Electrocatalytic activity of electrodeposited CoOx thin film on low-carbon unalloyed steel substrate toward electrochemical oxygen evolution reaction (OER).

In this study, we report elaboration of a thin film of CoOx on a low carbon unalloyed steel substrate by electrochemical route and the study of its electrocatalytic performances with respect to the evolution reaction of oxygen (OER) in NaOH medium. The elaborated deposits were well-characterized using X-ray diffraction. Kinetic and thermodynamic parameters such as exchange current density, Tafel slope, reaction order with respect to OH- ions and apparent activation energy were studied. The CoOx displays satisfactory OER performance in an alkaline medium, with a low overvoltage of 362 mV at 10 mA/cm2 and a Tafel slope of 81 mV/dec at 293 K. The apparent kinetic activation energy (= 29.79 kJ/mol) was similar to those obtained for the reported catalytic electrode materials. The O2 gas obtained on the cobalt oxide electrode was 2.865 mmol/s.cm2, which is 28 times higher than that obtained for the platinum electrode (0.102 mmol/s.cm2). Chronoamperometry demonstrates a better electrochemical stability under a polarization potential of 2 V in 1 M NaOH for nearly 25 h. The low cost, the high OER performance, as well as the good stability of the CoOx electrode make it a promising candidate for the industrial-scale water electrolysis.

Photodegradation of Organophosphorus Pesticides in Honey Medium by Solar Light Irradiation.

In this study, the photodegradation of organophosphorus (OPs) pesticides in the honey medium was evaluated under sunlight irradiation. Some of the 22 samples collected at different sites contained OPs pesticides (Methyl parathion, Coumaphos and Fenitrothion) with an average of 8 ng/g. Moreover, three samples were found with pesticide residue levels exceeding the maximum residue limits (MRL ≥ 50 ng/g) imposed by the standard water (WHO). Gas chromatography (GC) combined with a tritium electron capture detector system was used for the analysis of OPs pesticides in honey. Total degradation of the Methyl parathion was obtained in less than 60 min of irradiation. Moreover, the elimination of the other OPs found in the samples was also effective with a rate of 85% for Coumaphos and Fenitrothion after 50 min of sunlight irradiation. The kinetics of the photodegradation reaction of all OPs pesticides studied followed a pseudo-first order model.

Modeling biosorption of Cr(VI) onto Ulva compressa L. from aqueous solutions.

The marine biomass Ulva compressa L. (ECL) was used as a low-cost biosorbent for the removal of Cr(VI) from contaminated aqueous solutions. The operating variables were optimized: pH ∼ 2, initial concentration of 25 mg/L, solid/liquid ratio of 6 g/L and a temperature of 50 °C, leading to an uptake elimination of 96%. A full factorial experimental design technique enabled us to obtain a mathematical model describing the Cr(VI) biosorption and to study the main effects and interactions among operational parameters. The equilibrium isotherm was analyzed by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models; it has been found that the adsorption process follows well the Langmuir model. Kinetic studies showed that the pseudo-second order model describes suitably the experimental data. The thermodynamic parameters indicated an endothermic heat and a spontaneity of the Cr(VI) biosorption onto ECL.

Preparation and characterization of calcined Ni/Mo hydrotalcite for the effective removal of lead from wastewater.

In this investigation, calcined Ni/Mo hydrotalcite was prepared via co-precipitation method and used as a sorbent for efficient removal of lead from aqueous solutions. The Pb2+ removal efficiency reached 99% at pH 6 and a sorbent dose of 2 g/L. The equilibrium data were satisfactorily fitted by the Langmuir and Hill models with a maximum capacity of 196.87 mg/g, indicating the monolayer sorption for lead over calcined Ni/Mo hydrotalcite. The Pb2+ sorption kinetic follows a pseudo-second-order reaction due to high correlation coefficients (R2 > 0.99), while the Boyd's plots confirm the external mass transfer as the rate-limiting step in the Pb2+ sorption. The temperature effect indicated a spontaneous and exothermic Pb2+ uptake. Mechanisms involved in the removal process include surface precipitation, diffusion into the solid pores and isomorphic substitution with Ni2+ of the sheets. The results showed excellent selectivity for Pb2+ removal from multi-divalent cation solutions and good reusability of the sorbent for up to 10 consecutive sorption-regeneration cycles without significant loss of the removal efficiency. As an application, the treatment of wastewater containing Pb2+, generated from the battery industry has been undertaken. The Pb2+ concentration was reduced from 5.7 to 0.6 mg/L, corresponding to an abatement of 89.5%. Therefore, the sorption using calcined Ni/Mo hydrotalcite is an efficient and suitable method for the elimination of Pb2+.

