Félix R. Román

Antimicrobial nanomaterials as water disinfectant: Applications, limitations and future perspectives

Nanotechnology and its application is one of the rapidly developing sciences. As demand of fresh drinking water is increasing, nanotechnology can contribute noticeable development and improvement to water treatment process. Disinfection process is the last and most important step in water and wastewater treatment process. Some nanomaterials can be used as disinfectants due to their antimicrobial properties and reduce the possibility of harmful disinfection by-products (DBPs) formation during traditional disinfection process. A significant number of research efforts is done or going on to understand the mechanisms and enhance the efficiency of nanomaterials as antimicrobial agents, although it will take more time to understand the full potential of nanomaterials in this field. This review paper focuses on inactivation pathways of benign nanomaterials, their possible and probable application and limitations as disinfectants and future opportunities for their application in water cleaning processes.

Tuning of magnetic properties in cobalt ferrite nanocrystals

Cobalt ferrite (CoFe2O4) possesses excellent chemical stability, good mechanical hardness, and a large positive first order crystalline anisotropy constant, making it a promising candidate for magneto-optical recording media. In addition to precise control of the composition and structure of CoFe2O4, its practical application will require the capability to control particle size at the nanoscale. The results of a synthesis approach in which size control is achieved by modifying the oversaturation conditions during ferrite formation in water through a modified coprecipitation approach are reported. X-ray diffraction, transmission electron microscopy (TEM) diffraction, and TEM energy-dispersive x-ray spectroscopy analyses confirmed the formation of the nanoscale cobalt ferrite. M-H measurements verified the strong influence of synthesis conditions on crystal size and hence, on the magnetic properties of ferrite nanocrystals. The room-temperature coercivity values increased from 460 up to 4626Oe under optimum...

Transition metal modified and partially calcined inorganic-organic pillared clays for the adsorption of salicylic acid, clofibric acid, carbamazepine, and caffeine from water.

Pharmaceutical and Personal Care Products (PPCPs) are considered emerging contaminants, and their efficient removal from water is going to be a challenging endeavor. Microporous adsorbent materials, including pillared clays, could offer a potential solution if tailored properly. Although pillared clays have been employed previously for the removal of organics, the effective removal of PPCPs will only be possible if their surface and textural properties are manipulated from the bottom-up. This work presents the use of modified inorganic-organic pillared clays (IOCs) for the adsorption of salicylic acid, clofibric acid, carbamazepine, and caffeine. The IOCs have been modified with Co(2+), Cu(2+), or Ni(2+) to induce complexation-like adsorbate-adsorbent interactions at ambient conditions, in an attempt to provide an efficient and yet reversible driving force in the sub-ppm concentration range. Furthermore, the IOCs were partially calcined to increase effective surface area by an order of magnitude while preserving some hydrophobicity. In general, the Ni(2+) IOCs exhibited the greatest interaction with salicylic and clofibric acids, respectively, while the Co(2+) adsorbents excelled at adsorbing caffeine at low concentrations. All of the metal-modified IOCs showed comparable adsorption capacities for the case of carbamazepine, probably due to the lack of availability of particular functional groups in this adsorbate.

Effect of cobalt ferrite (CoFe2O4) nanoparticles on the growth and development of Lycopersicon lycopersicum (tomato plants).

Nanoparticles (NPs) have been synthetized and studied to be incorporated in many industrial and medical applications in recent decades. Due to their different physical and chemical properties compared with bulk materials, researchers are focused to understand their interactions with the surroundings. Living organisms such as plants are exposed to these materials and they are able to tolerate different concentrations and types of NPs. Cobalt ferrite (CoFe2O4) NPs are being studied for their application in medical sciences because of their high coercivity, anisotropy, and large magnetostriction. These properties are desirable in magnetic resonance imaging, drug delivery, and cell labeling. This study is aimed to explore the tolerance of Solanum lycopersicum L. (tomato) plants to CoFe2O4 NPs. Tomato plants were grown in hydroponic media amended with CoFe2O4 nanoparticles in a range from 0 to 1000mgL(-1). Exposure to CoFe2O4 NPs did not affect germination and growth of plants. Uptake of Fe and Co inside plant tissues increased as CoFe2O4 nanoparticle concentration was increased in the media. Mg uptake in plant leaves reached its maximum level of 4.9mgg(-1) DW (dry weight) at 125mgL(-1) of CoFe2O4 NPs exposure and decreased at high CoFe2O4 NPs concentrations. Similar pattern was observed for Ca uptake in leaves where the maximum concentration found was 10mgg(-1) DW at 125mgL(-1) of CoFe2O4 NPs exposure. Mn uptake in plant leaves was higher at 62.5mgL(-1) of CoFe2O4 NPs compared with 125 and 250mgL(-1) treatments. Catalase activity in tomato roots and leaves decreased in plants exposed to CoFe2O4 NPs. Tomato plants were able to tolerate CoFe2O4 NPs concentrations up to 1000mgL(-1) without visible toxicity symptoms. Macronutrient uptake in plants was affected when plants were exposed to 250, 500 and 1000mgL(-1) of CoFe2O4 NPs.

