Order Reaction Rate Research Articles

Ag induced plasmonic TiO2 for photocatalytic degradation of pharmaceutical under visible light: Insights into mechanism, antimicrobial and cytotoxicity studies

Global concerns include water scarcity and shortage, which are escalated by organic pollutants such as naproxen (NPX) that deteriorate drinking water and taint access to safe drinking water by humans. Moreover, NPX may cause gastrointestinal difficulties, cardiovascular risks, kidney damage, allergic reactions, liver toxicity, bleeding issues and pregnancy risks, hence it is essential to remove it in water. Ag-TiO2 was synthesized by hydrothermal method for NPX degradation. Ag on TiO2 reduced the band gap and surface area of TiO2 and resulted in a plasmonic Ag-TiO2 composite of 0.2 % Ag. The photocatalytic degradation of 0.2 % Ag-TiO2 was 80 % in 180 minutes using a solar simulator during NPX degradation with a first order reaction rate that was 3.6 times faster than that of pure TiO2 and the catalyst showed good stability for four cycles. The dual activity of Ag0 surface plasmon resonance improved light absorption capability and enhanced charge transfer for increased photodegradation rate and stability. The antibacterial studies demonstrated that 0.2 % Ag-TiO2 posted strong antibacterial properties under light irradiation and less in the dark, with a greater effect on gram-negative than gram-positive bacteria. The minimum inhibitory concentration (MIC) values of 620, 1250, 2500, 2500 µg/mL were attained against B. subtilis, S. aureus, E. coli and S. typhimurium bacteria, respectively. The low cell toxicity of 0.2 % Ag-TiO2 was determined using human embryonic kidney (HEK293) cells with an inhibitory concentration (IC50) of 61.09 ± 0.24 µg/mL under light irradiation. Radical trapping experiments demonstrated that hydroxyl radicals (OH•) played a vital role during the degradation and bactericidal activity of NPX under light irradiation. This work advances new insights on the synthesis of less toxic nanoparticles with high photocatalytic and bactericidal activity for possible applications at industrial scale.

Light switchable radical and non-radical periodate activation by Fe3O4/g-C3N4 for efficient organic contaminant elimination

Although the heterogeneous activation of periodate (PI) has recently garnered significant attention for organic pollutant degradation, regulating the non-radical and radical reaction pathways remains a challenge. Herein, a Z-scheme Fe3O4/g-C3N4 heterojunction (FCN) was developed to achieve controllable radical and non-radical PI activation using a light switch. In the dark, the interaction between FCN and PI gave rise to metastable surface-activated PI complexes (PI*) via the non-radical pathway, which served as the dominant reactive species for organic elimination. Upon light irradiation, FCN acted as an electron donor for PI activation via the radical pathway, forming iodate radicals (IO3•) for pollutant destruction. Consequently, the FCN/PI/VIS system achieved complete removal of acid orange 7 in 30 min, with a pseudo-first order reaction rate about 3.5 times higher than that of FCN/PI system. The involved reactive species were validated by scavenging tests, electron paramagnetic resonance (EPR) analysis, Raman spectra and electrochemical measurements. Moreover, the light switchable FCN-based PI activation system exhibited high recyclability and practicability for the treatment of various organic pollutants in water. This study provides new insights into the PI activation-mediated wastewater treatment processes.

Green synthesis of Z-scheme CeO2 decorated ZnO nanocomposites for photodegradation of organic pollutants, antioxidant activity and its effects on seed germination