Preparation, characterization and application of CuCrO2/ZnO photocatalysts for the reduction of Cr(VI).

The delafossite CuCrO2 elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstructure is fairly homogenous with a mean crystallite size of ca. 2 microm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of -0.26 V(SCE). As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO2/ZnO (1/1). CuCrO2 is photoactivated by visible light and the electrons in the conduction band (-1.34 V(SCE)) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25 degrees C, 5 x 10(-4) mol/L) because of the HCrO4- dark adsorption onto ZnO (4HCrO4- + 3C7H6O3 + 18O2 + 16H+ --> 4Cr3+ + 21CO2 + 19H2O, deltaG0 = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 micromol/(hr x g).

Efficient removal of the antibiotic Cefixime on Mg0.3Zn0.7O under solar light: kinetic and mechanism studies.

The heterogeneous photocatalysis is known to provide significant degradation and mineralization of emerging contaminants including antibiotics. For this, nanosized Mg0.3Zn0.7O (MZO) was prepared by nitrate route to be used as photocatalyst. The single-phase was confirmed by X-ray diffraction with a crystallite size of 33 nm. The morphology was visualized by scanning electron microscope/energy-dispersive X-ray analysis. The physicochemical properties were studied by the FTIR, XPS, and optical analyses. The diffuse reflectance gives a direct forbidden band of 3.26 eV. The electrochemical characterization showed an n-type semiconductor with a flat band of - 0.56 VAg/AgCl. The photodegradation of Cefixime (CFX) was carried out under solar light; the operating parameters such as the catalyst dose, solution pH, and initial CFX concentration (Co) were optimized. The best performance occurs at neutral pH ~ 6 within 4 h with an abatement of 94% for an initial CFX concentration of 5 mg/L and MZO dose of 0.75 g/L. The photodegradation follows a first-order kinetic with an apparent rate constant of 0.012 min-1. The effects of scavenging agents indicated the dominant role of hydroxyl •OH followed by the holes (h+). The results showed the potentiality of MZO as an environmentally friendly photocatalyst for CFX photodegradation.

Synthesis, structural, and opto-electrochemical properties of cobalt aluminate type spinel and its use with ZnO for Cr(VI) photoreduction.

The discovery of the occurrence of inorganic pollutants in surface waters is identified in the system assessment quality. The most harmful elements are pesticides, persistent organic pollutants, pharmaceuticals, personal care products, and heavy metals are still dangerous to the environment due to their general uses. Chromate has the largest concentration compared to the other metals in the wastewater industries. This work evaluates the application of the spinel p-CoAl2O4 as a photocatalyst prepared by the nitrate synthesis process to reduce Cr(VI), a hazardous metal for the environment. The photocatalyst was characterized using thermal analysis (TG), X-ray diffraction, UV-diffuse reflectance spectroscopy, scanning electron microscopy, fluorescent X-ray, Fourier transform infrared spectroscopy, electrical conductivity, and photoelectrochemically. The results showed that the efficiency of optimum reduction of Cr(Vl) to Cr(IIl) photoreduction is more effective (77%) for pH = 3.6 than that at high pH values up to 8 (7%). Moreover, the effect of the hetero-system CoAl2O4/ZnO on photocatalytic efficiency was investigated. The photocatalytic activity increases up to 99% with 1 g L-1, a total catalyst dosage over the hetero-system CoAl2O4/ZnO at a ratio of 75%/25%. This data is better relative to CoAl2O4 or ZnO alone. The Cr(VI) photoreduction activity improvement was caused by the best separation and the photogeneration of electron-hole on the CoAl2O4/ZnO surfaces. Finally, the Lagergren pseudo-first-order and the Langmuir-Hinshelwood models fit well the experimental kinetics.

