Synthesis,characterization, and thermal degradation of oligo‐2‐(morpholinoiminomethyl)phenol and its Pb(II) complex compound

The oxidative polycondensation reaction conditions of 2‐(morpholinoiminomethyl)phenol were studied with H₂O₂, air O₂, and sodium hypochloride (NaOCl) oxidants in an aqueous alkaline medium between 40 and 90°C. The structure of oligo‐2‐(morpholinoiminomethyl)phenol was characterized with ¹H‐ and ¹³C‐NMR, Fourier transform infrared, ultraviolet–visible, size exclusion chromatography, and elemental analysis techniques. Under the optimum reaction conditions, the yield of oligo‐2‐(morpholinoiminomethyl)phenol was 28% for the H₂O₂ oxidant, 12% for the air O₂ oxidant, and 58% for the NaOCl oxidant. According to the size exclusion chromatography analysis, the number‐average molecular weight, weight‐average molecular weight, and polydispersity index of oligo‐2‐(morpholinoiminomethyl)phenol were 2420 g/mol, 2740 g/mol, and 1.187 with H₂O₂, 1425 g/mol, 2060 g/mol, and 1.446 with air O₂, and 1309 g/mol, 1401 g/mol, and 1.070 with NaOCl, respectively. Thermogravimetry/dynamic thermal analysis showed that the oligo‐2‐(morpholinoiminomethyl)phenol–lead complex compound was more stable than 2‐(morpholinoiminomethyl)phenol and oligo‐2‐(morpholinoiminomethyl)phenol against thermal degradation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3795–3804, 2006     

Performance evaluation of a continuous flow Photo-Impinging Streams Cyclone Reactor for phenol degradation

In this study, an impinging streams cyclone reactor has been utilized as a novel apparatus in photocatalytic degradation of phenol. Degussa P25 TiO₂ nano particles have been applied as the photocatalyst under UV radiation. The operating parameters including catalyst loading, pH, initial phenol concentration and light Intensity have been found to affect the efficiency of the photocatalytic degradation process within this photoreactor. Photocatalytic degradation of phenol has been also investigated in a continuous flow impinging streams system. The results have shown a higher efficiency and an increased performance capability of the present reactor in comparison with the conventional processes.     

Highly selective homogeneous ethylene epoxidation in gas (ethylene)‐expanded liquid: Transport and kinetic studies

Recently a homogeneous liquid‐phase ethylene oxide (EO) process with nearly total EO selectivity, catalyzed by methyltrioxorhenium with H₂O₂ as an oxidant, was reported. Fundamental mass transfer and kinetic studies of this reaction are reported in the present work. Volumetric expansion studies revealed that the liquid reaction phase (methanol + H₂O₂/H₂O) is expanded by up to 12% by compressed ethylene in the 20–40^°C range and up to 50 bars. This represents an increase in ethylene solubility by approximately one‐order of magnitude, attributed to the unique exploitation of near‐critical ethylene (P_c = 50.76 bar; T_c = 9.5^°C). Interphase mass‐transfer coefficients for ethylene dissolution into the liquid phase were obtained experimentally. Operating at conditions that enhanced the ethylene solubility and eliminated interphase mass‐transfer limitations maximized the EO productivity (1.61–4.97 g EO/h/g cat), rendering it comparable to the conventional process. Intrinsic kinetic parameters, estimated from fixed‐time semibatch reactor studies, disclosed the moderate activation energy (57 ± 2 kJ/mol). © 2012 American Institute of Chemical Engineers AIChE J, 59: 180–187, 2013     

Photocatalytic Destruction of Phenol by TiO2Powders

In this study the photocatalytic destruction of phenol in an aqueous suspension of illuminated TiO₂ was investigated. The experiments were carried out using a Pyrex annular photoreactor. The effects of some parameters such as pH, loading of TiO₂, flow rate of O₂ and temperature on the photocatalytic destruction rate of phenol were examined. It was observed that the flow rate of O₂ has no considerable effect on the destruction of phenol over the range of 2–3.5 L min^–1. The photodestruction of phenol followed the pseudo first‐order kinetics of the Langmuir‐Hinshelwood model giving an activation energy of 16.2 kJ mol^–1.     