The present work aimed to report a green synthesis of CeO2@ZnO nanocomposites via co-precipitation method using azadirachta indica aqueous leaf extract. The characterization of the prepared CeO2@ZnO nanocomposites were done using XRD, FTIR, SEM, EDAX, UV–vis, and PL techniques to examine the structural properties, functional group, morphological and electronic properties. As prepared CeO2@ZnO nanocomposites have been used for photo degradation of Crystal Violet (CV), Methylene blue (MB) and Rhodamine B (RhB) dyes in presence of solar light in aqueous solution. From structural analysis the mean crystallite sizes of the synthesized nanocomposites varied from 27 nm to 9 nm. The degradation of MB, CV and RhB dyes follows pseudo-first order reaction rate with the rate constantsk1 for MB is 10.09 × 10−3 min−1, k1 for CV is 8.71 × 10−3 min−1, k1 for RhB is 0.92 × 10−3 min−1.The characterized nanocomposites were used for seedling growth, physiological and biochemical responses during seed germination. In CeO2@ZnO nanocomposites treatments, significantly higher values of shoot length and root length were observed in CZ1 (0.5, and 1 mg/ml) treated seedlings as compared to other samples. Similarly, the activities of ɑ-amylase and protease enzymes were recorded to be maximum for CZ1 nanocomposites. For instance, the increased activity of α-amylase was observed to be 2.12, 2.09, and 1.33 folds higher in CZ1, CZ2, and CZ3 (1 mg/ml) treated seedlings as compared to the control. Similarly, the protease activity was reported to be increased by 0.011 folds in CZ1 nanocomposites (1 mg/ml) treated seedlings as compared to the control. Furthermore, all the CeO2@ZnOnanocomposites have excellent DPPH, and ABTS free radical scavenging activities, confirmed by the Ferric-Reducing Antioxidant Power (FRAP) assay. The CZ1 nanocomposites showed the best results. The CeO2@ZnO nanocomposites were found to have no toxic effects on cellular division confirmed with improved mitotic index under different treatment regimens.

A multipurpose organometallic pyridyl Schiff base-modified poly(divinylbenzene) matrix for the catalytic removal of nitrophenols and polycyclic pollutants

Widespread organic pollutants in wastewater include toxic nitrophenols and polycyclic molecules. Here, we aim to develop a single multipurpose catalyst capable of degrading these structurally dissimilar contaminants by preparing a pyridyl Schiff base-functionalized poly(divinylbenzene) porous organic polymer displaying Ag complexes (PDVB-PA@Ag). PDVB-PA@Ag hydrogenated 4-nitrophenol (4-NP) efficiently to valuable and less toxic 4-aminophenol with an optimized reaction rate of 45.4 × 10−3 s−1 and apparent activation energy of only 20.1 kJ mol−1. The same catalyst also readily hydrogenated the isomers of 4-NP as well as nitrophenols with several nitro groups and halogenated nitrophenols with reaction rates ranging from 4.0 to 20.3 × 10−3 s−1. In addition, the multiuse PDVB-PA@Ag was capable of carrying out a second type of reaction and degraded multiple polycyclic dyes commonly found in wastewater including auramine O, basic blue 17, aniline blue, and malachite green through Fenton-like oxidation. PDVB-PA@Ag-based degradation processes for the four toxic dyes evaluated were efficient with pseudo-first order reaction rates varying between 1.2 × 10−2 to 3.7 × 10−2 min−1. By coordinating an array of versatile catalytic complexes on an extensive and stable porous support, PDVB-PA@Ag was made highly performant at completing different essential water-cleaning processes.

Entropy generated nonlinear mixed convective beyond constant characteristics nanomaterial wedge flow

Background and objectiveNanomaterial flows at present have received much attention of the researchers. Such motivation stems for their utilization in pharmaceutical, industrial, petroleum, manufacturing and engineering applications including regenerative medicine, treatment of cancer, electronic device cooling, solar collector, mineral oil, antimicrobial agents, thermal storage system, transformer cooling and X-imaging etc. Higher thermal energy requirement in several electrical and mechanical systems is desired in recent time due to high advancement of science and technology. For important application here the stagnation point flow due to wedge with nonlinear convection is explored. For porous media, the Darcy-Forchheimer relation is considered. Characteristics of nanofluid is added by utilizing Buongiorno's model. Variable fluid characteristics are under consideration. Applied magnetic field is accounted. Energy expression comprises thermal radiation, Brownian motion, Ohmic heating, thermophoresis and heat generation. First order reaction and entropy rate are considered. MethodologyNonlinear differential expressions are changed into dimensionless ordinary systems through adequate transformations. The resultant nonlinear ordinary systems are solved through optimal homotopy analysis technique (OHAM). ResultsOutcomes for influential variables about temperature, velocity, concentration and entropy rate have been arranged. Here results show that for magnetic field the liquid flow and entropy rate have opposite scenarios. Thermal distribution and concentration have reverse effects for random motion variable while similar effect holds for thermophoresis parameter. Magnetic field and diffusion parameters contribute to augment entropy generation. Higher values of temperature dependent electrical conductivity variable lead to increase entropy rate. Thermal distribution for radiation and Eckert number is similar.

