Kinetic Studies Research Articles

Amino-functionalization of PVA/TiO2-CeO2 nanohybrid adsorbent for the removal of selenium ions from aqueous solutions: Equilibrium and kinetics studies

ABSTRACT In this study, a hybrid nanoadsorbent (HnA), (PVA/TiO2-CeO2), was synthesized and amino-functionalized by 3-aminopropyltriethoxysilane (APTES) to produce AHnA, for use in an advanced selenium adsorption study focusing on nonlinear equilibrium and kinetics models. AHnA was characterized using XRD, FTIR spectroscopy, SEM, and EDX elemental analyses, as well as BET-BJH techniques. According to the FTIR results, APTES has successfully cross-linked the PVA chain and introduced amine groups on the surface. Moreover, the modification resulted in an increase in the total pore volume from 0.0061 cm3/g in HnA to 0.021 cm3/g in AHnA. Several adsorption experiments were conducted to determine the impact of varying contact times within a pH range of 1 to 8 and concentrations ranging from 5 to 200 mg/L, using a One-Variable-At-a-Time (OVAT) procedure. Accordingly, a dosage of 2 g/L of modified nanocomposite exhibits optimal performance for removing selenium from a 20 mg/L solution at an acidic pH of 3 during 300 minutes of contact with selenium ions, while conforming to a pseudo-second-order kinetic model. The assessment of various nonlinear isotherm models for analyzing equilibrium data revealed that the experimental data of selenium adsorption conformed to a generalized isotherm, showing a maximum monolayer adsorption capacity of 17.643 mg/g.

Effective degradation of bentazone by two-dimensional and three-phase, three-dimensional electro-oxidation system: kinetic studies and optimization using ANN.

Bentazone is a broad-leaved weed-specific herbicide in the pesticide industry. This study focused on removing bentazone from water using three different methods: a two and three-dimensional electro-oxidation process (2D/EOP and 3D/EOP) with a fluid-type reactor arrangement using tetraethylenepentamine-loaded particle electrodes and an adsorption method. Additionally, we analysed the effects of two types of supporting electrolytes (Na2SO4 and NaCl) on the degradation process. The energy consumption amounts were calculated to evaluate the obtained results. The degradation reaction occurs 3.5 times faster in 3D/EOP than in 2D/EOP at 6 V in Na2SO4. Similarly, the degradation reaction of bentazone in NaCl occurs 2.5 times faster in 3D/EOP than in 2D/EOP at a value of 7.2 mA/cm2. Removal of bentazone is significantly better in 3D/EOPs than in 2D/EOPs. The use of particle electrodes can significantly enhance the degradation efficiency. The study further assessed the prediction abilities of the machine learning model (ANN). The ANN presented reasonable accuracy in bentazone degradation with high R2 values of 0.97953, 0.98561, 0.98563, and 0.99649 for 2D with Na2SO4, 2D with NaCl, 3D with Na2SO4, and 3D with NaCl, respectively.

Fugacity and kinetic models reveal specific-fate of geosmin in air-water-fish microcosm and channel catfish (Ictalurus punctatus)

Geosmin (GSM) is a ubiquitous odorant found in aquatic environments and organisms, with significant impacts on drinking water and aquaculture. However, its transfer from contaminated water to fish tissues is poorly investigated, resulting in limited information on its bioconcentration and environmental behavior. Fugacity and one-compartment models were developed to describe the fate, transformation, and transport of GSM in an air-water-fish system and analyze its uptake, distribution, and elimination kinetics in channel catfish (Ictalurus punctatus). The results showed that the fugacity model calculations indicated that 81.3 % of GSM was found in water for all microcosm. The primary mass transfer processes from water were water-air diffusion process (T21v) and that from water to fish (T2 f), with values of 67.3 and 22.54 μg/h, respectively. The emission rate (E2) and area (A2) in water parameters are most sensitive to GSM concentration, impacting the distribution and variance of contaminant concentration. Kinetic studies in fish revealed that GSM primarily accumulate in the muscle and skin, with the earthy-odor burden of fish contributed by the former, reaching 86.59 %. The uptake rate constant (kup), depuration rate constant (kde), and half-lives (t1/2) fell within the ranges of 0.737–3.534 L/(kg·h), 0.024–0.097 1/h, and 7.1–28.9 h, respectively. Bioaccumulation factors (BAFs) for GSM in fish skin, muscle, and liver tissues were 105.79, 61.71, and 51.22 L/kg, respectively. GSM was effectively depurated by other tissues within 72 h, while 18.16 % remained in skin. The liver demonstrated the most accurate curve (R2=0.97), followed by skin and muscle, with the gill showing the worst simulation. This work offers insights into understanding the fate and mass transfer flux of trace odorants in environmental and biological phases.