An optimization study on microwave irradiated decomposition of phenol in the presence of H2O2

BACKGROUND Removal of phenol from industrial waste waters involves basic techniques namely extraction, biodegradation, photocatalytic degradation, etc. Among the available processes, the oxidation of phenols using H₂O₂ is a suitable alternative because of low cost and high oxidizing power. The application of an oxidation process for the decomposition of stable organic compounds in waste water leads to the total degradation of the compounds rather than transferring from one form to another. Since oxidation using Fenton's reagent is more dependent on pH, in this present work it was proposed to use H₂O₂ coupled with microwave irradiation. The effects of initial phenol concentration, microwave power and the irradiation time on the amount of decomposition were studied. RESULTS: In the present work experiments were conducted to estimate the percentage degradation of phenol for different initial concentrations of phenol (100, 200, 300, 400 and 500 mg L^?1), microwave power input (180, 360, 540, 720 and 900 W) for different irradiation times. The kinetics of the degradation process were examined through experimental data and the decomposition rate follows first‐order kinetics. Response surface methodology (RSM) was employed to optimize the design parameters for the present process. The interaction effect between the variables and the effect of interaction on to the responses (percentage decomposition of phenol) of the process was analysed and discussed in detail. The optimum values for the design parameters of the process were evaluated (initial phenol concentration 300 mg L^?1, microwave power output 668 W, and microwave irradiation time 60 s, giving phenol degradation 82.39%) through RSM by differential approximation, and were confirmed by experiment. CONCLUSION: The decomposition of phenol was carried out using H₂O₂ coupled with microwave irradiation for different initial phenol concentrations, microwave power input and irradiation times. The phenol degradation process follows first‐order kinetics. Optimization of the process was carried out through RSM by forming a design matrix using CCD. The optimized conditions were validated using experiments. The information is of value for the scale up of the oxidation process for the removal of phenol from wastewater. Copyright © 2008 Society of Chemical Industry     

Synthesis,characterization, and antimicrobial properties of oligo‐4‐[(pyridine‐3‐yl‐methylene) amino] phenol

The oxidative polycondensation reaction conditions of 4‐[(pyridine‐3‐yl‐methylene) amino]phenol (4‐PMAP) were studied using H₂O₂, atmospheric O₂, and NaOCl oxidants in an aqueous alkaline medium between 30°C and 90°C. Synthesized oligo‐4‐[(pyridine‐3‐yl‐methylene) amino] phenol (O‐4‐PMAP) was characterized by ¹H‐, ¹³C NMR, FTIR, UV–vis, size exclusion chromatography (SEC), and elemental analysis techniques. The yield of O‐4‐PMAP was found to be 32% (for H₂O₂ oxidant), 68% (for atmospheric O₂ oxidant), and 82% (for NaOCl oxidant). According to the SEC analysis, the number–average molecular weight, weight–average molecular weight, and polydispersity index values of O‐4‐PMAP was found to be 5767, 6646 g mol^?1, and 1.152, respectively, using H₂O₂, and 4540, 5139 g mol^?1, and 1.132, respectively, using atmospheric O₂, and 9037, 9235 g mol^?1, and 1.022, using NaOCl, respectively. According to TG and DSC analyses, O‐4‐PMAP was more stable than 4‐PMAP against thermal decomposition. The weight loss of O‐4‐PMAP was found to be 94.80% at 1000°C. Also, antimicrobial activities of the oligomer were tested against B. cereus, L. monocytogenes, B. megaterium, B. subtilis, E. coli, Str. thermophilus, M. smegmatis, B. brevis, E. aeroginesa, P. vulgaris, M. luteus, S. aureus, and B. jeoreseens. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3327–3333, 2006     

Photocatalytic conversion of benzene to phenol using modified TiO2 and polyoxometalates