Single and multi-component adsorption of salicylic acid, clofibric acid, carbamazepine and caffeine from water onto transition metal modified and partially calcined inorganic-organic pillared clay fixed beds.

Fixed-beds of transition metal (Co(2+), Ni(2+) or Cu(2+)) inorganic-organic pillared clays (IOCs) were prepared to study single- and multi-component non-equilibrium adsorption of a set of pharmaceutical and personal care products (PPCPs: salicylic acid, clofibric acid, carbamazepine and caffeine) from water. Adsorption capacities for single components revealed that the copper(II) IOCs have better affinity toward salicylic and clofibric acid. However, multi-component adsorption tests showed a considerable decrease in adsorption capacity for the acids and an unusual selectivity toward carbamazepine depending on the transition metal. This was attributed to a combination of competition between PPCPs for adsorption sites, adsorbate-adsorbate interactions, and plausible pore blocking caused by carbamazepine. The cobalt(II) IOC bed that was partially calcined to fractionate the surfactant moiety showcased the best selectivity toward caffeine, even during multi-component adsorption. This was due to a combination of a mildly hydrophobic surface and interaction between the PPCP and cobalt(II). In general, the tests suggest that these IOCs may be a potential solution for the removal of PPCPs if employed in a layered-bed configuration, to take care of families of adsorbates in a sequence that would produce sharpened concentration wavefronts.

Synthesis and Characterization of Palladium and Palladium–Cobalt Nanoparticles on Vulcan XC-72R for the Oxygen Reduction Reaction

A single-source approach was used to synthesize bimetallic nanoparticles on a high-surface-area carbon-support surface. The synthesis of palladium and palladium-cobalt nanoparticles on carbon black (Vulcan XC-72R) by chemical and thermal reduction using organometallic complexes as precursors is described. The electrocatalysts studied were Pd/C, Pd2Co/C, and PdCo2/C. The nanoparticles composition and morphology were characterized using inductively coupled plasma mass spectrophotometer (ICP-MS), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray fluorescence spectroscopy (EDS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) techniques. Electrocatalytic activity towards the oxygen reduction reaction (ORR) and methanol tolerance in oxygen-saturated acid solution were determined. The bimetallic catalyst on carbon support synthetized by thermal reduction of the Pd2Co precursor has ORR electrocatalytic activity and a higher methanol tolerance than a Pt/C catalyst.

Single and multi-component adsorptive removal of bisphenol A and 2,4-dichlorophenol from aqueous solutions with transition metal modified inorganic-organic pillared clay composites: Effect of pH and presence of humic acid.

Pillared clay based composites containing transition metals and a surfactant, namely MAlOr-NaBt (Bt=bentonite; Or=surfactant; M=Ni(2+), Cu(2+)or Co(2+)), were prepared to study selectivity and capacity toward single and multiple-component adsorption of bisphenol A (BPA) and 2,4-diclorophenol (DCP) from water. Tests were also performed to account for the presence of natural organic matter in the form of humic acid (HA). Equilibrium adsorption capacities for single components increased as follows: NaBt<Al-NaBt<AlOr-NaBt<MAlOr-NaBt. The observed equilibrium loadings were ca. 5 and 3mgg(-1) for BPA and DCP, respectively, at neutral pH conditions and ambient temperature, representing an ordered of magnitude increase over the unmodified pillared clay capacities. Inclusion of the transition metal brought an increase of nearly two-fold in adsorption capacity over the materials modified only with surfactant. The MAlOr-NaBt adsorbents displayed remarkable selectivity for BPA. Multi-component fixed-bed tests, however, revealed competition between the adsorbates, with the exception of the CuAlOr-NaBt beds. Inclusion of HA, surprisingly, enhanced the phenols adsorption capacity. Preliminary regeneration tests suggested that the adsorbent capacity can be recovered via thermal treatment or by washing with alkaline solutions. The former strategy, however, requires surfactant replenishment. More complex schemes would be needed to deal with absorbed HA.