Determining the critical time points for hydrate formation in the presence of kinetic hydrate inhibitors: A rheological and kinetic study

Kinetic hydrate inhibitors have the characteristics of delaying hydrate nucleation and reducing hydrate growth rate. The utilized of kinetic hydrate inhibitors for hydrate blockage risk management is a promising technology for hydrate prevention in oil and gas industry. In this study, the rheological and kinetic properties of gas–water systems contained pure water, polyvinyl pyrrolidone and newly-synthesized inhibitor during hydrate formation at different subcooling degrees were in situ characterized using a high-pressure rheometer. By analyzing the experimental results, the concept of ‘critical time’ have been proposed to divide the time-varying process of hydrate formation into multiple stages. The three critical times indicated distinct trends in viscosity and pressure changes, as well as varying risks of hydrate blockage in hydrate prevention. The results further compared the differences in determining critical time through pressure and viscosity. The critical time of hydrate nucleation determined by viscosity was earlier than pressure due to the hypothesis of lag in gas consumption. The critical time of rapid hydrate growth determined by viscosity was later than gas consumption, which may be due to that the sharp increase in viscosity requires the aggregation of hydrates. According to the inhibition effect evaluation results determined by three critical times, it was found that the newly-synthesized inhibitor was more effective than polyvinyl pyrrolidone in inhibiting nucleation, delaying rapid hydrate growth time and reaching high viscosity time. This study can provide a comprehensive evaluation method for assessing the performance of kinetic hydrate inhibitors from both kinetic and rheological perspectives.

Gas-Phase Reaction Kinetic Study of a Series of Methyl-Butenols with Ozone under Atmospherically Relevant Conditions.

Methyl-butenols are a category of oxygenated biogenic volatile organic compounds emitted by plants as part of their natural metabolic processes. This study examines the gas-phase reactions of ozone (O3) with five methyl-butenols (2-methyl-3-buten-2-ol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, 2-methyl-3-buten-1-ol, and 3-methyl-3-buten-2-ol) under atmospheric conditions at a temperature of (298 ± 2) K and pressure of (1000 ± 10) mbar. The experimental values for the gas-phase reaction rate coefficients obtained in this study, by using the relative rate method, are as follows (in cm3 molecule-1 s-1): k(3-methyl-2-buten-1-ol + O3) = (311 ± 20) × 10-18, k(2-methyl-3-buten-2-ol + O3) = (9.55 ± 1.04) × 10-18, k(3-methyl-3-buten-1-ol + O3) = (7.29 ± 0.46) × 10-18, k(2-methyl-3-buten-1-ol + O3) = (4.25 ± 0.29) × 10-18, and k(3-methyl-3-buten-2-ol + O3) = (62.9 ± 6.8) × 10-18. The results are discussed in detail, with particular emphasis on the degree and type of substitutions of the double bond. The determined rate coefficient values are also compared to the available literature data and with estimates of the structure-activity relationship. Additionally, the atmospheric implications toward the tropospheric lifetime and photochemical ozone generation potential for the investigated compounds are provided, which highlight the atmospheric impact of methyl-butenol decomposition into the lower atmosphere.

