Rate Constant K1 Research Articles

Calculation of the Rate Constants of Vacuum Residue Hydrogenation Reactions in the Presence of a Chrysotile/NiTi Nanocatalyst

The paper presents the results of an investigation into the kinetics of catalytic hydrogenation of vacuum residue at temperatures of 380, 400 and 420 °C and different durations, ranging from 30 to 70 min, using a nanocatalyst containing the active metals nickel and titanium supported on chrysotile. It was found that the yield of oils from 30 to 50 wt.% and tars from 12 to 18 wt.% increased with increasing temperatures and reaction times. A slight increase in the proportion of solids in the range of 2.0 to 6.0 wt.% is explained by the activity of the nanocatalyst used. In the study of the kinetics of vacuum residue hydrogenation, using the nanocatalyst developed by the authors, we were able to achieve a low yield of solids with a short contact time as well as a high yield of low-molecular-weight compounds such as oils and tars. To determine the kinetic parameters (rate constants and activation energies), Simpson’s integral method and a random search engine optimization method were used. High values of rate constants are characteristic of reactions in the formation of oils k1, tars k2 and asphaltenes k3 in the temperature range of 380–420 °C. The high values of the rate constants k1, k2 and k3 in the catalytic hydrogenation of the vacuum residue indicate the high reaction rate and activity of the nanocatalyst used. With an increase in temperature from 380 to 420 °C, the rate constant of the formation of gas products from vacuum residue and the conversion of asphaltenes into oils significantly increase, which indicates the accumulation of low-molecular-weight compounds in oils. The activation energy for reactions leading to the formation of oils, tars, asphaltenes, gas and solid products was 75.7, 124.8, 40.7, 205.4 and 57.2 kJ/mol, respectively. These data indicate that the processes of vacuum residue hydrogenation with the formation of oils and asphaltenes require the lowest energy inputs. Reducing the process temperature to increase the selectivity of the vacuum residue hydrogenation process when using the prepared nanocatalyst is recommended. The formation of oils at the initial stage plays a key role in the technology of the heavy hydrocarbon feedstock (HHF) hydrogenation process. Perhaps the resulting oils can serve as an additional solvent for high-molecular-weight products such as asphaltenes, as evidenced by the low activation energy of the process.

Peroxydisulfate activation by copper nanoparticles doped highly graphitized hollow carbon spheres for thiocyanate degradation

Thiocyanate (SCN-) is a toxic and refractory inorganic pollutant commonly found in industrial wastewater. This paper proposes an innovative solution to enhance the activation of peroxydisulfate (PDS) by designing a highly graphitized hollow carbon nanosphere structure catalyst doped with copper nanoparticles, thereby achieving efficient and complete degradation of SCN-. Specifically, the active sites and electron transfer ability of the catalyst were improved by controlling the pyrolysis temperature and acid etching time during the catalyst preparation process, thereby optimizing the PDS activation rate and SCN- degradation rate. In the optimized Cu-NPs@C/PDS system, a low dose of Cu-NPs@C-650–6 catalyst (0.2 g/L) and PDS ([PDS]0: [SCN-]0 = 3: 1) was sufficient to achieve 100 % degradation of 100 mg/L SCN- within 20 min. The non-radical oxidation pathway combined with singlet oxygen (1O2) and direct electron transfer process was identified as the main degradation mechanism of SCN-. The unique oxidation mechanism provided a higher SCN- degradation reaction rate constant (k1 = 0.39 min−1) and stronger environmental ion resistance. Density functional theory (DFT) calculations show that the CO bond is the primary PDS active site for the formation of inside-out electron delocalization, and the S atom in SCN- is a vulnerable site. This work offers technological support for the treatment of water bodies holding emerging electron-rich pollutants in addition to fresh insights into the creation of efficient catalysts for metal-carbon composites.