A Study of Micellar Catalyses on Oxidation of Glycine by QDC in the Presence of Sodium Dodecyl Sulphate (SDS) in Aqueous Perchloric Acid Medium

Aims: To study the micellar effect of SDS on the oxidation of glycine by Quinolinium Dichromate (QDC) in perchloric acid medium. Background: Among the amino acids, glycine plays a major role in multiple metabolic reactions, such as glutathione synthesis and one-carbon metabolism. The oxidation of glycine has received importance because it is the major neurotransmitter inhibitor in the spinal cord and brainstem. In the oxidation process of amino acids, highly toxic chromium (VI) compounds are converted into non-toxic chromium (III) by quinolinium dichromate (QDC) oxidant in an appropriate pH value medium. Objective: 1. To study the catalytic role of anionic surfactant (SDS) on the oxidation of glycine by QDC through micellization, evaluation of critical micelles concentration (CMC) in the presence and absence of glycine and other surface properties along with thermodynamic quantities. 2. Determination of rate constant and order of reaction with respect to QDC, glycine, acid and surfactant which will help to study the kinetics of the reaction 3. Analysis of oxidation product by FT-IR and calculation of activation parameters. 4. Synthesis of oxidant (QDC) and its characterization by UV-Visible spectrophotometer and NMR spectroscopy. Results: First-order kinetics was observed with respect to oxidant, glycine and hydrogen ions. The rate of reaction increased remarkably with an increase in the concentration of surfactant (SDS). The kinetic results show that the ionic strength variation does not have any significant effect on the rate whereas the increase in the dielectric constant of the medium shows a remarkable effect on the rate constant. From stoichiometry study, it was found that 2 moles of oxidant (QDC) consumed 3 moles of glycine to produce aldehyde (Formaldehyde). Conclusion: The observed negative value of (ΔS) entropy of activation and positive (ΔH) enthalpy of activation suggests a more ordered activated complex formation and highly solvated transition state. The kinetics of the reaction in a perchloric acid medium is found to be accelerated in the presence of surfactant (SDS). The kinetics of the reaction follow pseudo first-order decay of Cr(VI) species (QDC), a unity dependence of rate on glycine and perchloric acid. The oxidation product formaldehyde was identified by FTIR. NMR spectrum analysis of synthesized QDC shows a resemblance with pure QDC.

Photo Fenton-like oxidation of real textile wastewater: Operating conditions, kinetic modelling and cost analysis

The reusability of the pretreated textile wastewater was improved by using bismuth ferrite/activated carbon hybrid photocatalysts in photo-Fenton-like oxidation process. BiFeO3/WAC (WAC: walnut shell based activated carbon) and BiFeO3/CAC (CAC: Commercial activated carbon) catalysts were synthesized and used for the photocatalytic oxidation of in-situ pretreated textile wastewater. The influences of the mixing speed, oxidant dosage, light source, catalyst loading, and temperature were studied. The highest TOC removal efficiencies were evaluated as 56.3% and 76.2% in the presence of BiFeO3/WAC and BiFeO3/CAC, respectively. A kinetic study was performed to derive the kinetic models expressing the TOC removal as a basis for the semi-pilot and industrial scale studies. The kinetic data fit to a two-step second order reaction rate model in the presence of both of the catalysts. The activation energies of the first and the second steps were calculated as 36.0 and 16.0 kJ/mol, respectively, on BiFeO3/WAC catalyst while 43.4 and 13.3 kJ/mol of activation energies were calculated on BiFeO3/CAC.