The application of photocatalytic reactions to organic synthesis has attracted interests in view of the development of environmentally benign synthetic processes. This study investigated the effects of various parameters (electron acceptor, surface modification, and the combination of photocatalysts) on the direct synthesis of phenol from benzene using photocatalytic oxidation processes. The OH radicals generated on UV-illuminated TiO₂ photocatalyst directly hydroxylate benzene to produce phenol, hydroquinone, and catechol. The addition of Fe³⁺, H₂O₂, or Fe³⁺ + H₂O₂ highly enhanced the phenol production yield and selectivity in TiO₂ suspension. Surface modifications of TiO₂ had significant influence on the phenol synthetic reaction. Depositing Pt nanoparticles on TiO₂ (Pt/TiO₂) markedly enhanced the yield and selectivity. Surface fluorination of TiO₂ (F-TiO₂) increased the phenol yield two-fold because of the enhanced production of mobile (free) OH radicals on F-TiO₂. Polyoxometalate (POM) in phenol synthesis played the dual role both as a homogeneous photocatalyst and as a reversible electron acceptor in TiO₂ suspension. POM alone was as efficient as TiO₂ alone in the phenol production. In particular, the addition of POM to the TiO₂ suspension increased the phenol yield from 2.6% to 11% (the highest yield obtained in this study). Reaction mechanisms for each photocatalytic system were discussed in relation to the phenol synthesis.     

Synthesis,characterization, thermal stability,conductivity, and band gap of a new aromatic polyether containing an azomethine as a side

In this study, the oxidative polycondensation reaction conditions of 4‐[(4‐methylphenyl)iminomethyl]phenol (4‐MPIMP) were studied by using oxidants such as air O₂, H₂O₂, and NaOCl in an aqueous alkaline medium between 50 and 90°C. The structures of the synthesized monomer and polymer were confirmed by FTIR, UV–vis, ¹H–¹³C‐NMR, and elemental analysis. The characterization was made by TGA‐DTA, size exclusion chromatography (SEC), and solubility tests. At the optimum reaction conditions, the yield of poly‐4‐[(4‐methylphenyl)iminomethyl]phenol (P‐4‐MPIMP) was found to be 28% for air O₂ oxidant, 42% for H₂O₂ oxidant, and 62% for NaOCl oxidant. According to the SEC analysis, the number–average molecular weight (M_n), weight–average molecular weight (M_w), and polydispersity index values of P‐4‐MPIMP were found to be 4400 g mol^?1, 5100 g mol^?1, and 1.159, using H₂O₂, and 4650 g mol^?1, 5200 g mol^?1, and 1.118, using air O₂, and 5100 g mol^?1, 5900 g mol^?1, and 1.157, using NaOCl, respectively. According to TG analysis, the weight losses of 4‐MPIMP and P‐4‐MPIMP were found to be 85.37% and 72.19% at 1000°C, respectively. P‐4‐MPIMP showed higher stability against thermal decomposition. Also, electrical conductivity of the P‐4‐MPIMP was measured, showing that the polymer is a typical semiconductor. The highest occupied molecular orbital and the lowest unoccupied molecular orbital energy levels and electrochemical energy gaps (E) of 4‐MPIMP and P‐4‐MPIMP were found to be ?5.76, ?5.19; ?3.00, ?3.24; 2.76 and 1.95 eV, respectively. According to UV–vis measurements, optical band gaps (E_g) of 4‐MPIMP and P‐4‐MPIMP were found to be 3.34 and 2.82 eV, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Solar‐assisted photochemical and photocatalytic degradation of phenol

Photocatalytic (TiO₂, air and solar radiation) and photochemical (H₂O₂ and solar radiation) mineralizations of phenol solutions (up to 500 mg dm^?3) in a batch reactor using concentric solar radiation were studied. A compound parabolic reflector as a concentrating reflector was used to obtain concentrated solar radiation in both cases. Considerable enhancement (Five‐fold) in the rate of degradation was obtained when concentrated solar radiation was used instead of plain solar radiation in photocatalytic degradation. The effect of initial phenol concentration, intensity and presence of anions has been studied in both the cases. Low concentrations of intermediates were observed, during the reaction, over the entire range of phenol concentrations studied in the case of photocatalytic degradation using Degussa‐P25 TiO₂ as photocatalyst and in the absence of anions; whereas significant quantities of intermediates were observed in the case of the photochemical degradation. The presence of anions generally had a detrimental effect on the mineralization process in both cases. Different anions showed different effects. Total organic carbon (TOC) variations with time were also studied. A rational explanation has been given for the decrease in the rate in the presence of anions. © 2001 Society of Chemical Industry     