Electrode reactions on the aluminum electrode in 1-butyl-3-methylimidazolium chloride chloroaluminate ionic liquid: A comprehensive study

Mechanisms of Al electrochemical deposition/dissolution in acidic AlCl3–1-butyl-3-methylimidazolium chloride (BMImCl) ionic liquids are studied. Stationary polarization curves (SPCs) are obtained in the anodic range of potentials. The anodic SPCs are characteristic of electrode processes, which are complicated by passivation phenomena. The peaks intensity of AlCl4−, Al2Cl7− ions were obtained by in-situ Raman spectroscopy during the aluminum electrode polarization and correlated with the behavior of the SPCs. Based on the results obtained, a mechanism of electrochemical oxidation of aluminum in AlCl3–BMImCl IL is proposed. According to the mechanism in question, the anodic process is complicated by the presence of a following chemical reaction involving AlCl3. Chronopotentiometric studies were carried out to determine diffusion coefficients of Al2Cl7− anion, which are unaffected by the change in the molar ratio of AlCl3 to BMImCl (N). The activation energy (Ea) for the Al2Cl7− diffusion coefficient is independent of N and equals 14.5 ± 0.4 kJ mol−1. Exchange current density (i0) at the Al | AlCl3–BMImCl interface was determined using impedance spectroscopy for the compositions with 1.1 ≤ N ≤ 2.0 at temperatures from 303 to 386 K. The i0 increases from 0.54 ± 0.13 to 2.73 ± 0.22 mA cm−2 with the concentration of the electrochemically active Al2Cl7− anion in the concentration range indicated above at 303 K. The data on i0 is used to calculate the transfer coefficient of cathodic reaction (α = 0.18 ± 0.02), the electrochemical reaction rate constant (ks= (1.1 ± 0.3)∙10−6 cm s−1 (at T = 303 K)) and the Ea for the ks (Eaks = 36.5 ± 0.9 kJ mol−1), which do not depend on the IL composition.

Phytochemical preparation of Zinc Stannate nanoparticles by using lemon and grapefruit peels for removal of cadmium ions

The synthesis of Zinc Stannate (Zn2SnO4) nanoparticles may be achieved by utilizing lemon and grapefruit peels, as indicated by the results of this study. This analysis outlines a sustainable, cost-effective, and readily available approach. The Zn2SnO4 nanoparticles were generated biologically and were discovered to have a cubic crystalline structure, as established by structural analysis using Rietveld refinement. TEM microstructural examinations revealed that Zn2SnO4 nanoparticles exhibit a homogeneous distribution and possess an average diameter of around 21 nm. The Zn2SnO4 nanoparticles have an optical energy band gap of 3.05 eV and demonstrate a UV region peak, which showed that Zn2SnO4 nanoparticles were being formed. More precisely, the pH of the solution greatly affects the absorption of Cd2+ ions. Kinetic analysis involves the use of two types of models: pseudo-first-order and pseudo-second-order. The previous model yields an R2 value of 0.9031 and a rate constant (k1) of 0.41 × 10−2 min−1. However, the pseudo-second-order model provides a better match, as seen by its very high R2 value of 0.9932 and rate constant (k2) value of 4.4 × 10−3 g.(mg.min)−1. In addition, isotherm modeling shows that the experimental data closely match the Freundlich isotherm model.

Investigating the structural and magnetic properties of Fe3Se4 nanoparticles and it's photocatalytic application

This study explores the potential of synthesized Fe3Se4 nanoparticles by solid-state reaction method and it's photocatalytic application. The structural parameters validated by X-ray diffraction (XRD) demonstrate a monoclinic structure. The particle size of the prepared material was estimated at approximately 95 nm, as observed by field emission scanning electron microscopy (FE-SEM) and it's composition was verified by energy dispersive spectroscopy (EDS). Strong Raman modes were observed at 225 cm−1 which is responsible for lattice vibration in Fe3Se4. Both Fe2+ and Fe3+ oxidation states were present in Fe3Se4, as characterized by X-ray photoelectron spectroscopy (XPS). From the thermal gravimetric analysis (TGA) curves, the Fe3Se4 was confirmed to be stable up to 295 °C. vibrating sample magnetometer (VSM) tests revealed that the coercivity was 151 Oe at ambient temperature and increased 20 times to 2425 Oe at 15 K. Tauc's plot indicated an optical band gap value of 1.12 eV. Fe3Se4 nanoparticles achieved an 80.79 % dye degradation efficiency and exhibited photocatalytic activity against methylene blue dye. In photocatalysis, the apparent pseudo-first-order k1 and pseudo-second-order k2 rate constants are 0.018 min−1 and 0.058 min−1.