Enhancing visible-light-driven photocatalysis: unveiling the remarkable potential of H2O2-assisted MOF/COF hybrid material for organic pollutant degradation.

In this study, we synthesized MOF/COF hybrid material (NH2-MOF-5/MCOF) by integrating NH2-MOF-5 (Zn) with a melamine-based COF (MCOF) to target the photocatalytic degradation of methylene blue (MB) dye. Characterization using SEM, XRD, XPS, FT-IR, and UV-DRS confirmed the synthesized MOF/COF hybrid's exceptional photocatalytic performance under visible light. The addition of H2O2 significantly enhanced the photocatalytic degradation, achieving removal rates of 90%, 92%, and 57% for 11.75mg L-1, 30mg L-1, and 83mg L-1 of MB, respectively. Kinetic studies revealed first-order kinetics, with a rate constant nearly 3.5 times higher with added H2O2. We proposed a comprehensive photocatalytic mechanism elucidated through energy band structure analysis and scavenger tests. Our findings revealed the formation of a heterojunction between NH2-MOF-5 and MCOF, which mitigates electron-hole recombination, with ∙OH identified as the principal species governing methylene blue degradation. Moreover, the NH2-MOF-5/MCOF hybrid displayed excellent reusability and chemical stability over six cycles. Notably, this H2O2-assisted hybrid material demonstrated the removal of 99% of ibuprofen, a pharmaceutical drug, showcasing its broad applicability in removing organic contaminants in aqueous solutions, thereby holding great promise for wastewater treatment.

Optimization and Kinetic Study of Manganese Leaching from Pyrolusite Ore in Hydrochloric Acid Solutions with Oxalic Acid

AbstractThe leaching behavior of pyrolusite minerals was examined in hydrochloric acid solutions, including oxalic acid, to evaluate the influence of various experimental conditions. The optimum parameters for the leaching process were found in the first stage, and the process's kinetics were assessed in the second. The concentrations of oxalic acid, hydrochloric acid, and temperature were chosen as independent variables in the optimization experiments, with the central composite design used to analyze the experimental data. The optimum concentrations for oxalic acid, hydrochloric acid, and temperature were determined to be 0.75 mol/L, 1.2 mol/L, and 60 °C, respectively. The leaching rate was determined to be 97.4% for 120 min of response time in optimum situations. The kinetic assessment experiments studied the effects of solid/liquid ratio, particle size, stirring speed, and temperature on the manganese leaching rate from pyrolusite. In the studies, the leaching rate was shown to rise with increasing temperature and stirring speed, as well as with decreasing particle size and solid/liquid ratio. The kinetic analysis revealed that the leaching kinetics matched the mixed kinetic model, and a mathematical model for the leaching process was developed. This process's activation energy was determined to be 29.05 kJ/mol. Graphical Abstract

Unveiling the kinetic versatility of aryl-alcohol oxidases with different electron acceptors

Introduction: Aryl-alcohol oxidase (AAO) shows a pronounced duality as oxidase and dehydrogenase similar to that described for other glucose-methanol-choline (GMC) oxidase/dehydrogenase superfamily proteins involved in lignocellulose decomposition. In this work, we detail the overall mechanism of AAOs from Pleurotus eryngii and Bjerkandera adusta for catalyzing the oxidation of natural aryl-alcohol substrates using either oxygen or quinones as electron acceptors and describe the crystallographic structure of AAO from B. adusta in complex with a product analogue.Methods: Kinetic studies with 4-methoxybenzyl and 3-chloro-4- methoxybenzyl alcohols, including both transient-state and steady-state analyses, along with interaction studies, provide insight into the oxidase and dehydrogenase mechanisms of these enzymes. Moreover, the resolution of the crystal structure of AAO from B. adusta allowed us to compare their overall folding and the structure of the active sites of both AAOs in relation to their activities.Results and Discussion: Although both enzymes show similar mechanistic properties, notable differences are highlighted in this study. In B. adusta, the AAO oxidase activity is limited by the reoxidation of the flavin, while in P. eryngii the slower step takes place during the reductive half-reaction, which determines the overall reaction rate. By contrast, dehydrogenase activity in both enzymes, irrespective of the alcohol participating in the reaction, is limited by the hydroquinone release from the active site. Despite these differences, both AAOs are more efficient as dehydrogenases, supporting the physiological role of this activity in lignocellulosic decay. This dual activity would allow these enzymes to adapt to different environments based on the available electron acceptors.

