A Comparative Study of the Catalytic Performance of Pt-Based Bi and Trimetallic Nanocatalysts Towards Methanol, Ethanol, Ethylene Glycol, and Glycerol Electro-Oxidation.

Carbon-supported platinum is used as an anode and cathode electrocatalyst in low-temperature fuel cells fueled with low-molecular-weight alcohols in fuel cells. The cost of Pt and its low activity towards the complete oxidation of these fuels are significant barriers to the widespread use of these types of fuel cells. Here, we report on the development of PtRhNi nanocatalysts supported on carbon made using a reduction chemistry method with different atomic rates. The catalytic activity of the developed catalysts towards the electro-oxidation of methanol, ethanol, ethylene glycol, and glycerol in acidic media was studied. The obtained catalysts performances were compared with both commercial Pt/C and binary Pt75Ni25/C catalyst. The nanostructures were characterized, employing inductively coupled plasma optical emission spectrometer, X-ray diffraction, scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The binary catalyst presents a mean particle size of around 2 nm. Whereas the ternary catalysts present particles of similar size and with some large alloy and core-shell structures. The alcohol oxidation onset potential and the current density measured after 3600 s of chronoamperometry were used to classify the catalytic activity of the catalysts towards the oxidation of methanol, ethanol, ethylene glycol, and glycerol. The best PtRhNi/C catalyst composition (i.e., Pt43Rh43Ni14/C) presented the highest activity for alcohols oxidation compared with all catalysts studied, indicating the proper tuning composition influence in the catalytic activity. The enhanced activity of Pt43Rh43Ni14/C can be attributed to the synergic effect of trimetallic compounds, Pt, Ni, and Rh.

A preconcentration system for determination of copper and nickel in water and food samples employing flame atomic absorption spectrometry.

A separation/preconcentration procedure using solid phase extraction has been proposed for the flame atomic absorption spectrometric determination of copper and nickel at trace level in food samples. The solid phase is Dowex Optipore SD-2 resin contained on a minicolumn, where analyte ions are sorbed as 5-methyl-4-(2-thiazolylazo) resorcinol chelates. After elution using 1 mol L(-1) nitric acid solution, the analytes are determinate employing flame atomic absorption spectrometry. The optimization step was performed using a full two-level factorial design and the variables studied were: pH, reagent concentration (RC) and amount of resin on the column (AR). Under the experimental conditions established in the optimization step, the procedure allows the determination of copper and nickel with limit of detection of 1.03 and 1.90 microg L(-1), respectively and precision of 7 and 8%, for concentrations of copper and nickel of 200 microg L(-1). The effect of matrix ions was also evaluated. The accuracy was confirmed by analyzing of the followings certified reference materials: NIST SRM 1515 Apple leaves and GBW 07603 Aquatic and Terrestrial Biological Products. The developed method was successfully applied for the determination of copper and nickel in real samples including human hair, chicken meat, black tea and canned fish.

Direct determination of iron and manganese in wine using the reference element technique and fast sequential multi-element flame atomic absorption spectrometry.

A procedure is proposed for the direct determination of manganese and iron in wine employing fast sequential flame atomic absorption spectrometry and the reference element technique to correct for matrix effects. Cobalt, silver, nickel and indium have been tested as reference elements. The results demonstrated that cobalt and indium at a concentration of 2 and 10mgL(-1) were efficient for quantification of manganese and iron, respectively. Under these conditions, manganese and iron could be determined with quantification limits of 27 and 40microg L(-1), respectively. The proposed method was applied to the determination of manganese and iron in 16 wine samples. The content of manganese varied from 0.78 to 2.89mgL(-1) and that of iron from 0.88 to 9.22mgL(-1). The analytical results were compared with those obtained by inductively coupled plasma optical emission spectrometry after complete mineralization using acid digestion. The statistical comparison by a t-test (95% confidence level) showed no significant difference between the results.

Development of method for the speciation of inorganic iron in wine samples.

In this paper, we proposed a procedure for the determination of iron(II) and total iron in wine samples employing molecular absorption spectrophotometry. The ligand used is 2-(5-bromo-2-pyridylazo)-5-(diethylamino)-phenol (Br-PADAP) and the chromogenic reaction in absence or presence of ascorbic acid (reducing agent) allows the determination of iron(II) or total iron, respectively. The optimization step was performed using a multivariate technique (Box Behnken design) involving the factors pH, acid ascorbic concentration and reaction time. The method allows the determination of iron(II) and iron(III) in wine samples, with limits of detection and quantification 0.22 and 0.72 microg L(-1), respectively. The precision expressed as relative standard deviation (R.S.D.) was 1.43 and 0.56% (both, n=11) for content of iron(II) in wine samples of 1.68 and 4.65 mg L(-1), and 1.66 and 0.87% (both, n=11) for content of total iron in wine samples of 1.72 and 5.48 mg L(-1). This method was applied for determination of iron(II) and total iron in six different wine samples. In these, the iron(II) content varied from 0.76 to 4.65 mg L(-1) and from 1.01 to 5.48 mg L(-1) for total iron. The results obtained in the determination of total iron by Br-PADAP method were compared with those that were performed after complete acid digestion in open system and determination of total iron employing FAAS. The method of regression linear was used for comparison of these results and demonstrated that there is no significant difference between the results obtained with these two procedures.

Review of procedures involving separation and preconcentration for the determination of cadmium using spectrometric techniques.

Spectrometric techniques for the analysis of trace cadmium have developed rapidly due to the increasing need for accurate measurements at extremely low levels of this element in diverse matrices. This review covers separation and preconcentration procedures, such as electrochemical deposition, precipitation, coprecipitation, solid phase extraction, liquid-liquid extraction (LLE) and cloud point extraction (CPE), and consider the features of the their application with several spectrometric techniques.