Voltammetry of the ferric/ferrous redox couple at platinum microelectrodes in aqueous hydrochloric acid

In this paper, the Fe3+/Fe2+ redox system was investigated in 0.5 M HCl solutions, using steady-state voltammetry at a Pt microelectrode. Measurements were performed in solutions containing each ion alone or in mixtures containing both ions. The reduction of Fe3+ to Fe2+ provided a single sigmoidal wave, regardless of the ion concentration. For the oxidation process of Fe2+ to Fe3+, a wave split was observed at relatively high ion concentrations (i.e., ≥ about 10 mM). This feature, not observed or not considered in previous studies, was rationalized by considering that the Fe2+ oxidation process occurs over the potential region where passivating Pt oxides form on the electrode surface. Standard rate constant (k0′), and transfer coefficient (α) of the electrode process were evaluated using the method based on the quartile potentials ΔE1/4=E1/4-E1/2 and ΔE3/4=E1/2-E3/4, which can be obtained from the experimental steady-state voltammograms. k0′ and α values varied in the range 1.4 x10-3 cm s−1 – 3.1 x 10-2 cm s−1, and 0.44 – 0.64, respectively, depending on the specific status of the electrode surface, in turn depending on the care adopted in cleaning the electrode surface from the Pt oxides. From the quartile potentials approach, the formal potential of the redox system, equal to 0.495 (±0.005) V, vs. Ag/AgCl (KCl saturated) could also be evaluated. This value resulted in good agreement with 0.494 (±0.002) V, formal potential obtained from the cathodic-anodic voltammograms recorded in the mixtures of the two ions at equal concentration. Chronoamperometry was employed to determine the diffusion coefficients on the two ions by fitting the experimental current against time profiles and the theoretical equation that holds for microdisk electrodes. The values found where 4.67 x 10-6 cm2 s−1 and 5.61 x 10-6 cm2 s−1 for Fe3+ and Fe2+ ions, respectively.

Auto ignition assisted synthesis of magnetic CaFe2O4: Exploring role of fuel molecule and amplest dye dismissal

The present work explores the pioneering use of different fuels for the synthesis of CaFe2O4 (CF) nanopowder through auto-ignition synthesis (AIS) with potential application in the acid fuchsine (AF) dye removal. The results showed significant alternation in structure, morphology, and magnetic properties depending on fuel type. The morphology of the CaFe2O4 nanopowders changed from a rock-like appearance for dextrose to a porous, thick-walled network structure for sucrose. All synthesized particles showed superparamagnetic behavior, with a crystallite size of 9 nm to 16 nm. The different adsorption process parameters, including the solution pH, adsorbent amount, and contact time, were studied and optimized. The Langmuir isotherm well explains the adsorption of AF, and the maximum monolayer capacity of CF-dextrose, CF-xylitol, CF-sorbitol, and CF-sucrose was found to be 788, 1024, 1125, and 1297 mg/g, respectively. The pseudo-second-order (PSO) kinetic model describes the adsorption data and the value of rate constant (k2 = 2.36E-05 for CF-dextrose, 3.11E-05 for CF-xylitol, 2.70E-05 for CF-sorbitol, and 5.36E-05 for CF-sucrose) explain fast adsorption process. Furthermore, the CF nanopowder exhibits better regeneration and reusability capacity after multiple consecutive cycles, and magnetic separation aptitude makes it more convenient to isolate the adsorbent after the adsorption process.