The impact of material design on the photocatalytic removal efficiency and toxicity of two textile dyes.

This study deals with the toxicity of the treated solutions of two types of dyes, namely, the anthraquinonic Reactive Bleu 19 dye (RB19) and the bi-azoic Direct Red 227 dye (DR227), which are treated in single and binary mixture systems. The target molecules were removed by the photocatalysis process using ZnO as a catalyst, which was calcined at two temperatures 250 and 420 °C (ZnO250 and ZnO420) prepared in the lab by the one-step calcination method. XRD, TEM, EDX, XPS, FT-IR, BET, RAMAN, and EPR analyses were carried out to characterize the catalyst material. While the phytotoxicity was being conducted using watercress seeds, the cytotoxicity took place using a cell line (raw) and an intestinal cell (caco-2). The XRD analysis showed the partial calcination of ZnO250 and the presence of anhydrous zinc acetate along with the ZnO nanoparticles (NPs). This result was not observed for ZnO420. Despite the complete discoloration (100%) of all the final solutions, ZnO250 exhibited a high cytotoxicity and phytotoxicity against the RB19 dye after the photocatalytic treatment; however, it was not the case of ZnO420 which was selected as an eco-friendly photocatalyst for the degradation of organic dyes based on the results of removal efficiency, cytotoxicity, and phytotoxicity.

Removal efficiency of pharmaceutical drugs (Mebeverine hydrochloride MEB) by an activated carbon prepared from dates stems.

The removal efficiency of the pharmaceutical drug Mebeverine Hydrochloride (MEB) from solutions by an activated carbon (AC) prepared from dates stems was investigated in the present research work. The surface properties of the activated carbon were investigated by elementary analysis, BET surface area, SEM, FTIR and pHpzc. The operating parameters effect on the MEB adsorption efficiency was investigated by using batch experiments. The adsorption isotherms study indicated that the experimental data were well described by Freundlich and DR isotherms, with the maximum adsorption capacity (qmax) of 4105 mg/g. This result suggests the multilayer adsorption of MEB on the activated carbon. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40201-021-00658-1.

High efficiency photocatalytic degradation of Ambroxol over Mn doped TiO2: Experimental designs, identification of transformation products, mineralization and mechanism.

Ambroxol (AMB) is a drug commonly used for chronic bronchitis prevention. Once released in surface water, this recalcitrant chemical becomes a hazardous pollutant. Here, we investigated the ability of 1% Mn-doped TiO2 (Mn-TiO2) to mineralize AMB by photocatalysis. We studied the morphology, and the physical and electrochemical properties of Mn-TiO2 using X-ray diffraction, Scanning electron microscopy, Transmission electron microscopy, X-ray fluorescence, BET method, UV-visible, and electrochemical study and optimized the AMB degrading experimental conditions through response surface methodology (RSM). Mn-TiO2 at the dose of 0.625 g·L-1 allowed the complete photodegradation of AMB (30 ppm) at pH 7 under UVA light irradiation for 30 min while total mineralization in CO2 (>96%) was achieved after 24 h of irradiation. Mn-TiO2 was 1.6-time more efficient than TiO2 Degussa P25. Product studies were also carried out by liquid chromatography coupled to electrospray high resolution mass spectrometry. Twenty-one photodegradation products were detected and identified. In addition, ionic chromatography analyses revealed the release of Br-, NH4+, and NO3- at respectively 97, 63 and 35% of the total Br, and N initially present in AMB. Finally, the reusability of the photocatalyst was also tested. After four cycles, the almost complete photodegradation of AMB was achieved showing that Mn-TiO2 was highly stable. This work brings new physical characteristics on Mn-TiO2 photocatalyst. Moreover, it is the first study investigating the photocatalytic degradation of recalcitrant AMB drug.