The effect of carbon coating on the arsenite sorption by magnetic carbon nanocomposites

AbstractArsenic pollution has emerged through anthropogenic activities and natural mineral leaching processes. This study aims to advance the use of magnetic carbon nanocomposites (MCNs) in the sorption of arsenic, studying the influence of feedstock and the presence of carbon coating on magnetic nanoparticles. Previous works have shown that post-pyrolysis treatment improves the stability of MCNs by reducing iron leaching due to the formation of a carbon coating that encapsulates the iron oxide nanoparticles. However, this carbon coating could influence the adsorption properties of MCNs. This investigation deals with arsenic adsorption by four MCNs prepared by co-precipitation of magnetite (Fe3O4) nanoparticle into four carbonaceous matrixes, followed by a post-pyrolysis treatment. The pristine carbonaceous matrixes used in the present work were commercial activated carbon (CAC), charcoal (CC), hydrochar from the orange residue (HCOR), and biochar from sunflower husk (BCSFH). Pristine carbonaceous materials and MCNs without post-pyrolyzed were also used as arsenic sorbents in water solutions. Additionally, kinetic studies were carried out to explore the sorption properties of different MCNs and pristine materials, concerning the removal efficiencies (expressed as a percentage) and adsorption capacities, determining the equilibrium time. The results demonstrated that the presence of magnetite increases the adsorption of arsenic, being higher in the case of materials obtained by direct co-precipitation than in materials subjected to a post-pyrolysis process. The presence of a carbon layerprotecting the magnetite slightly decreases the adsorption of arsenic.

Assessing the adsorption of a diverse range of pharmaceuticals to virgin and aged poly (ethylene terephthalate) microplastics in different environmental matrices.

In this study, the adsorption of a mixture of high-consumed drugs onto virgin and aged PET microplastics has been studied for the time ever. The target mixture comprised two anti-inflammatory drugs, diclofenac and ketoprofen, one anti-hypertensive, valsartan, and four common antibiotics, indomethacin, trimethoprim, isoniazid, and metronidazole. Two types of PET MPs (virgin and UV-aged) were used in the experimental procedure. Kinetic studies were conducted, and adsorption isotherms were obtained revealing the possible interactions that take place between adsorbents and adsorbates. Among the studied pharmaceuticals, diclofenac presents the highest uptake due to its hydrophobic nature, while aging appears to induce the adsorption of the drugs in MPs. Factors like pH or the environmental matrix were also evaluated. The results revealed that sorption is pH-dependent, while more complicated matrices like wastewater or seawater exhibit lower uptake than distilled water due to the natural organic matter present or the increased salinity, respectively. Finally, desorption studies were also conducted in three different aqueous solutions examining the pH effect. The desorption of the compounds was higher for diclofenac, followed by valsartan, and ketoprofen. The desorption percentages of antibiotics were quite low.