Experimental analysis of a photoreactor packed with Pd-BiVO4-Coated glass beads

A photoreactor packed with glass beads coated by palladium nanoparticles-modified BiVO₄ was tested and analyzed in phenol degradation under UV–Visible light. The photocatalytic activity of Pd-BiVO₄ under visible light is higher than TiO₂ under UV light, as we previously reported. In this work, we try to use the Pd-BiVO₄ in a large scale by coating the glass beads with it, a potentially industrial-scale use. For comparison, a flat-plate reactor and a slurry reactor were also examined. The photocatalytic activity of Pd-BiVO₄ in phenol degradation was found to be higher than that of TiO₂ in all systems (slurry, flat-plate, and packed beads reactor [PBR]). Furthermore, PBR exhibited higher energy efficiency compared to the flat-plate reactor in phenol oxidation. The superior performance of this reactor is due primarily to the highly exposed catalyst surface area, high mass transfer coefficient, and effective delivery of both photons and reactants to the catalyst surfaces. © 2018 American Institute of Chemical Engineers AIChE J, 65: 132–139, 2019     

Photocatalytic Performance of Nitrogen‐Doped and Cu2+ and Ag+ Co‐Doped Sodium Trititanate

Nano‐sized (i) N‐doped sodium trititanate and (ii) N and Cu²⁺ (Ag⁺) co‐doped sodium trititanates CuTi₃NO_6?x (Ag₂Ti₃NO_6?x) were prepared by a solid‐state and ion‐exchange methods, respectively. The materials were characterized by EDS, PXRD, XPS, FESEM, TEM, UV–visible DRS, and Raman spectroscopy. All the materials were crystallized in monoclinic lattice with P21/m space group. The bandgap energy of all the samples was deduced from their UV–visible DRS profiles. Visible‐light‐induced photocatalytic oxidation of the methylene blue (MB) and methyl orange (MO), cyclohexene and phenol, was examined. The Ag⁺ co‐doped trititanate exhibited the highest photocatalytic activity among the materials investigated.     

Diclofenac removal from water by ozone and photolytic TiO2 catalysed processes

BACKGROUND: The aim of this work was to establish the efficiency of single ozonation at different pH levels (5, 7 and 9) and with different TiO₂ photolytic oxidizing systems (O₂/UV‐A/TiO₂, O₃/UV‐A/TiO₂ or UV‐A/TiO₂) for diclofenac removal from water, with especial emphasis on mineralization of the organic matter. RESULTS: In the case of single ozonation processes, results show fast and practically complete elimination of diclofenac, with little differences in removal rates that depend on pH and buffering conditions. In contrast, total organic carbon (TOC) removal rates are slow and mineralization degree reaches 50% at best. As far as photocatalytic processes are concerned, diclofenac is completely removed from the aqueous solutions at high rates. However, unlike single ozonation processes, TOC removal can reach 80%. CONCLUSION: In single ozonation processes, direct ozone reaction is mainly responsible for diclofenac elimination. Once diclofenac has disappeared, its by‐products are removed by reaction with hydroxyl radicals formed in the ozone decomposition and also from the reaction of diclofenac with ozone. In the photocatalytic processes hydroxyl radicals are responsible oxidant species of diclofenac removal as well as by‐products. Copyright © 2010 Society of Chemical Industry     

Energy‐Transfer Modulation for Enhanced Photocatalytic Activity of Near‐Infrared Upconversion Photocatalyst

One of the major challenges of near‐infrared upconversion photocatalyst concerns strengthening the cooperation between Rare‐earth (RE) ions and semiconductor materials for enhancing NIR photocatalytic activity. Herein, the basic energy‐transfer (ET) process between RE ions and semiconductor materials is discussed and the appropriate mode, nonradiative ET, is proposed for efficiently coupling them. As an example, a novel NIR‐based UC photocatalyst, CaIn₂O₄:Yb³⁺,Tb³⁺ was designed and successfully fabricated, which exhibited high photocatalytic activity under 980 nm irradiation. The present report highlights the potential of ET tuning between RE ions and semiconductors toward high performance of NIR photocatalysis.     

