Physico-chemical characterization of metal-doped bone chars and their adsorption behavior for water defluoridation

New bone chars for fluoride adsorption from drinking water have been synthetized via metallic doping using aluminum and iron salts. A detailed statistical analysis of the metal doping process using the signal-to-noise ratios from Taguchi's experimental designs and its impact on the fluoride adsorption properties of modified bone chars have been performed. The best conditions, including the proper metallic salt, for metal doping were identified to improve the fluoride uptakes of modified bone chars. Results showed that the fluoride adsorption properties of bone chars can be enhanced up to 600% using aluminum sulfate for the surface modification. This aluminum-based adsorbent showed an adsorption capacity of 31 mg/g, which outperformed the fluoride uptakes reported for several adsorbents. Surface interactions involved in the defluoridation process were established using FTIR, DRX and XPS analysis. Defluoridation using the metal-doped bone chars occurred via an ion exchange process between fluoride ions and the hydroxyl groups on the adsorbent surface, whereas the Al(OH)xFy, FexFy, and CaF2 interactions could play also an important role in the removal process. These metal-doped adsorbents anticipate a promising behavior in water treatment, especially in developing countries where the efficiency – cost tradeoff is crucial for implementing new defluoridation technologies.

The contribution of sulfate ions and protons to the specific capacitance of microporous carbon monoliths

The monoliths studied in this work show large specific surface areas (up to 1600 m2 g-1), high densities (up to 1.17 g cm-3) and high electrical conductivities (up to 9.5 S cm-1). They are microporous carbons with pore sizes up to 1.3 nm but most of them below 0.75 nm. They also show oxygen functionalities. The electrochemical behavior of the monoliths is studied in three-electrode cells with aqueous H2SO4 solution as electrolyte. This work deals with the contribution of the sulfate ions and protons to the specific capacitance of carbon monoliths having different surface areas and different contents of oxygen groups. Protons contribute with a pseudocapacitance (up to 152 F g-1) in addition to the double layer capacitance. Sulfate ions contribute with a double layer capacitance only. At the double layer, the capacitance of the sulfate ions (up to 291 F g-1) is slightly higher than that of protons (up to 251 F g-1); both capacitances increase as the surface area increases. The preference of protons to be electroadsorbed at the double layer and the broader voltage window of these ions account for their higher contribution (70 %) to the double layer capacitance.

Modification of Hematite Electronic Properties with Trimethyl Aluminum to Enhance the Efficiency of Photoelectrodes

The electronic properties of hematite were investigated by means of synchrotron radiation photoemission (SR-PES) and X-ray absorption spectroscopy (XAS). Hematite samples were exposed to trimethyl aluminum (TMA) pulses, a widely used Al-precursor for the atomic layer deposition (ALD) of Al2O3. SR-PES and XAS showed that the electronic properties of hematite were modified by the interaction with TMA. In particular, the hybridization of O 2p states with Fe 3d and Fe 4s4p changed upon TMA pulses due to electron inclusion as polarons. The change of hybridization correlates with an enhancement of the photocurrent density due to water oxidation for the hematite electrodes. Such an enhancement has been associated with an improvement in charge carrier transport. Our findings open new perspectives for the understanding and utilization of electrode modifications by very thin ALD films and show that the interactions between metal precursors and substrates seem to be important factors in defining their electronic and photoelectrocatalytic properties.

Enzyme mediated synthesis of polypyrrole in the presence of chondroitin sulfate and redox mediators of natural origin

Polypyrrole (PPy) was synthesized by enzyme mediated oxidation of pyrrole using naturally occurring compounds as redox mediators. The catalytic mechanism is an enzymatic cascade reaction in which hydrogen peroxide is the oxidizer and soybean peroxidase, in the presence of acetosyringone, syringaldehyde or vanillin, acts as a natural catalysts. The effect of the initial reaction composition on the polymerization yield and electrical conductivity of PPy was analyzed. Morphology of the PPy particles was studied by scanning electron microscopy and transmission electron microscopy whereas the chemical structure was studied by X-ray photoelectron and Fourier transformed infrared spectroscopic techniques. The redox mediators increased the polymerization yield without a significant modification of the electronic structure of PPy. The highest conductivity of PPy was reached when chondroitin sulfate was used simultaneously as dopant and template during pyrrole polymerization. Electroactive properties of PPy obtained from natural precursors were successfully used in the amperometric quantification of uric acid concentrations. PPy increases the amperometric sensitivity of carbon nanotube screen-printed electrodes toward uric acid detection.