A Green Approach to Oil Spill Mitigation: New Hybrid Materials for Wastewater Treatment

This study focuses on the development of adsorptive materials to retain degraded 5w40 motor oil. The materials were prepared using xanthan (XG) and XG esterified with acrylic acid (XGAC) as the polymeric matrix. LignoBoost lignin (LB), LB esterified with oleic (LBOL), stearic acid (LBST) and montmorillonite (CL) were added into XG and XGAC matrices to obtain the adsorbents. Adsorption experiments revealed that XG/CL/LBOL had the highest adsorption capacity at 46.80 g/g, followed by XGAC/CL at 45.73 g/g, and XG/CL at 37.58 g/g. The kinetic studies, employing the pseudo-second-order (PSO) model, indicated rapid sorption rates with a good correlation to experimental data. FTIR spectra analysis have evidenced the physical nature of adsorption process, involving interactions such as hydrogen bonding, van der Waals forces, and π–π interactions. Equilibrium data fitting to the Henry, Freundlich, and Temkin isotherm models showed that the adsorption occurs within materials diverse pore structures, enhancing oil retention. Structural parameters like density, porosity, and surface area were pivotal, with XG/CL/LBOL showing the most favorable properties for high oil adsorption. Additionally, it was found that the adsorption efficiency was influenced by the material’s morphology and the presence of chemical modifications. This comprehensive evaluation highlights the potential of these novel adsorptive materials for environmental remediation applications, offering an efficient and sustainable approach to reducing degraded motor oil pollution.

Structural and kinetic characterization of DUSP5 with a Di-phosphorylated tripeptide substrate from the ERK activation loop

Introduction: Dual specific phosphatases (DUSPs) are mitogen-activated protein kinase (MAPK) regulators, which also serve as drug targets for treating various vascular diseases. Previously, we have presented mechanistic characterizations of DUSP5 and its interaction with pERK, proposing a dual active site.Methods: Herein, we characterize the interactions between the DUSP5 phosphatase domain and the pT-E-pY activation loop of ERK2, with specific active site assignments. We also report the full NMR chemical shift assignments of DUSP5 that now enable chemical shift perturbation and dynamics studies.Results and Discussion: Both phosphates of the pT-E-pY tripeptide are dephosphorylated, based on 31P NMR; but, steady state kinetic studies of the tripeptide both as a substrate and as an inhibitor indicate a preference for binding and dephosphorylation of the phospho-tyrosine before the phospho-threonine. Catalytic efficiency (kcat/Km) is 3.7 M−1S−1 for T-E-pY vs 1.3 M−1S−1 for pT-E-Y, although the diphosphorylated peptide (pT-E-pY) is a better substrate than both, with kcat/Km = 18.2 M−1S−1 . Steady state inhibition studies with the pNPP substrate yields Kis values for the peptide inhibitors of: 15.82 mM (pT-E-Y), 4.932 mM (T-E-pY), 1.672 mM (pT-E-pY). Steady state inhibition studies with pNPP substrate and with vanadate or phosphate inhibitors indicated competitive inhibition with Kis values of 0.0006122 mM (sodium vanadate) and 17.32 mM (sodium phosphate), similar to other Protein Tyrosine Phosphatases with an active site cysteine nucleophile that go through a five-coordinate high energy transition state or intermediate. Molecular dynamics (MD) studies confirm preferential binding of the diphosphorylated peptide, but with preference for binding the pY over the pT reside in the catalytic site proximal to the Cys263 nucleophile. Based on MD, the monophosphorylated peptide binds tighter if phosphorylated on the Tyr vs the Thr. And, if the starting pose of the docked diphosphorylated peptide has pT in the catalytic site, it will adjust to have the pY in the catalytic site, suggesting a dynamic shifting of the peptide orientation. 2D 1H-15N HSQC chemical shift perturbation studies confirm that DUSP5 with tripeptide bound is in a dynamic state, with extensive exchange broadening observed—especially of catalytic site residues. The availability of NMR chemical shift assignments enables additional future studies of DUSP5 binding to the ERK2 diphosphorylated activation loop.Summary: These studies indicate a preference for pY before pT binding, but with ability to bind and dephosphorylate both residues, and with a dynamic active site pocket that accommodates multiple tripeptide orientations.