ELECTROSYNTHESIS OF Cu2O IN THE Cu(s)|CuSO4(aq)|Fe(s) REACTOR AND DEGRADATION POTENT FOR METHYLENE BLUE

Research on Cu synthesis2O uses the electrolysis method in the Cu(s)|CuSO4(aq)|Fe(s) system and degradation tests on methylene blue. Cu2O is a blackish-red solid which has properties as a semiconductor with a band gap of around 2-2.2 eV. These transition metal oxides are widely used as catalysts, solar cell components, and photodetectors. This research aims to synthesize Cu2O with variations in electrolysis time, determine the characteristics of Cu2O using FTIR and XRD, and test the degradation of methylene blue. The method used is electrolysis with a fixed potential and time variations. Research stages include solution preparation, determination of decomposition potential, electrolysis of samples under various conditions, and analysis. The results of determining the decomposition potential are used as the application potential value in the copper electrolysis process, namely 3.25 V. Sample electrolysis was carried out at a potential of 3.25 V, solution pH 4.0 in a volume of 100 mL at 30, 60, 90, and 120 respectively. and 150 minutes. The products obtained were analyzed using Fourier Transform Infra-Red (FTIR) and X-ray diffraction (XRD). The results of FTIR analysis show that before calcination there is a Cu-O functional group with a wave number of 477.23 cm-1 and after calcination, there is a Cu-O functional group with a wave number of 538.28 cm-1 which indicates the formation of oxide. The results of XRD analysis show that the value of 2θ before calcination is 36.553; 50,481 ; 62.855 which shows the peak of Cu and after calcination 29.928; 36,027 ; 61.568 shows the Cu2O peak. The highest photocatalytic activity test results for Cu2O against methylene blue were 85.96%. The rate of degradation of methylene blue by Cu2O follows the second order reaction rate equation with the R2 value and reaction rate constant being 0.9418 and 0.00769572 L mol-1 s-1, respectively.

Preparation of an efficient and reusable cobalt doped vermiculite ore catalyst for hydrogen production from sodium borohydride

In this study, the applicability of a Co2+-doped catalyst [(Co-Ver)cat] fabricated from clay vermiculite ore for the synthesis of hydrogen from sodium borohydride was investigated. FT-IR, XRD, SEM, Brunauer-Emmett-Teller (BET) analysis, and X-ray fluorescence (XRF) studies were used to characterize the synthesized (Co-Ver)cat. After activation with 1 M HCl, 0.15 g the 30% Co2+-doped catalyst (7% NaOH, 2.5% NaBH4, 30 °C process temperature) produced the maximum catalytic activity. Under these conditions, the hydrogen generation rate of 1991,39 ml gCo−1 min−1was achieved with the (Co-Ver)cat. The NaBH4 hydrolysis reaction had an activation energy of 43.58 kJ mol−1 and a reaction rate order (n) of 0.18. It was also determined that the prepared (Co-Ver)cat exhibited good reusability. The reusability of the (Co-Ver)cat prepared from vermiculite ore was high, and 91.78% of the expected hydrogen amount was obtained as a result of its 10th use.

Development of novel API-based deep eutectic solvents for esterification of high free fatty acid

Low-value feedstocks containing high free fatty acid (FFA) content are incompatible with direct alkali-catalysed transesterification, and require a deacidification step through esterification to reduce its FFA level. Herein, innovative acid catalysts were developed based on deep eutectic solvents (DESs) to pretreat low-quality palm oil (12.43 % FFA). DESs were formed using Brønsted acids (5-sulfosalicylic acid and benzenesulfonic acid) and an active pharmaceutical ingredient (paracetamol) at a 3:1 molar ratio. The DESs were characterized using ATR-FTIR and Hammett acidity function (H0). DES catalyst dosage, methanol requirement, reaction time and temperature parameters were optimized, and its recyclability was evaluated. The FFA contents were reduced to below the limit of < 2 % using acidic DESs at optimized conditions. Reaction kinetics revealed that DES-catalysed reactions followed the pseudo first order rate of reaction and required the lowest activation energy of 40.91 kJ/mol. Through the Eyring-Polanyi thermodynamic study, the DES-catalysed esterification reactions were endothermic (ΔH° > 0), non-spontaneous (ΔS° < 0 and ΔG° > 0) and endergonic. COSMO-RS computational calculations reveal the viable formation of the DESs based on its moieties, and supports the good solubility of the DESs in methanol. This study demonstrates the feasible valorisation of low-value feedstocks using innovative catalysts in enabling biodiesel production.