Degradation of 1‐amino‐4‐bromoanthraquinone‐2‐sulfonic acid using combined airlift bioreactor and TiO2‐photocatalytic ozonation

BACKGROUND: Traditional treatment systems failed to achieve efficient degradation of anthraquinone dye intermediates at high loading. Thus, an airlift internal loop reactor (AILR) in combination with the TiO₂‐photocatalytic ozonation (TiO₂/UV/O₃) process was investigated for the degradaton of 1‐amino‐ 4‐bromoanthraquinone‐2‐ sulfonic acid (ABAS). RESULTS: The AILR using Sphingomonas xenophaga as inoculum and granular activated carbon (GAC) as biocarrier, could run steadily for 4 months at 1000 mg L^?1 of the influent ABAS. The efficiencies of ABAS decolorization and chemical oxygen demand (COD) removal in AILR reached about 90% and 50% in 12 h, respectively. However, when the influent ABAS concentration was further increased, a yellow intermediate with maximum absorbance at 447 nm appeared in AILR, resulting in the decrease of the decolorization and COD removal efficiencies. Advanced treatment of AILR effluent indicated that TiO₂/UV/O₃ process more significantly improved the mineralization rate of ABAS bio‐decolorization products with over 90% TOC removal efficiency, compared with O₃, TiO₂/UV and UV/O₃ processes. Furthermore, the release efficiencies of Br^? and SO₄^2? could reach 84.5% and 80.2% during TiO₂/UV/O₃ treatment, respectively, when 91.5% TOC removal was achieved in 2 h. CONCLUSION: The combination of AILR and TiO₂/UV/O₃ was an economic and efficient system for the treatment of ABAS wastewater. © 2012 Society of Chemical Industry     

Gas‐Liquid Mass Transfer in a Bench‐Scale Trickle Bed Reactor used for Benzene Hydrogenation

The gas‐liquid mass transfer coefficients (MTCs) of a trickle bed reactor used for the study of benzene hydrogenation were investigated. The Ni/Al₂O₃ catalyst bed was diluted with a coarse‐grained inert carborundum (SiC) particle catalyst. Gas‐liquid mass transfer coefficients were estimated by using a heterogeneous model for reactor simulation, incorporating reaction kinetics, vapor‐liquid equilibrium, and catalyst particle internal mass transfer apart from gas‐liquid interface mass transfer. The effects of liquid axial dispersion and the catalyst wetting efficiency are shown to be negligible. Partial external mass transfer coefficients are correlated with gas superficial velocity, and comparison between them and those obtained from experiments conducted on a bed diluted with fine particles is also presented. On both sides of the gas‐liquid interface the hydrogen mass transfer coefficient is higher than the corresponding benzene one and both increase significantly with gas velocity. The gas‐side mass transfer limitations appear to be higher in the case of dilution with fine particles. On the liquid side, the mass transfer resistances are higher in the case of dilution with coarse inerts for gas velocities up to 3 · 10^–2 cm/sec, while for higher gas velocities this was inversed and higher mass transfer limitations were obtained for the beds diluted with fine inerts.     

Fabrication of BaZr0.1Ce0.7Y0.2O3 – δ ‐Based Proton‐Conducting Solid Oxide Fuel Cells Co‐Fired at 1,150 °C

Dense proton‐conducting BaZr_0.1Ce_0.7Y_0.2O_{3 – δ} (BZCY) electrolyte membranes were successfully fabricated on NiO–BZCY anode substrates at a low temperature of 1,150 °C via a combined co‐press and co‐firing process. To fabricate full cells, the LaSr₃Co_1.5Fe_1.5O_{10 – δ}–BZCY composite cathode layer was fixed to the electrolyte membrane by two means of one‐step co‐firing and two‐step co‐firing, respectively. The SEM results revealed that the cathode layer bonded more closely to the electrolyte membrane via the one‐step co‐firing process. Correspondingly, determined from the electrochemical impedance spectroscopy measured under open current conditions, the electrode polarisation and Ohmic resistances of the one‐step co‐fired cell were dramatically lower than the other one for its excellent interface adhesion. With humidified hydrogen (2% H₂O) as the fuel and static air as the oxidant, the maximum power density of the one‐step co‐fired single cell achieved 328 mW cm^–2 at 700 °C, showing a much better performance than that of the two‐step co‐fired single cell, which was 264 mW cm^–2 at 700 °C.     