A three-step “ping-pong” mechanism of a GH20 β-N-acetylglucosaminidase from Vibrio campbellii belonging to a major Clade A-I of the phylogenetic tree of the enzyme superfamily

β-N-acetylglucosaminidase (GlcNAcase) is an essential biocatalyst in chitin assimilation by marine Vibrio species, which rely on chitin as their main carbon source. Structure-based phylogenetic analysis of the GlcNAcase superfamily revealed that a GlcNAcase from Vibrio campbellii, formerly named V. harveyi, (VhGlcNAcase) belongs to a major clade, Clade A-I, of the phylogenetic tree. Pre-steady-state and steady-state kinetic analysis of the reaction catalysed by VhGlcNAcase with the fluorogenic substrate 4-methylumbelliferyl N-acetyl-β-D-glucosaminide suggested the following mechanism: (1) the Michaelis-Menten complex is formed in a rapid enzyme-substrate equilibrium with a Kd of 99.1 ± 1 μM. (2) The glycosidic bond is cleaved by the action of the catalytic residue Glu438, followed by the rapid release of the aglycone product with a rate constant (k2) of 53.3 ± 1 s−1. (3) After the formation of an oxazolinium ion intermediate with the assistance of Asp437, the anomeric carbon of the transition state is attacked by a catalytic water, followed by release of the glycone product with a rate constant (k3) of 14.6 s−1, which is rate-limiting. The result clearly indicated a three-step “ping-pong” mechanism for VhGlcNAcase.

Solar-light-driven photocatalytic degradation and detoxification of ciprofloxacin using sodium niobate nanocubes decorated g-C3N4 with built-in electric field

Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6•H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4-1 was a type-I heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4-1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.

Removal of Methyl Orange in Aqueous Medium using ZnO/Bentonite as Semiconductor by Photocatalytic Process

Pillarization of bentonites (from East Java) with ZnO semiconductors has been synthesized using co-precipitation methods into a ZnO/Bentonite composite and applied as a catalyst in a photocatalytic process to remove Methyl Orange (MO) dyes. The optimum pH condition of MO dyes is at pH 2 with a degradation rate of 22.91% (from 15 mg/L to 11.523 mg/L). The optimum ZnO/Bentonite catalyst weight condition is 200 mg, with a degradation rate of 29.11% (from 15 mg/L to 10.596 mg/L). The optimum time condition for UV lamp irradiation is 60 minutes, with a degradation rate of 64.92% (from 15 mg/L to 5.244 mg/L). The kinetics of MO photocatalytic reaction using ZnO/Bentonite catalyst follows the pseudo-first-order Langmuir Hinshelwood-Santosa kinetic model with photocatalytic reaction rate constant (k1) of 0.014 and photocatalytic equilibrium constant (K) of 0.012.

Unveiling the adsorption mechanisms of macrolides by mesoporous carbons through molecular dynamics simulation and multilinear regression modelling

Mesoporous carbon materials (MCs) are known for their high specific surface area and porous structure, rendering them promising candidates for efficient antibiotic adsorption. However, the influence of antibiotic properties and the porous structure of MCs on adsorption remains unclear. This study investigated the adsorption behaviors of ten macrolides (MLs) onto four MCs with porous structures, aiming to understanding the key factors governing their adsorption. The results revealed that the adsorption rate constant (k2) and adsorption constant of Freundlich isotherm (KF) were influenced by the McGowan molar volume of MLs. Molecular dynamics simulations uncovered that a distance of approximately 4 Å between adsorbed MLs from the material surface, suggesting hydrophobic interactions play a crucial role. Moreover, ML diffusion was more favorable on the surface of 10 nm pore compared to 2 nm pores, highlighting the impact of pore size on diffusion. Additionally, the diffusion coefficient of MLs was mainly determined by logKow, emphasizing the significance of hydrophobic interactions in diffusion. Multilinear regression modelling further supports hydrophobic interactions as the main adsorption mechanism for MLs. Overall, this study provides valuable insights into the complex adsorption mechanisms of MLs on MCs, informing the development of more effective antibiotic removal strategies.