Enhanced removal of tetrabromobisphenolA (TBBPA) from e-waste by Fe–S nanoparticles and Fe–S/CuS nanocomposite with response surface methodology (RSM)

TetrabromobisphenolA is a well-known member of the brominated flame retardant group and is widely used as a highly effective fire-retardant additive in electronic and electrical equipment. TBBPA is commonly found in various environmental sources and can be harmful to human health. This study presents a simple approach to preparing a magnetic nanocomposite, offering a straightforward method that results in consistent quality and low resource consumption. The nanocomposite has a high surface-to-volume ratio for the removal of tetrabromobisphenolA. Various characterization techniques, including XRD, FTIR, EDX, FESEM, VSM, TEM, and BET analyses were used to characterize the Fe–S nanoparticles and Fe–S/CuS. The results showed that Fe–S/CuS nanocomposite successfully removed over 97% of the initial TBBPA (15 mg L−1) under optimized conditions determined by RSM, such as a contact time of 15 min, pH of 7, Fe–S/CuS nanocomposite dosage of 0.69 g L−1, and salt concentration of 0.10%. The RSM analysis provided a second-order polynomial model with a confidence level of 93% (F = 29.58; p < 0.0001) to predict the TBBPA removal efficiency at various concentrations. In the adsorption kinetic studies, the second-order kinetic model provided the best fit for the experimental data. Additionally, Fe–S/CuS nanocomposite shows great potential for practical applications and environmental remediation efforts, making it a valuable asset for real-sample use in environmental settings.

A kinetic modelling approach to explore mechanism of Cr(VI) detoxification by a novel strain Pseudochrobactrum saccharolyticum NBRI-CRB 13 using response surface methodology.

A novel Pseudochrobactrum saccharolyticum strain NBRI-CRB 13, isolated from tannery sludge, was studied to grow up to 500 mgL-1 of Cr(VI) and showed Cr(VI) detoxification by reducing > 90% of Cr(VI) at different concentrations 25, 50 and 100 mgL-1. Kinetic studies showed that first-order models were fitted (R2 = 0.998) to the time-dependent Cr(VI) reduction with degradation rate constant (k) (1.03-0.429h-1). Cr(VI) detoxification was primarily related to the extracellular fraction of microbial cells, which showed a maximum extracellular reductase enzyme activity led to 94.6% reduction of Cr(VI). Moreover, the strain showed maximum extracellular polymeric substances (EPS) production at 100 mgL-1 Cr(VI), which is presumably the reason for Cr(VI) removal as EPS serves as the metal binding site for Cr(VI) ions. Further, an optimization study using Box-Behnken design was conducted considering parameters viz., pH, temperature, and initial concentration of Cr(VI). The maximum percent reduction of Cr(VI) was obtained at pH 6.5, temperature 30°C with 62.5 mgL-1Cr(VI) concentration. Further, the Cr(VI) reduction and adsorption ability of strain P. saccharolyticum NBRI-CRB13 were confirmed by SEM-EDS, FTIR, and XRD analyses. FTIR analysis confirmed the presence of functional groups (-OH, -COOH, -PO4) on bacterial cell walls, which were more likely to interact with positively charged chromium ions. The study elucidated the reduction of Cr(VI) by the novel bacterium within 24h using the response surface methodology approach and advocated its application in real-time situations.