Influence of TiO2‐Layer Thickness of Spray‐Coated Glass Beads on Their Photocatalytic Performance

TiO₂ is a suitable catalyst for potential photocatalytic processes, e.g., in wastewater treatment. For a technical realization of such processes, the application of immobilized TiO₂ in a continuous process would be desirable. However, since UV radiation has a limited penetration depth into a packed bed of pure TiO₂, supporting it on UV‐transparent glass beads offers the possibility to implement continuous photocatalytic processes in a fixed‐bed reactor. Considering this fact, glass beads were coated with TiO₂ powder in a fluidized‐bed reactor. The coated glass beads with varying TiO₂ layer thickness were tested in the photocatalytic degradation of methylene blue, and the influence of an addition of methyl cellulose during the coating process on the photocatalytic performance was investigated.     

Phenol photodegradation with oxygen and hydrogen peroxide over TiO2 and Fe-doped TiO2

Photodegradation of phenol was investigated with two types of oxidant agents in water, oxygen and hydrogen peroxide, at two different reaction pH with a series of nanosized iron-doped anatase TiO₂ catalysts with different iron contents. The catalysts have been prepared by a sol–gel/microemulsion method. Firstly, iron-doped titania catalysts were studied with respect to their activity behavior when oxygen was used as oxidant agent in the photocatalytic degradation of aqueous phenol in comparison with un-doped reference catalysts. Secondly, two catalysts (TiO₂ and 0.7 wt.% Fe-doped TiO₂) were selected to extend the study for the employment of hydrogen peroxide as oxidant at different concentrations and two initial reaction pHs. An enhancement of the photocatalytic activity is observed only for relatively low doping level (ca. 0.7 wt.%) in catalyst calcined at 450 °C preferably using hydrogen peroxide as oxidant agent which is attributable to the partial introduction of Fe³⁺ cations into the anatase structure. Nevertheless, it has been demonstrated that catalyst surface properties can play an important role during phenol photodegradation process on the basis of the analysis of differences found in the photoactivity as a function of reaction pH.     

Effects of anions on the photocatalytic and photoelectrocatalytic degradation of reactive dye in a packed‐bed reactor

The effects of various anions, Cl^?, ClO₄^?, SO₄^2?, NO₃^?, HCO₃^?, H₂PO₄^? and C₂O₄^2?, on the photocatalytic and photoelectrocatalytic degradation of reactive Brilliant Orange K‐R have been investigated in a packed‐bed photoelectrocatalytic reactor. It was found that the nature and concentrations of these inorganic anions significantly affected the photocatalytic and photoelectrocatalytic degradation performance of the reactive dye. The results indicated that the external electric field was successfully applied to improve the photocatalytic efficiency of reactive Brilliant Orange K‐R in the presence of Cl^?, especially at higher concentrations, while other inorganic anions displayed more or less negative effects on the degradation of the dye. The strongest inhibition effect on photocatalytic and photoelectrocatalytic degradation of the dye was observed in the presence of HCO₃^? ions. Copyright © 2004 Society of Chemical Industry     

Kinetics and Reactor Modeling of the Steam Reforming of Methanol over a Mn‐Promoted Cu/Al Catalyst

The kinetics of the steam reforming of methanol (SRM) was studied in a packed‐bed reactor over a Mn‐promoted Cu/Al₂O₃ catalyst under defined conditions. A Langmuir‐Hinshelwood‐Hogan‐Watson (LHHW)‐type mechanism that assumes the dissociative adsorption of methanol on two distinct active sites as the rate‐controlling step was found to satisfactorily describe the SRM reaction with activation energies of 77.3 and 64.5 kJ mol^?1 at low and high temperature, respectively. No mass or heat transfer limitations were observed under the experimental conditions used in this study. A reactor model was also developed, validated, and employed to predict the conversion, temperature, and concentration profiles. The axial dispersion had no influence on the temperature distribution but the effect was more pronounced on the methanol conversion.