Nanomolar detection of organic pollutant -tartrazine in food samples using zinc-metal organic framework/carbon nano fiber - composite modified screen-printed electrode

In this study, we achieved a significant breakthrough by applying a binder-free Zn-MOF@CNF composite as a modifier on a screen-printed electrode (SPE) to achieve highly sensitive and selective detection of tartrazine (TRZ). This composite, with its unique rod-like structure for Zn-MOF and a curl thread-like morphology for carbon nanofibers (CNF), demonstrated a remarkable threefold increase in the sensing current of TRZ at a lower anodic oxidation potential (0.92 V) compared to the bare SPE. The Zn-MOF@CNF/SPE also exhibited a reduced charge transfer resistance of 61.9 Ω, elevated electrochemical active surface area of 0.416 cm2, and high heterogeneous electron transfer rate constant (k0) of 9.77×10−5 cm s−1. Furthermore, it displayed a broad linear range from 0.2 μM to 1000 μM with a remarkable sensitivity of 0.136 µAµM−1cm−2 and an impressive detection limit of 54 nM. Ultimately, the developed Zn-MOF@CNF/SPE sensor demonstrated excellent selectivity amidst various structurally similar overlapping species, outstanding repeatability, reproducibility, and stability in TRZ detection. The practical applicability of Zn-MOF@CNF/SPE was validated through 97 – 100.9 % recovery results in food samples such as jelly, ice cream, soft drinks, and candies.

An Ultrasensitive Electrochemical Sensor Using Banana Peel Activated Carbon/NiFe2O4/MnCoFe-LDH Nanocomposites for Anticancer Drug Determination.

In the current study, we report the synthesis of a novel composite material composed of banana peel activated carbon (BPAC), nickel iron oxide (NiFe2O4), and manganese cobalt iron layered double hydroxide (MnCoFe-LDH) to create a high-performance electrochemical sensor to detect Palbociclib (PLB). The composite was successfully immobilized on a glassy carbon electrode (GCE) surface to create a modified electrode. The performance of the electrode was thoroughly evaluated, considering parameters such as electroactive surface areas (ESA), electron transfer rate constant (k0), and exchange current density (j0). The developed BPAC/NiFe2O4/MnCoFe-LDH/GCE exhibited a wide linear dynamic range of 0.01-13.0 μM for PLB concentration, accompanied by a detection limit at a low level (3.5 nM). Furthermore, it can be applied to the determination of PLB in human urine and pharmaceutical samples with excellent recoveries (98.5-102.9%) and RSD values lower than 3%, establishing its potential for precise PLB determination in pharmaceutical and biological samples. This research contributes to the advancement of electrochemical sensor technology for the detection of important anticancer drugs in real-world applications.

Sulfur autotrophic electrodialysis ion exchange membrane bioreactor (SEDIMB) for nitrate removal in water: Synergism and adaptability of electrodialysis and sulfur autotrophy

In this study, the novel sulfur autotrophic electrodialysis ion-exchange membrane bioreactor (SEDIMB) with high denitrification performance was developed without the addition of carbon source. Sulfur autotrophic denitrification occurs at the same time of nitrate enrichment by electric field to achieve harmless nitrate transformation in water. The final nitrate concentration in water chamber was 2.16 mg-N/L (removal efficiency of 94.49 %) at an initial nitrate concentration of 40 mg-N/L, with the maximum nitrate concentration in biological chamber of 4.09 mg-N/L. Nitrate removal in water chamber of the SEDIMB conformed to the first-order kinetic model (R2 = 0.98) and reaction rate constant K1 = 0.0030 (1/min). The effect of environmental variables (i.e., voltage, initial nitrate concentration and water body) on the SEDIMB denitrification performance was investigated. Increasing voltage could promote nitrate migration in water chamber, and when the voltage was 7 V, initial nitrate concentrations of 20 ∼ 60 mg-N/L was effectively removed (all > 93.54 %). Moreover, the change of water body (i.e., tap water, lake water and deionized water) did not affect denitrification performance of SEDIMB. Microbial community structure analysis indicated that Betaproteobacteria were dominant in the SEDIMB. Membrane characterizations (ATR-IR, SEM and CLSM) confirmed that the bacteria in biological chamber tended to accumulate and grow on one side of the anion exchange membrane (AEM), while could not affect the selective permeability of AEM.