Preparation of high-purity magnetite from iron ore concentrate

In pursuit of environmental protection and green, low-carbon economic development, China has proposed the dual-carbon strategies of carbon peak and carbon neutrality. To achieve the dual-carbon goals, traditional steel metallurgical production processes are gradually shifting towards green and low-carbon hydrogen metallurgical processes. However, hydrogen metallurgical processes have strict requirements for raw materials and typically require the utilization of high-grade iron concentrates. The scarcity of high-grade iron ore in China severely constrains the development of hydrogen metallurgical processes. Therefore, this study proposes the utilization of ordinary magnetite concentrate to produce high-grade magnetite. Comprehensive analytical methods, including chemical analysis, X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD) analysis, laser particle size testing, optical microscopy, scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), and mineral liberation analysis, were employed to elucidate the mineralogical characteristics of the iron concentrate. The analysis revealed that the iron concentrate had a total iron (TFe) grade of 65.56 %, with SiO2 and Al2O3 contents of 8.28 % and 0.38 %, respectively. Subsequently, a combined beneficiation process involving magnetic separation, flotation, and chemical leaching was conducted. Experimental results showed that a single magnetic separation obtained an iron concentrate grade of 67.52 % with an overall recovery of 86.18 %. Following magnetic separation, flotation was conducted to increase the concentrate grade. With one roughing and four cleaning flotation stages, a concentrate grade of 72.19 % and a 36.36 % overall recovery were achieved. A subsequent leaching operation after flotation yielded high-purity magnetite with a Fe grade of 72.30 % and an overall recovery of 35.68 %. The high-purity magnetite was confirmed to have a purity of up to 99.9 % based on chemical titration, XRD analysis, magnetic susceptibility measurement, and SEM analysis. Furthermore, detailed kinetics studies on leaching were conducted to elucidate the reaction mechanism, revealing an apparent activation energy of 25.70 kJ/mol. The successful implementation of this process will provide a benchmark for producing similar high-purity magnetite concentrates and contribute to China’s dual-carbon goals.

Visible‐Light‐Mediated Activation of Remote C(sp3)−H Bonds by Carbon‐Centered Biradical via Intramolecular 1,5‐ or 1,6‐Hydrogen Atom Transfer

AbstractIn this study, we introduce a novel intramolecular hydrogen atom transfer (HAT) reaction that efficiently yields azetidine, oxetane, and indoline derivatives through a mechanism resembling the carbon analogue of the Norrish‐Yang reaction. This process is facilitated by excited triplet‐state carbon‐centered biradicals, enabling the 1,5‐HAT reaction by suppressing the critical 1,4‐biradical intermediates from undergoing the Norrish Type II cleavage reaction, and pioneering unprecedented 1,6‐HAT reactions initiated by excited triplet‐state alkenes. We demonstrate the synthetic utility and compatibility of this method across various functional groups, validated through scope evaluation, large‐scale synthesis, and derivatization. Our findings are supported by control experiments, deuterium labeling, kinetic studies, cyclic voltammetry, Stern–Volmer experiments, and density functional theory (DFT) calculations.

N-doped nano-casted carbon monolith for Pb (II) removal and photocatalytic degradation of thiamethoxam from aqueous solution.

Single rock-like N-doped carbon monolith (ND-PFCM) was successfully constructed via nanocasting method. Phenol formaldehyde resin was taken as carbon source and nitrogen was incorporated in monoliths through NaNH2 activation. The synthesized monoliths were used for the removal of Pb (II) from aqueous solution. Various characterization techniques, namely Brunauer-Emmett-Teller (BET), Raman spectroscopy, UV-visible diffuse reflectance spectra (DRS) UV-DRS, zeta potential, scanning electron microscopy (SEM), TEM (transmission electron microscopy), TGA (thermogravimetric analysis), and XPS (X-ray photoelectron spectroscopy), were utilized to characterize synthesized monolithic samples. The different parameters such as pH, adsorbent dosage, and time were enquired on the removal efficiency of monoliths toward Pb(II). ND-PFCM exhibited the highest adsorption capacity of 330.03mgg-1 in 180min at pH 6. This is attributed to the fact that the better texture properties and presence of nitrogen functional groups enhance the uptake of Pb (II) ions on the monolith surface. In the kinetic studies, pseudo-second-order model fitted best with the experimental data. Furthermore, the removal of thiamethoxam (TM) from aqueous solution was done by using different weight ratios of ND-PFCM under the visible light. The maximum removal efficiency of 97.35% with rate constant of 0.02085min-1was obtained in 160min. Moreover, monoliths exhibited good reusability for five consecutive cycles. The findings suggest that the synthesized monoliths exhibit characteristics suitable and eco-friendly for sustainable use in water treatment applications.