Combustion performance of hydrogen fueled parallel wall-jet used for drag reduction in a supersonic combustor

Hydrogen fueled parallel wall-jet combustion is considered to be one of the most promising drag reduction technologies in supersonic combustors, researchers mainly focus on its drag reduction mechanism, while balancing its combustion efficiency and drag reduction performance is of great significance for engine performance and energy conservation. In this paper, combustion performance of hydrogen fueled parallel wall-jet is numerically investigated. Kinetic reaction rate and scalar dissipation rate are defined to decouple the chemical reaction and mixing processes. Results indicate that although hydrogen fueled parallel wall-jet combustion is a nonequilibrium chemical reaction process, the combustion process is dominated by mixing due to the much larger magnitude order of kinetic reaction rate. The investigation also reveals that, compared to the effects of mainstream total temperature, mainstream Mach number presents a more significant effect on combustion efficiency. Moreover, combustion efficiency increase first brings negative and then brings beneficial effects on drag reduction performance, which is due to the different sensibilities of the two skin friction determinants viscosity and velocity gradient to combustion efficiency. It is found that, viscosity is more sensitive to combustion efficiency, with combustion efficiency increases by 5.4 %, viscosity increases by 4.15 %, while velocity gradient only decreases by 2.19 %.

Degradation and mineralization of anti-cancer drugs Capecitabine, Bicalutamide and Irinotecan by UV-irradiation and ozone

The degradation of three anti-cancer drugs (ADs), Capecitabine (CAP), Bicalutamide (BIC) and Irinotecan (IRI), in ultrapure water by ozonation and UV-irradiation was tested in a bench-scale reactor and AD concentrations were measured through ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). A low-pressure mercury UV (LP-UV) lamp was used and degradation by UV (λ = 254 nm) followed pseudo-first order kinetics. Incident radiation in the reactor was measured via chemical actinometry using uridine. The quantum yields (φ) for the degradation of CAP, BIC and IRI were 0.012, 0.0020 and 0.0045 mol Einstein−1, respectively. Ozone experiments with CAP and IRI were conducted by adding ozone stock solution to the reactor either with or without addition of tert-butanol (t-BuOH) as radical quencher. Using this experimental arrangement, no degradation of BIC was observed, so a semi-batch setup was employed for the ozone degradation experiments of BIC. Without t-BuOH, apparent second order reaction rate constants for the reaction of the ADs with molecular ozone were determined to be 3.5 ± 0.8 ∙ 103 L mol−1 s−1 (CAP), 7.9 ± 2.1 ∙ 10−1 L mol−1 s−1 (BIC) and 1.0 ± 0.3 ∙ 103 L mol−1 s−1 (IRI). When OH-radicals (∙OH) were quenched, rate constants were virtually the same for CAP and IRI. For BIC, a significantly lower constant of 1.0 ± 0.5 ∙ 10−1 L mol−1 s−1 was determined. Of the tested substances, BIC was the most recalcitrant, with the slowest degradation during both ozonation and UV-irradiation. The extent of mineralization was also determined for both processes. UV irradiation was able to fully degrade up to 80% of DOC, ozonation up to 30%. Toxicity tests with Daphnia magna (D. magna) did not find toxicity for fully degraded solutions of the three ADs at environmentally relevant concentrations.