Facile hydrothermal assembly of three-dimensional GO-MTZE composite and its adsorption properties toward Cu2.

Three-dimensional (3D) graphene oxide (GO)-based aerogels, GO and 4-methyl-5-thiazoleethanol (MTZE) composites, were prepared by a facile hydrothermal method. Due to the hydrogen bonding and π-π stacking interactions, the produced 3D GO-MTZE composites possessed large cylindrical structures. The morphologies, composition, and chemical states of 3D GO-MTZE3:1 composite were characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and N2 adsorption-desorption isotherms based on the Brunauer-Emmett-Teller (BET) method. The existence of nitrogen (N)-containing heterocyclic system and oxygen (O)-containing branched chain of MTZE contributed to the formation of 3D structures, while the complexation effect of heterocyclic sulfur (S)- and N-containing functional groups of MTZE for metal cations dominated the adsorption performance of 3D GO-MTZE3:1 composite, which could selectively adsorb copper ions (Cu2+). In addition, the better hydrophobic property of 3D GO-MTZE3:1 composite facilitates its facile recycling from aqueous solution after adsorption. The adsorption data of 3D GO-MTZE3:1 composite toward Cu2+ fitted well (R2 = 0.9996) with the linear pseudo-second-order kinetic model, giving an equilibrium rate constant (k2) of 0.0187gmg-1min-1. The linear Langmuir isothermal model could more accurately describe the experimental data, indicating the adsorption process is mainly dominated by the complexation interactions between MTZE and Cu2+. The thermodynamic parameters of ΔG° (< 0), ΔH° (> 0), and ΔS° (> 0) further indicate that the adsorption is a spontaneous and endothermic, confirming that the complexation between Cu2+ and 3D GO-MTZE3:1 composite occurs. Due to its high selectivity for Cu2+, good hydrophobicity, and excellent stability, the developed 3D GO-MTZE3:1 composite possesses might be promisingly used in the aqueous selective enrichment/removal of Cu2+.

Comparative study of the quick action effect of multiple enzyme-based nano-emulsified oils in enhancing nitrate contamination remediation in groundwater

Emulsified vegetable oil (EVO), as a novel green slow-releasing substrate, has performed great potential in subsurface bioremediation due to its slow release and longevity. Nevertheless, the long time it takes to initiate this process still exposed some limitations. Herein, multiple enzyme-based EVOs (EN-EVOs) were developed to enhance the quick-acting effect in nitrate-contaminated bioremediation. This study demonstrated that EN-EVOs loaded with cellulose (c-EVO) and protein enzymes (p-EVO) performed best, not only did not change the advantages of traditional EVO, but also optimized the stability and particle size to the level of 0.8–0.9 and 247.95–252.25 nm, respectively. Nitrate (NO3–N) degradation further confirmed the superiority of c-EVO in rapidly initiating degradation and achieving stable denitrification. Compared with traditional EVO, the maximum start-up efficiency and the rapid achieving stable denitrification efficiency were improved by 37.6% and 1.71 times, respectively. In such situation, the corresponding NO3–N removal efficiency, kinetics rate constant (k1), and half-life period (t1/2) reached as high as 85.39%, as quick as 1.079 d−1, and as short as 0.64 d after 30-day cultivation. Meanwhile, the rapid conversion efficiency of NO2–N was observed (k2 = 0.083 d−1). High-throughput 16S rRNA gene sequencing indicated that the quick-acting process of NO3–N reduction coupled to c-EVO was mediated by microbial reducers (e.g., Ralstonia, Gulbenkiania, and Sphingobacterium) with regulations of narG, nirS and norB genes. Microorganisms with these genes could achieve quick-acting not only by enhancing microbial activity and the synthesis and metabolism of volatile fatty acids, but also by reducing the production and accumulation of loosely bound-extracellular polymeric substances (LB-EPS). These findings advance our understanding on fast-acting of NO3–N degradation supported by c-EVO and also offer a promising direction for groundwater remediation.

