Solvothermal synthesis of organoclay/Cu-MOF composite and its application in film modified GCE for simultaneous electrochemical detection of deoxyepinephrine, acetaminophen and tyrosine.

An organoclay/copper-based metal-organic framework (MOF) composite was synthesized using a solvothermal method by growing a Cu-BTC (copper(ii) benzene-1,3,5-tricarboxylate) MOF from a mixture of the MOF precursor solution in which various amounts of organoclay had been dispersed. The organoclay was obtained by intercalating a cationic dye, namely thionin, into a natural Cameroonian clay sampled in Sagba deposit (North West of Cameroon). The organoclay and the as-synthesized composites were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and Brunauer, Emmett and Teller (BET) techniques. From Scherrer's equation, the crystallite size of the composite was found to be between 55 and 58 nm, twice as large as the pristine MOF's crystallite size. The organoclay/Cu-MOF composite (Sa-TN50/Cu3(BTC)2) exhibiting a BET surface area of 192 m2 g-1, about twice that of pristine clay and about one seventh that of pristine MOF, was then utilized to form a stable thin film onto glassy carbon electrodes (GCE) by drop coating (Sa-TN50/Cu3(BTC)2/GCE). These electrodes demonstrated electrocatalytic behavior toward deoxyepinephrine (DXEP) and thus enabled selective and simultaneous sensitive detection of three analytes: DXEP, acetaminophen (AC) and tyrosine (TYR) compared with bare GCE and clay modified electrode. Under optimum conditions, Sa-TN50/Cu3(BTC)2/GCE exhibited good performance including large calibration curves ranging from 5.0 µM to 138.0 µM for DXEP, 4.0 µM to 153.0 µM for AC and 1.0 µM to 29.4 µM for TYR. The detection limits were found to be, 0.4 µM, 0.7 µM and 0.2 µM for DXEP, AC and TYR, respectively. The developed sensors have been applied successfully in the quantification of AC in a commercial tablet of AC, and DXEP, AC and TYR in tap water.

Performances of Alkaloid Extract from Rauvolfia macrophylla Stapf toward Corrosion Inhibition of C38 Steel in Acidic Media.

Alkaloid extract from Rauvolfia macrophylla Stapf (AERMS) was studied as the corrosion inhibitor for C38 steel in 1 M HCl and 0.5 M H2SO4 using electrochemistry and surface analysis. The corrosion inhibition was efficient and proceeds via adsorption of AERMS on the steel surface due to the active functional groups present in the molecules. AERMS acts as a mixed inhibitor in HCl and as a cathodic inhibitor in H2SO4. In H2SO4 corrosive medium, the presence of iodides improves the adsorption of the alkaloid molecules by reducing the surface charge of the electrode and thus substantially decreases the corrosion rate. Two pure alkaloids (tetrahydroalastonine (THA) and perakine (PER)) were quantitatively isolated from AERMS, and their anticorrosive properties for C38 steel in 1 M HCl and 0.5 M H2SO4 were evaluated. THA showed the highest efficiency while the performance of PER was less important compared to the extract. This confirms that the efficiency of AERMS was the result of the complementary action of the chemical compounds present in the extract.

Characterizing the reactivity of metallic iron for water defluoridation in batch studies.

The suitability of metallic iron (Fe(0)) for water defluoridation is yet to be understood. Fluoride removal ([F-]0 = 20.0 mg L-1) and Orange II discoloration ([Orange II]0 = 10.0 mg L-1) by Fe(0)/H2O batch systems are compared herein. A steel wool (SW) and a granular iron (GI) are used as Fe(0) specimens. Each essay tube contains 0.5 g sand and 0.1 g of the used Fe(0). Investigated systems were: (i) SW/sand at pH 5.0, (ii) GI/sand at pH 5.0 and (iii) SW/sand at pH 8.0. Prior to contaminant addition, Fe(0) was allowed to pre-corrode within the systems for up to 46 days. The systems were then equilibrated for 30 days with a mixture of the two model contaminants. Result confirmed (i) the higher efficiency of SW over GI in removing both contaminants, (ii) the higher efficiency of Fe(0) for Orange II discoloration and (iii) the positive impact of initial low pH values on the efficiency of Fe(0)/H2O systems. The major output of this research is that conventional Fe(0)/H2O systems are not suitable for quantitative water defluoridation. It is suggested that ways to avoid defluoridation using Fe0 must be explored. One affordable opportunity is blending fluoride-polluted water with carefully harvested rainwater.

Removal of Cd (II) from synthetic wastewater by alginate-Ayous wood sawdust (Triplochiton scleroxylon) composite material.

The biosorption characteristics of Cd (II) ions from synthetic wastewater using raw Ayous wood sawdust (Triplochiton scleroxylon), r-AS, immobilized by sodium alginate were investigated with respect to pH, biomass quantity, contact time, initial concentration of heavy metal, temperature and stirring rate. The experimental data fitted well with the Langmuir isotherm, suggesting that monolayer adsorption of the cadmium ions onto alginate-Ayous sawdust composite (a-ASC). The obtained monolayer adsorption capacity of a-ASC for Cd (II) was 6.21 mg/g. From the Dubinin-Radushkevich isotherm model, a 5.39 kJ/mol value for the mean free energy was calculated, indicating that Cd (II) biosorption could include an important physisorption stage. Thermodynamic calculations showed that the Cd (II) biosorption process was feasible, endothermic and spontaneous in nature under examined conditions. The results indicated that a-ASC could be an alternative material replacing more costly adsorbents used for the removal of heavy metals.