Valorization of Crataegus azarolus stones for the removal of textile anionic dye by central composite rotatable design using cubic model: optimization, isotherm, and kinetic studies.

In this study, the central composite rotatable design (CCRD) was used in the optimization of the operating parameters for the removal of the direct blue 86 (DB86), an anionic dye, because of its hazardous impact on human health and aquatic environment. In addition, DB86 is a recalcitrant and non-biodegradable dye whose presence considerably inhibits photosynthesis. Its removal in aqueous medium was achieved by biosorption onto the novel biosorbent Crataegus azarolus stones (CAS). The parameters like the solution pH, biosorbent dose, initial DB86 concentration, and temperature were studied in the ranges 2-6, 0.8-4 g L-1, 20-100 mg L-1, and 10-50 °C, respectively. The significance of the experimental parameters and their interactions was investigated by the Student's t test and p values with 5% error limits using JMP 11.0.0 software. The regression analysis of the experimental data obtained from 31 batch runs provides a cubic model. The optimum conditions obtained for the maximum DB86 elimination from the synthetic solution were found to be pH 2, biosorbent dose of 4 g L-1, initial DB86 concentration of 20 mg L-1, and temperature of 10 °C, leading to a theoretical maximum removal of 123%. The experimental data were analyzed by the Langmuir, Freundlich, and Temkin equilibrium models. The Langmuir isotherm gave the best fit with a maximum biosorption capacity of 24.02 mg g-1. The results of the kinetic study revealed that the biosorption kinetic of DB86 follows a pseudo-second-order model. All results confirmed that CAS are an efficient, economic, and ecological alternative for the treatment of industrial wastewaters loaded with anionic dyes.

Optimization of a novel biocomposite synthesis (Ammi Visnaga extraction waste/alginate) for Cd(2+) biosorption.

A novel environmentally friendly biocomposite namely calcium alginate immobilized Ammi Visnaga (Khella) extraction waste was prepared by electrostatic extrusion method. A full factorial design 2(3) was used to optimize the beads preparation conditions. The effect of sodium alginate concentration (X1), biomass concentration (X2) and cross-linker concentration (X3) on the Cd(2+) removal efficiency was examined in a batch system with a fixed biocomposite dose of 1g/L. Using the experimental results, a linear mathematical model representing the influence of different variables and their interactions was obtained. The optimized values of X1, X2 and X3 were found to be 4.35%, 2.5% and 1.99% respectively. The biocomposite beads were characterized by ATR spectroscopy, scanning electron microscopy for the surface morphology and optical microscopic for the particles size measurements.

Nickel removal by biosorption onto medlar male flowers coupled with photocatalysis on the spinel ZnMn2O4.

Ni2+ is a highly toxic above 0.07 mg/L and its removal is of high significance. The biosorption of Ni2+ onto medlar male flowers (MMF) was studied in relation with the physical parameters like pH, contact time, biosorbent dosage, Ni2+ concentration and temperature. The interaction biosorbent-Ni2+ was examined by the FTIR technique. The equilibrium was achieved within 40 min and the data were well fitted by the Langmuir and Redlich-Peterson (R-P) models. The maximum Ni2+ uptake capacity was 17.073 mg/g at 25°C and the Ni2+ removal follows a pseudo-second order kinetic with activation energy of 13.3 kJ/mol. The thermodynamic parameters: ΔS°, ΔH° and ΔG° showed that the biosorption was spontaneous and endothermic. MMF was used as a post treatment technique and the biosorption was coupled with the visible light driven Ni2+ reduction over the spinel ZnMn2O4. The effect of the pH, ZnMn2O4 loading and light intensity on the photoactivity was investigated. 77.5% of Ni2+ was reduced after ~140 min under optimal conditions. The Ni2+ removal reached a rate conversion of 96% of with the coupled system biosorption/photocatalysis is very promising for the water treatment.