Biogenic synthesis of CuO/ZnO nanocomposite from Bauhinia variegate flower extract for highly sensitive electrochemical detection of vitamin B2

In this study, we report the preparation of bio-inspired binary CuO/ZnO nanocomposite (bb-CuO/ZnO nanocomposite) via the biological route using Bauhinia variegata flower extract following hydrothermal treatment. The prepared bb-CuO/ZnO nanocomposite was electrophoretically deposited (EPD) on indium tin oxide (ITO) substrate to develop bb-CuO/ZnO/ITO biosensing electrode which is employed for the determination of vitamin B2 (Riboflavin) through electrochemical techniques. Physicochemical assets of the prepared bb-CuO/ZnO nanocomposite have been extensively evaluated and make use of different characterization techniques including powder XRD, FT-IR, AFM, SEM, TEM, EDX, XPS, Raman, and TGA. Electrochemical characteristics of the bb-CuO/ZnO/ITO biosensing electrode have been studied towards vitamin B2 determination. Furthermore, different biosensing parameters such as response time, reusability, stability, interference, and real sample analysis were also estimated. From the linear plot of scan rate, charge transfer rate constant (Ks), surface concentration of electrode (γ), and diffusion coefficient (D) have been calculated, and these are found to be 6.56 × 10−1 s−1, 1.21 × 10−7 mol cm−2, and 6.99 × 10−3 cm2 s−1, respectively. This biosensor exhibits the linear range of vitamin B2 detection from 1 to 40 μM, including sensitivity and limit of detection (LOD) of 1.37 × 10−3 mA/μM cm2 and 0.254 μM, respectively. For higher concentration range detection linearity is 50–100 μM, with sensitivity and the LOD of 1.26 × 10−3 mA/μM cm2 and 0.145 μM, respectively. The results indicate that the bio-inspired nanomaterials are promising sustainable biosensing platforms for various food and health-based biosensing devices.

Suppressed atmospheric chemical aging of cooking organic aerosol particles in wintertime conditions

Abstract. Cooking organic aerosol (COA) is one of the major constituents of particulate matter in urban areas. COA is oxidized by atmospheric oxidants such as ozone, changing its physical, chemical and toxicological properties. However, atmospheric chemical lifetimes of COA and its tracers such as oleic acid are typically longer than those that have been estimated by laboratory studies. We tackled the issue by considering temperature. Namely, we hypothesize that increased viscosity of COA at ambient temperature accounts for its prolonged atmospheric chemical lifetimes in wintertime. Laboratory-generated COA particles from cooking oil were exposed to ozone in an aerosol flow tube reactor for the temperature range of −20 to 35 °C. The pseudo-second-order chemical reaction rate constants (k2) were estimated from the experimental data by assuming a constant ozone concentration in the flow tube. The estimated values of k2 decreased by orders of magnitude for lower temperatures. The temperature dependence in k2 was fit well by considering the diffusion-limited chemical reaction mechanism. The result suggested that increased viscosity was likely the key factor to account for the decrease in chemical reactivity at the reduced temperature range, though the idea will still need to be verified by temperature-dependent viscosity data in the future. In combination with the observed global surface temperature, the atmospheric chemical lifetimes of COA were estimated to be much longer in wintertime (&gt; 1 h) than in summertime (a few minutes) for temperate and boreal regions. Our present study demonstrates that the oxidation lifetimes of COA particles will need to be parameterized as a function of temperature in the future for estimating environmental impacts and fates of this category of particulate matter.