Photocatalytic activity of quantum dot–magnetite nanocomposites to degrade organic dyes in the aqueous phase

Quantum dots of Cd(Se,S) and fluorescent magnetic nanocomposites (Cd(Se,S)–magnetite) were used as photocatalytic agents in the photodegradation of methylene blue (MB) under UV irradiation at pH 6.5. Quantum dots and magnetic nanocomposites were characterized by X-ray diffraction (XRD), UV-Vis, photoluminescence and Fourier Transform Infrared (FT-IR) spectroscopy. The photo-induced degradation of MB was monitored using High Performance Liquid Chromatography (HPLC) at 660 nm and titanium dioxide (anatase and aeroxide P25 forms) was used as the photocatalyst standard. A degradation of 99.1% and 90.0% of MB was achieved in the presence of 160 mg L−1-quantum dots and the magnetic nanocomposite, respectively, after 4.5 hours of UV-irradiation. Instead, 45.9% and 100% of MB degradation was achieved using 160 mg L−1 of TiO2 anatase and aeroxide P25, respectively. The degradation products were studied by mass spectrometry (MS) and the results evidenced the formation of azure B, A, C and phenothiazine. The reuse of the magnetic nanocomposites (i.e., after one photo-degradation cycle) allowed a maximum photo-degradation capacity of 65%. The results suggested that the nanocomposite has 10% less photodegradation capacity than the widely used catalytic agents such as TiO2 aeroxide P25.

Preparative size-exclusion chromatography for separation and purification of water-stable Cd-based quantum dots

Size-exclusion chromatography (SEC) associated with High Performance Liquid Chromatography (HPLC) is a powerful tool to separate, purify and fractionalize materials based on size. In this paper, we present a SEC method that was developed for the separation of thiol-capped Cd(Se,S) quantum dots (QDs) synthesized in the aqueous phase. A HPLC system with a SEC column and a cascade of three detectors (UV/Vis, FLD and ELSD) was used to analyze the different size fractions of QDs. Nanocrystals–HPLC column interactions were suppressed using thioglycolic acid (TGA) as an ion pair agent. Five fractions, namely F1 to F5, of different sizes and tunable optical properties were isolated from the original QDs sample. The emission peaks for fractions F1 and F2 were red-shifted and the fractions F4 and F5 were blue-shifted compared with the original sample, which suggested the presence of nanocrystals having different sizes. Dynamic Light Scattering (DLS) confirmed that collected fractions exhibited different hydrodynamic diameters ranging from 98.2 nm (fraction F1) to 24.9 nm (fraction F5). Also, fractions F2 and F4 were functionalized with glutathione and analyzed by HPLC-SEC. Glutathione-capped Cd(Se,S) QDs showed an increase in their molecular weight, when compared to bare TGA-capped Cd(Se,S) QDs, without a remarkable change of their crystal size and optical properties. The developed SEC technique allows a fast and reproducible separation of water-stable Cd(Se,S) QDs. Collected fractions with tunable optical properties could have potential applications in the nanotechnology area such as bio-imaging and diagnostics, e.g. cell sorting.

Use of recycled tires crumb rubber to remove organic contaminants from aqueous and gaseous phases

Abstract Tire crumb rubber (TCR) was used to remove poly-aromatic hydrocarbons (acenaphthene and phenanthrene) and gasoline components in aqueous phase and toluene in gaseous phase. The initial concentrations were below the solubility of each contaminant. To better understand the role of the main components of TCR, the removal was also evaluated using carbon black (CB) and styrene-butadiene polymer (SBP). The Scatchard plots suggested multiple interactions between adsorbates and TCR, whereas a single interaction became evident for CB and SBP. The removal of gasoline components, and toluene and o-xylene in gasoline was evaluated using total ion current mode and selective ion monitoring mode, respectively. A gas chromatographer was modified to evaluate the removal of gaseous toluene. Toluene was injected at a rate of 30 μL/h. The isotherm was elaborated using pressures between 2.5 and 40 psi. The maximum uptake capacities (K f) for TCR calculated from Freundlich’s equation for acenaphthene and phenanthrene ...