Kinetic study of reaction formation of phosphate products from thermal dissolution of wolframite using fusion technique

This study examined an alternative technique of extracting tungsten from wolframite ore using a fusion method with ammonium phosphate salt. Current techniques use alkali salts to decompose tungsten ores and use various purification methods to produce ammonium paratungstate, which is a key intermediate precursor in the extraction of tungsten. In this study, a two-step extraction process, which involves thermal decomposition of the ore using fusion and a separation stage, is examined. The novelty of this technique is the ability to completely decompose wolframite ore and form an unstable tungsten oxide phosphate (WO2(PO3)2) compound. The instability of WO2(PO3)2 in deionized water enables selective isolation of tungsten as insoluble precipitates of WO3 and WO2. The decomposition reaction of WO2(PO3)2 is influenced by the presence of oxygen and determined to be first order under ambient conditions. Scanning electron micrographs and X-ray diffraction analysis showed above 80% of the tungsten precipitated compared with the amount that remained in the filtrate solution.

The role of cyclodextrins in the acceleration of the reaction rate in a biphasic hydroformylations

Water based biphasic hydroformylation assisted by cyclodextrins is known for enhanced reaction rates in comparison to the non-assisted biphasic hydroformylation. In this paper, the liquid–liquid interface of the hydroformylation of 1–octene, enhanced by randomly methylated-β cyclodextrins (RAME-β cyclodextrins), was examined for the first time using an in-situ image-based boroscopic technology. This technique enables the observation of the liquid–liquid interfacial area (aLL) during the reaction and under reaction conditions, facilitating an explicit analysis of the droplet population.In this study defined mixtures of the reaction components with RAME-β cyclodextrins increased the aLL by 84 %. A kinetic study showed that RAME-β cyclodextrins reduce the rate limiting effect of the nonanal concentration in the two phasic water/octene system on the interphase. The kinetic expression shows consequently higher reaction rates for this three-phase conversion, leading to a 387 % increase in aldehyde yield. When comparing four different amounts of RAME-β cyclodextrins (nCD:nRh(acac)(CO)2 = 0 / 12:1 / 24:1 / 50:1), we observed a decreasing dependency of the reaction rates on the conversion progress and therefore on the nonanal formation for higher cyclodextrin concentrations. A recovery test of the aqueous phase involving nonanal and 1-octene reveals a drastically increased concentration of 1029 % 1-octene (coctene = 1.08 10-3 mg mg−1) and 13676 % nonanal (cnonanal = 14.41 10–3 mg mg−1) after the addition of 0.002 mol RAME–β cyclodextrins. These findings affirm that RAME-β cyclodextrins primarily remove nonanal from the interfacial region while facilitating an increased availability of 1-octene for the surface bound reaction.

Tenebrio Molitor breeding rejects as a high source of pure chitin and chitosan: Role of the processes, influence of the life cycle stages and comparison with Hermetia illucens

This work valorizes rejects from Tenebrio Molitor TM breeding through the production of chitin and chitosan. Two processes are proposed for extracting chitin from larval exuviae and adult. The first process P1 provides chitin with high contents compared to literature data but the characterization shows the presence of impurities in the exuviae chitin responsible for the shifts in the values of the physicochemical characteristics towards those presented by γ chitin. These impurities are removed by delipidation and pure α chitin is obtained. The effective delipidation of this chitin would be linked to its fibrous surface structure. The analysis of the results of P1 led us to develop a second extraction process P2 which provides pure chitin with improved yields using delipidation followed by deproteinization. The N-deacetylation of chitin according to Kurita or Broussignac process makes possible the preparation of pure, highly deacetylated chitosan samples (2 % < DA < 12 %) with high yields and controlled molar masses (Mv). A kinetic study of molecular degradation during deacetylation is carried out. A comparison with Hermetia illucens allows to extend the use of insects as a potential source of chitin and chitosan and confirms the role of the source and the processes in the determination of their characteristics.