Nitrofurazone biodegradation kinetics by batch fermentation of Aspergillus tamarii

Nitrofurazone (NFZ) compound contains a 5-nitrofuran ring structure that has been widely used as feed additives in animal husbandry. Due to the benzene ring structure, the residues are highly toxic to humans and animals. A kinetics study of NFZ biodegradation in batch fermentation with Aspergillus tamarii KX610719.1 was conducted. The main objectives were to determine the kinetic parameters of fungal growth, glucose consumption, protein production, and biodegradation of NFZ using fungal biomass. Kinetic parameters were determined using Polymath 6.0 software, and regression analysis was done using linear and non-linear methods. After 168 hours of batch fermentation, the maximum specific growth rate (µmax), and maximum cell concentration (Xmax) for cultivation without NFZ were 0.062 h-1, and 0.529 g L-1, respectively. The maximum specific growth rate (µmax), and maximum cell concentration (Xmax) for cultivation with NFZ were 0.092 h-1, and 0.327 g L-1, respectively. For glucose consumption, kinetic parameters of Yield of biomass over the substrate (YXS) and cell maintenance (mS) were estimated at 0.139 g g-1 and 0.239 h-1, respectively. Based on the Luedeking Piret model, the estimated growth-associated (α) and non-growth-associated (β) constants were 1.142×10-2 g g-1 and 5.680×10-5 h-1, respectively. The rate constant (k1) of NFZ biodegradation was estimated at 2.696×10-2 h-1 following the first-order model where the rate constant of NFZ removal is dependent on the NFZ concentration. The application of A. tamarii batch fermentation in the removal of NFZ compound was sufficient with a total percentage removal of 85.9 % or 0.430 g L-1 recorded.

Multiparameter optimization of non-thermal plasma-driven synthesis of carbohydrate-stabilized rhenium nanoparticles towards enhancement of their catalytical activity for reduction of nitroaromatic compounds

This study aims to optimize the synthesis of carbohydrate-stabilized rhenium nanoparticles (ReNPs) utilizing cold atmospheric pressure plasma (CAPP), specifically direct current atmospheric pressure glow discharge (dc-APGD), hypothesizing that controlling synthesis parameters will enhance catalytic efficiency in the reduction of nitroaromatic compounds (NACs). The dc-APGD system operated in flowing liquid cathode (FLC-dc-APGD) and flowing liquid anode (FLA-dc-APGD) modes. Design of experiments (DOE) and response surface methodology (RSM) were employed for the first time to optimize ReNPs synthesis by adjustment of the concentration of ReO4- in ReNPs precursor solution, its flow rate, as well as the discharge current. ReNPs were characterized using high-resolution transmission electron microscopy (HRTEM), dynamic light scattering (DLS), and X-Ray photoelectron spectroscopy (XPS). In turn, optical emission spectroscopy (OES) was employed for the identification of reactive species generated in the plasma phase that contributed to the synthesis of ReNPs. The resultant sizes, surface charges, and phase compositions were linked with synthesis parameters and then with catalytic activities revealed by the variety of ReNPs. HRTEM photomicrographs showed spherical and spherical-like morphologies of the obtained ReNPs synthesized using FLC-dc-APGD and FLA-dc-APGD modes with the actual sizes of 7.28 ± 2.90 nm and 3.24 ± 0.57 nm, respectively. The optimized conditions yielded ReNPs of exceptional catalytic activity, that reduced 94.9 % (FLC-dc-APGD) and 90.5 % (FLA-dc-APGD) of 4-nitrophenol (4-NP) with the apparent rate constants (k1) 0.269 and 0.107 min−1, respectively. Further, the conversions of 90 % were achieved over FLC-dc-APGD-based ReNPs for nitrobenzene (NB), 2,4,6-trinitrophenol (2,4,6-TNP), 2,4-dinitrophenol (2,4-DNP), and 4-nitroaniline (4-NA). In these cases, the k1 values were 0.235, 0.174, 0.070, 0.001 min−1, respectively. The results allowed to find a correlation between ReNP size distribution, oxidation state, and catalytic activity that suggested a potential for tailored Re nanocatalysts in environmental remediation.