Key role of carbon as an efficient electron bridge in CuO@C@Fe2O3 for enhancing H2O2 activation during photo-assisted Fenton-like reaction

The Fe3+/Fe2+ cycle has been identified as the rate-limiting step in the Fenton system, and many efforts have been made to promote the Fe3+ reduction via external electrons provided by various electron donors. However, how to design an efficient electron transport pathway and then inhibit the invalid electron shuttle has been largely underestimated. In this study, two kinds of heterogeneous Fenton catalysts of CuO@Fe2O3 and CuO@C@Fe2O3 were prepared. The key role of carbon in transporting electrons as an electron bridge and its enhancement mechanism in photo-assisted Fenton-like performances were explored in detail. Compared with CuO@Fe2O3, the removal efficiency of tetracycline (TC) and the corresponding pseudo-first order reaction rate constants over CuO@C@Fe2O3 increased significantly from 88.6 % and 0.1054 min−1 to 99.7 % and 0.2058 min−1, respectively. Based on a series of probe experiments, visible light irradiation can promote the reduction of Cu2+ to Cu+, then the carbon in CuO@C@Fe2O3 can effectively transfer electrons from Cu+ to Fe3+, enhancing the Fe3+/Fe2+ cycle and the following Fenton-like efficiency. Since more ·OH while less ∙O2- was produced over CuO@C@Fe2O3, which further supports the fact that the enhanced Fe3+/Fe2+ cycle was due to the transfer electron from Cu+ to Fe3+ instead of the Haber-Wiss mechanism. Hence, this study provides new insight for effectively improving the transfer efficiency and effective utilization of electrons in Fenton systems.

Analysis and design of antithetic proportional-integral-derivative biocontrol-systems with species dilution

The nonlinearity and non-separability of the antithetic PID (aPID) controller have provided greater flexibility in the design of biochemical reaction networks (BCRNs), resulting in significant impacts on biocontrol-systems. Nevertheless, the dilution of control species is disregarded in designs of aPID controllers, which would lead to the failure of inhibition mechanism in the controller and loss of robust perfect adaptation (RPA)—the biological counterpart of robust steady-state tracking. Here, the impact of dilution processes on the structure of aPID is investigated in this study. It is discovered that the proportional and low-pass filters are altered when the dilution processes is present in control species, which increases the coupling between the controller parameters. Moreover, additional integrations for the reference signal and control output generated by control species dilution further leads to the loss of RPA. Subsequently, a novel aPID controller represented by BCRNs, termed quasi-aPID, has been designed to eliminate the detrimental effects of the dilution processes. In an effort to ameliorate the interdependencies among controller parameters, a degradation inhibition mechanism is employed within this controller. Furthermore, this work establishes the limiting relationship between the controller’s reaction rates in order to guarantee RPA, while abstaining from the introduction of supplementary species and biochemical reactions. By using the quasi-aPID controller in both the Escherichia coli gene expression model and the whole-body cholesterol metabolism model, its effectiveness is confirmed. Simulation results demonstrate that, the quasi-aPID exhibits a smaller absolute steady-state error in both models and guarantees the RPA property.

Enhanced photocatalytic gaseous formaldehyde degradation using N-CQDs/OVs-TiO2 composite under visible light: Unraveling the synergistic effects of N-CQDs and oxygen vacancies

Limited utilization of photogenerated charge carriers in titanium dioxide under visible light have hinder its application development. To address this challenge, a novel N-doped carbon quantum dots (N-CQDs) and oxygen vacancies (OVs) synergistically decorated on TiO2 (P25) was synthesized through a facile one-step hydrothermal method. Under visible light irradiation, the first order reaction rate constants of formaldehyde (HCHO) photocatalytic oxidation by OVs-TiO2 and N-CQDs/OVs-TiO2 was significantly higher than that of pristine P25, with 10.1 and 16.7 folds increase, respectively. Characterization results confirmed the generation of OVs on the surface of N-CQDs/TiO2 composite. The optical and electrochemical experiments suggested the electron capture center effect of OVs and the properties of N-CQDs in unique up-converted photoluminescence, efficient charge separation, as well as significant adsorption in visible light region. In addition, the work function also clarified that photoelectrons could transfer from N-CQDs to OVs-TiO2. Furthermore, different relative humidity and electron paramagnetic resonance (EPR) experiments demonstrated that the hydroxyl radical (•OH) was the dominant reactive radical in HCHO photodegradation. The •O2− could also enhance the photodegradation efficiency of HCHO. This work provides an in-depth understanding on the complementary roles of N-CQDs and OVs and is helpful for designing metallic oxide photocatalysts for volatile organic compounds removal.

