedstock. According to the reaction results, the catalyst without and with a low ratio of TNPs showed a low catalytic activity. In contrast, the 3Ca-3Ti nano-catalyst had the highest catalytic activity and a strong potential for reusability, producing a maximum biodiesel yield of 97.2% for a 3 wt% catalyst, 1:20 oil to methanol molar ratio for the dairy scum, and a reaction temperature of 70 °C for a period of 120 min under a 300 kPa pressure. The physical properties of the produced biodiesel are within the EN14214 standards.
Recently, rubber seed oil (RSO) has been considered as a promising potential oil source for biodiesel production. However, RSO is a non-edible feedstock with a significant high free fatty acid (FFA) content which has an adverse impact on the process of biodiesel production. In this study, ultrasonic-assisted esterification process was conducted as a pre-treatment step to reduce the high FFA content of RSO from 40.14% to 0.75%. Response surface methodology (RSM) using central composite design (CCD) was applied to the design of experiments (DOE) and the optimization of esterification process. The result showed that methanol to oil molar ratio was the most influential factor for FFA reduction whereas the effect of amount of catalyst and the reaction were both insignificant. The kinetic study revealed that the activation energy and the frequency factor of the process are 52.577kJ/mol and 3.53×108min-1, respectively.
The industrial discharge of dye pollutant contaminated wastewater is the major cause of water and soil pollution. Photocatalysis is a promising and green remediation technology, which has received widespread attention in the remediation of hazardous dyes from aqueous environment and convert them into harmless compounds. Herein, we report the synthesis of chitosan (CS) functionalized bismuth oxychloride/zinc oxide (BiOCl/ZnO) nanocomposite by a modified hydrothermal route. The physiochemical characterization revealed that the synthesized nanocomposite have crystalline, agglomerated spherical along with rod shaped morphology and size range from 35 to 160 nm. FTIR peaks at 825, 727, 662 and 622 cm-1 specified the presence of BiO and ZnO bonds, whereas peak at 1635 cm-1 revealed the existence of amine groups which confirms the presence of CS in the synthesized CS-BiOCl/ZnO nanocomposite. Catalytic property of synthesized nanocomposite was evaluated by the degradation of Congo red (CR) under UV-light irradiation. CR dye degradation percentage was found to be 93 % within a short period of 40 min by utilizing UV-light. Furthermore, reusability of CS-BiOCl/ZnO photocatalyst was also investigated, and it remained significant photocatalytic activity after three consecutive cycles. Hence, the results obtained in this study revealed that CS-BiOCl/ZnO nanocomposite can be used as a potential photocatalyst to remediate organic pollutants in various industries.
Nickel-impregnated TiO2 photocatalyst (NiTP) responding to visible light was prepared by the liquid phase plasma (LPP) method, and its photoactivity was evaluated in degrading an antibiotic (oxytetracycline, OTC). For preparing the photocatalyst, nickel was uniformly impregnated onto TiO2 (P-25) powder, and the nickel content increased as the number of LPP reactions increased. In addition, the morphology and lattice of NiTP were observed through various instrumental analyses, and it was confirmed that NiO-type nanoparticles were impregnated in NiTP. Fundamentally, as the amount of impregnated nickel in the TiO2 powder increased sufficiently, the band gap energy of TiO2 decreased, and eventually, the NiTP excited by visible light was synthesized. Further, OTC had a decomposition reaction pathway in which active radicals generated in OTC photocatalytic reaction under NiTP were finally mineralized through reactions such as decarboxamidation, hydration, deamination, demethylation, and dehydroxylation. In effect, we succeeded in synthesizing a photocatalyst useable under visible light by performing only the LPP single process and developed a new advanced oxidation process (AOP) that can remove toxic antibiotics.