Synthesis of modified polymer inclusion membranes for photo-electrodeposition of cadmium using polarized electrodes.

In this work, we have developed a novel class of polymeric inclusion membranes (PIMs) for the cations separation. The membrane is made up of cellulose triacetate modified by poly-electrolytes (poly-phosphoric acid, polyvinyl pyrolidone, polyacrylic acid, polyvinyl alcohol and poly-anetholsulfonic acid) using 2-hydroxy-5-dodecylbenzaldehyde incorporated into the polymer as carrier and tris ethyl hexyl phosphate or glycerine as plasticizers. Different PIMs are synthesized and characterized by the Fourier transform infrared, X-ray diffraction, thermal analysis and scanning electron microscopy. The influence of the membrane nature is studied using supports with different physical characteristics (porosity, thickness, hydrophobia). As application, the transport of Cd(2+) using PIMs coupled with photo-electrodes is investigated. The photo-catalytic results indicate that the combined system p-CuFeO(2)/membrane/n-WO(3) enhances considerably the electrons transfer toward the delafossite CuFeO(2). The position of the conduction band of CuFeO(2) is looked to be the key issue for the photo electrochemical Cd(2+) reduction.

Cadmium (II) and lead (II) transport in a polymer inclusion membrane using tributyl phosphate as mobile carrier and CuFeO(2) as a polarized photo electrode.

In this work, a development of polymeric inclusion membranes for the cations separation is reported. The membrane was made up of cellulose triacetate (CTA) with a tributyl phosphate (TBP) incorporated into the polymer as metal ions carrier. The transport of lead (II) and cadmium (II) ions in two membrane systems polymer inclusion membrane (PIM), PIM coupled with photo-chemical electrode using TBP as carrier and 2-nitro phenyl octyl ether (NPOE) or tris ethylhexyl phosphate (TEHP) as plasticizer have been investigated. The membranes: polymer+plasticizer+carrier were synthesized and characterized by FTIR, X-ray diffraction and scanning electron microscopy (SEM). Transports of lead and cadmium have been studied using these systems and the results were compared to commercial cation exchange membrane (CRA). The obtained results showed that for Pb(2+) ion, the concentrations of the strip phase increases using synthesized membranes. The conduction band of the delafossite CuFeO(2) (-1.25 V(SCE)) yields a thermodynamically M(2+) (=Pb(2+), Cd(2+)) photo electrodeposition and speeds up the diffusion process. In all the cases, the potential of the electrode M/M(2+) in the feed compartment increases until a maximum value, reached at approximately 100 min above which it undergoes a diminution.

An assembled poly-4-vinyl pyridine and cellulose triacetate membrane and Bi2S3 electrode for photoelectrochemical diffusion of metallic ions.

The transport phenomena across ion exchange membrane may be enhanced by applying various strengths inside or outside the system. The electrical current, generated by n-type semiconductor, is used to catalyse the separation of metal ions. The cation exchange membrane located between the two compartments allows both the separation and concentration of M(n+) (Ag(+), Cu(2+), Pb(2+) and Ni(2+)). The flows of M(n+) from the aqueous solution to-and inside the membrane are monitored by the determination of the fluxes and the potentials. In this study, the four cations are investigated alone or in quaternary systems. From photoelectrochemical measurement, the gap of Bi(2)S(3) is found to be indirect at 1.65 eV. The shape of photocurrent potential curve and the negative flat band potential (-1.02 V(SCE)) give evidence of n-type character. The conduction band (-1.25 V(SCE)) yields thermodynamically M(2+) photoreduction and catalyzes the diffusion process. The photoelectrode Bi(2)S(3) makes the flux twofold greater than that observed in the dark. In all cases, the potential of the electrode M(2+)/M in the feed compartment increases until a maximal value, reached at approximately 100 min above which it undergoes a diminution. The membrane is more selective to Cu(2+) and this selectivity decreases in the quaternary system.