Application of electro oxidation process for treating wastewater from petrochemical with mixed metal oxide electrode

Petrochemicals require a large volume of water for their operation, which results in the production of a large volume of wastewater. Treatment of petrochemical wastewater is an important process before discharging it into the environment. This research examines the treatment of real petrochemical wastewater using the electrochemical oxidation process. Direct anodic oxidation is an effective advanced electrochemical oxidation process (AEOP), with different electrodes using a parallel plate electrochemical reactor. Four types of real wastewater were received from different petrochemical units were treated by AEOP. Real wastewater samples with chemical oxygen demand (COD) concentrations ranging from 20,450 to 52,300 mg/l. The main goal of this research is to make electrodes of Mixed Metal Oxide (MMO), which can reduce the treatment time and electricity consumption for oxidation, greater stability of the surface of the electrodes. Investigation of the rate constant kinetics shows that high COD removal efficiency can be achieved following the pseudo-second order reaction rate (R2 > 98%). When the wastewater pH is less than 5, COD removal efficiency is higher and the treatment process will be successful, which succeeded in removing 79% COD, but in alkaline wastewater, COD reduction efficiency was not satisfactory. The electricity consumption for 79% removal during 6 min was 117 kWh/m3. As a result, due to the very short time of the process (6 min), it can be used as one of the pre-treatment steps of petrochemical wastewater with acidic pH.

Theoretical and experimental study on the N2O reduction by H2 over char decorated with transition metal at low temperatures

In this study, a catalytic system for N2O reduction by H2 onto char decorated with transition metals is proposed, which have excellent reduction efficiency at low temperatures below 200 °C and efficiently utilizes pyrolysis char and hydrogen. Density functional theory (DFT) is used to reveal the reaction mechanism and found that transition metal decoration can significantly promote reaction rate and decrease the activation energy required for N2O reduction by H2 on char, from 383.7 kJ/mol to 50–160 kJ/mol. Furthermore, transition states in the process of reducing N2O by H2 over metal-char were observed, including reduction of N2O and the removal of the surface oxygen complex. Through kinetic analysis, the activation energy and reaction rate order was found as Ni-char (50.0 kJ/mol)>Co-char (95.1 kJ/mol)>Fe-char (151.0 kJ/mol)>Cu-char (158.8 kJ/mol). According to experiments phenomenon, the sequence of reduction efficiency over different metal-char was consistent with the simulation results and it was even possible to convert N2O to N2 below 200 ℃. This research contributes to a more mechanistic understanding of the N2O-H2 reaction over char and provides new insights for improving the design of catalysts for N2O abatement at low temperatures.

Comparative study of metal nanoparticles anchored TiO2 using polyoxometalate intermediate in photodegradation of azo dye pollutant in aquatic environments

Herein, metal nanoparticles (Au, Ag, and Pt) are locally deposited on TiO2 with an UV-switchable polyoxometalate intermediate to achieve highly active photocatalyst nanohybrids. The successful preparation of these nanohybrids was confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), Zeta potential (ZP), and UV–visible spectroscopy. TEM images showed the anchoring of metal nanoparticles of an average size of 20 nm on the TiO2 surface. A comparative study revealed that the bandgap energy was reduced in the order of Pt@PW-TiO2 (2.90 eV) > Ag@PW-TiO2 (2.95 eV) > Au@PW-TiO2 (3.05 eV). Likewise, the photocatalytic efficiency of fabricated nanohybrids was investigated in the degradation of reactive blue 19 (RB19), an azo dye model, under UV–visible light illumination and different experimental conditions. Optimal photodegradation occurred at pH = 3.8 with 0.33 gL−1 of photocatalyst exposed to light for 60 min. Under optimal conditions, the maximum and minimum photodegradation abilities were observed using Pt and Au deposited hybrids. A kinetic study of RB19 photodegradation was also conducted, resulting in pseudo-first order reaction rate constants of 0.0203, 0.025, and 0.0808 min−1, respectively, for the Au@PW-TiO2, Ag@PW-TiO2, and Pt@PW-TiO2 nanohybrids. Finally, the most probable mechanism for RB19 degradation using prepared photocatalysts is presented.