Amperometric sensors based on sawdust film modified electrodes: application to the electroanalysis of paraquat.

Natural or sodium hydroxide treated Ayous sawdusts were used to prepare thin film electrodes (denoted respectively as PSTFE and SSTFE). The sensors obtained exhibit good mechanical stability and a wide electrochemical potential range. Their electrochemical characterization revealed that they present a good capacity to accumulate cations, but are not useful for the electroanalysis of anions. In all cases, the signals were more intense and well defined on SSTFE compared to PSTFE. When applied to the electroanalysis of paraquat, a significant improvement of the current intensities was obtained on these electrodes compared to the bare glassy carbon electrode. The diffusion of this compound through the film which is the main process governing the electrochemical reaction at the electrode surface, is 2.2 times more important with SSTFE compared to PSTFE. After the optimization of the detection parameters, calibration curves were obtained in the concentration range 0.1-0.725 µmol L(-1) for PSTFE and 0.05-0.6 µmol L(-1) for SSTFE. The detection limits determined for a signal/noise ratio=3 are 5.49×10(-9) mol L(-1) for PSTFE and 3.02×10(-9) mol L(-1) for SSTFE.

Study of the removal of paraquat from aqueous solution by biosorption onto Ayous (Triplochiton schleroxylon) sawdust.

This study concerns the batch biosorption of paraquat on Ayous (Triplochiton schleroxylon) sawdust; the study centers on the evolution of biosorption parameters during the process. It appears that paraquat forms a monolayer on the sawdust surface as evidenced by the good correlation between the experimental data and the Langmuir model. The biosorption which is rather fast (the equilibrium was reached after ten minutes) follows a pseudo-second-order kinetic model and does not obey to the intra-particle diffusion model. According to the mathematical kinetic modeling, pore and surface mass transfer well describe the phenomenon. NaCl reduces the adsorption capacity of the material but has no significant effect on the kinetics. Alkaline solutions enhance the accumulation of the pollutant, the reverse being observed for acidic media. According to the thermodynamic data, this biosorption is a spontaneous and exothermic process. From these results we concluded that the adsorption of the pollutant is mainly due to cation exchange as indicated by the adsorption energy determined by the Dubinin-Radushkevich model (E=12.0736 kJ mol(-1)); some other interactions resulting from the affinity through organophilic interactions between paraquat and sawdust have also been pointed out. Desorption experiments conducted in HCl and HNO(3) solutions confirmed the proposed mechanism.

Mercury(II) removal from water by electrocoagulation using aluminium and iron electrodes.

In this work, electrocoagulation was used to evaluate the treatment of synthetic solutions containing mercury(II) of concentration 2 x 10(-5)M. The effects of the distance between the electrodes, current density, charge loading and initial pH on the removal efficiency were investigated, using aluminium and iron electrodes. Analysis of the filtrates resulting from the treatment was made by anodic redissolution in the differential pulse mode. The removal efficiency was above 99.9% when the distance between the electrodes was 3 cm, the current density ranging from 2.5 to 3.125 A dm(-2); for instance, 99.95% of the mercury(II) was eliminated when a charge loading of 9.33 and 15.55 F m(-3) were used for iron and aluminium respectively. In these conditions, by varying the pH of the mercury(II) solutions from 3 to 7, the removal efficiency remained higher than 99%. In addition, some experiments were carried out on a river water contaminated with mercury(II) ions, and the results obtained showed that the presence of organic matter do not influence the efficiency of the treatment. The elimination of mercury(II) ions is best performed with iron, where 15 min of electrolysis was sufficient to reach the highest removal compared to aluminium which required 25 min for the same result.

Electrolytic arsenic removal for recycling of washing solutions in a remediation process of CCA-treated wood.

The remediation of chromated copper arsenate or CCA-treated wood is a challenging problem in many countries. In a wet remediation, the recycling of the washing solutions is the key step for a successful process. Within this goal, owing to its solubility and its toxicity, the removal of arsenic from washing solution is the most difficult process. The efficiency of arsenic removal from As(III) solutions by electrolysis was investigated in view of the recycling of acidic washing solutions usable in the remediation of CCA-treated wood. Electrochemical reduction of As(III) is irreversible and thus difficult to perform at carbon electrodes. However the electrolytic extraction of arsenic can be performed by the concomitant reduction of the cupric cation and arsenite anion. The cathodic deposits obtained by controlled potential electrolysis were analyzed by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis. XRD diffraction data indicated that these deposits were mixtures of copper and copper arsenides Cu(3)As and Cu(5)As(2). Electrolysis was carried out in an undivided cell with graphite cathode and copper anode, under a controlled nitrogen atmosphere. The evolution of arsine gas AsH(3) was not observed under these conditions.