Theoretical Approach toward a Mild Condition Haber-Bosch Process on the Zeolite Catalyst with Confined Dual Active Sites.

The Haber-Bosch (H-B) process is today's dominant technology for ammonia production, but achieving a mild reaction condition is still challenging. Herein, we combined density functional theory (DFT) calculations and microkinetic modeling (MKM) to demonstrate the feasibility of conducting the H-B process under ambient conditions on a zeolite catalyst with confined dual active sites. Our designed dual Mo(II) cation-anchored ferrierite [2Mo(II)-FER] catalyst shows an energy barrier of only 0.58 eV for N≡N bond breaking due to the enhanced π-back-donation. Meanwhile, the three hydrogen sources (BH, FMH, and NMH) within 2Mo(II)-FER greatly enrich the hydrogenation mechanisms of NHx species, resulting in barriers of <1.1 eV for NHx (x = 0-2) hydrogenations. This dual-site catalyst properly decouples the N2 dissociation and NHx hydrogenation steps, which elegantly circumvents the linear scaling relation between the N2 dissociation barrier and the nitrogen binding energy. It is worth noting that our MKM results show 4 orders of magnitude higher reaction rates on 2Mo(II)-FER than the stepped sites of the FCC Ru catalyst at low temperatures, paving a solid basis to conduct the H-B process at low temperatures. We believe that our strategy will provide crucial guidance for synthesizing state-of-the-art zeolite catalysts to achieve the near-ambient condition H-B process and other chemical reactions in heterogeneous catalysis.

Kinetics of Essential Oil Extraction of Kaffir Lime Peel Using Microwave Assisted Hydrodistillation

The purpose of this study is to study the kinetics of kaffir lime peel essential oil extraction using microwave assisted hydrodistillation. Extraction was carried out at various powers and the ratios of material to solvent for 1 hour. Soxhlet extraction using n-hexane solvent was also carried out to determine the yield of essential oil. The extraction kinetics was investigated using a mass transfer-controlled approach and expressed by the 1st and 2nd order of reaction rate. The Soxhlet extraction results indicated that the yield of kaffir lime peel essential oil was 5.65% w/w. The higher the microwave power being applied (180, 300, 450, and 600 Watt), the higher the essential oil yielded (2.2; 2.8; 3; and 3.8% w/w), respectively, but at 800 Watt, the yield decreased (3.2% w/w). The smaller the ratio of material to solvent, which means more diluted, the lower the yield of oil were, namely from 4.56; 3.9; and 3.8% w/w, at ratios of material to solvent 1:3, 1:3.5, and 1:4 w/v. Different results were obtained at a ratio of 1:3 (4.56% w/w) which produced a yield greater than the ratio of 1:1.25 (2.88% w/w). Therefore, the optimum conditions for extracting kaffir lime peel essential oil were at 600 Watt and a ratio of material to solvent 1:3 w/w for 56 minutes with a yield of 4.58% and a density of 0.86 g/cm3. The kinetics of the 2nd order of homogeneous model better represented results of the experiments with extraction rate constants at 180, 300, 450, 600, and 800 Watt of 14.89; 14.95; 15.53; 21.32; and 19.85 L.g-1.min-1. While the extraction rate constants at the material to solvent ratio of 1:2.5; 1:3; 1:3.5; and 1:4 w/v of 17.38; 19.80; 22.09; and 32.31 L.g-1.min-1. The extraction capacity was also affected by the power and the ratio of material to solvent, the extraction capacity were 0.0095; 0.0100; 0.0104; 0.0125; and 0.0106 g.L-1, at 180, 300, 450, 600, and 800 Watt respectively, and 0.0094; 0.0134; 0.0134; and 0.0118 g.L-1, at material to solvent ratio of 1:2.5; 1:3; 1:3,5; and 1:4 w/v respectively.