Study of adsorption and preconcentration by using a new silica organomodified with [3-(2,2′-dipyridylamine)propyl] groups

In this work, a silica surface chemically modified with [3-(2,2′-dipyridylamine)propyl] groups, named [3-(2,2′- dipyridylamine)propyl]silica (Si-Pr-DPA) was prepared, characterized, and evaluated for its heavy metal adsorption characteristics from aqueous solution. To our knowledge, we are the first authors who have reported the present modification. The material was characterized using infrared spectroscopy, SEM, and NMR 29Si and 13C solid state. Batch and column experiments were conducted to investigate for heavy metal removal from dilute aqueous solution by sorption onto Si-Pr-DPA. From a number of studies the affinity of various metal ions for the Si-Pr-DPA sorbent was determined to follow the order Fe(III) > Cr(III) >> Cu(II) > Cd(II) > Pb(II) > Ni(II). Two standard reference materials were used for checking the accuracy and precision of the method. The proposed method was successfully applied to the analysis of environmental samples. This ligand material has great advantage for adsorption of transition-metal ions from aqueous medium due to its high degree of organofunctionalization associated with the large adsorption capacity, reutilization possibility, and rapidity in reaching the equilibrium. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Desorption of heavy metals from ion exchange resin with water and carbon dioxide

Adsorption and regeneration of ion exchange resins were studied using a subcritical solution of a CO₂-H₂O mixture and a fixed bed column. The commercial Amberlite IRC-50/IRC-86 cation exchange resins and Amberlite IRA-67 anion exchange resin were tested for heavy metals (Pb, Cu, Cd) adsorption from a solution with different initial metal concentrations at different temperatures. After adsorption, the loaded resins were regenerated with water and carbon dioxide at different temperatures and a pressure of 25 MPa. The efficiency of the IRC-50 resin was lower than that of the IRC-86 resin for the adsorption of metals like Cd, Cu and Pb. Results obtained for desorption of these metals indicated that the process could be used for Cd and in principle for Cu. Sorption of metal ions depended strongly on feed concentration. Mathematical modeling of the metal desorption process was carried out successfully as an extraction process. For this purpose, the VTII Model, which is applied to extraction from solids using supercritical solvents, was used in this work.

Application of mesoporous SBA-15 silica functionalized with 4-amino-2-mercaptopyrimidine for the adsorption of Cu(II), Zn(II), Cd(II), Ni(II), and Pb(II) from water

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis of polycationic bentonite-ionene complexes and their benzene adsorption capacity

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Tailored SERS substrates obtained with cathodic arc plasma ion implantation of gold nanoparticles into a polymer matrix

This manuscript reports on the fabrication of plasmonic substrates using cathodic arc plasma ion implantation, in addition to their performance as SERS substrates. The technique allows for the incorporation of a wide layer of metallic nanoparticles into a polymer matrix, such as PMMA. The ability to pattern different structures using the PMMA matrix is one of the main advantages of the fabrication method. This opens up new possibilities for obtaining tailored substrates with enhanced performance for SERS and other surface-enhanced spectroscopies, as well as for exploring the basic physics of patterned metal nanostructures. The architecture of the SERS-active substrate was varied using three adsorption strategies for incorporating a laser dye (rhodamine): alongside the nanoparticles into the polymer matrix, during the polymer cure and within nanoholes lithographed on the polymer. As a proof-of-concept, we obtained the SERS spectra of rhodamine for the three types of substrates. The hypothesis of incorporation of rhodamine molecules into the polymer matrix during the cathodic arc plasma ion implantation was supported by FDTD (Finite-Difference Time-Domain) simulations. In the case of arrays of nanoholes, rhodamine molecules could be adsorbed directly on the gold surface, then yielding a well-resolved SERS spectrum for a small amount of analyte owing to the short-range interactions and the large longitudinal field component inside the nanoholes. The results shown here demonstrate that the approach based on ion implantation can be adapted to produce reproducible tailored substrates for SERS and other surface-enhanced spectroscopies.

Developments in target-ion source chemistry for ISOL facilities

This work investigates the influence of chemical reactions on the release of elements from target-ion source units for ISOL facilities. Methods employed are thermochromatography, yield and hold-up time measurements; adsorption enthalpies have been determined for Ag and In. The results obtained with these methods are consistent. Elements exhibit reversible or irreversible reactions on different surfaces (Tantalum, quartz, sapphire). The interactions with surfaces inside the target-ion source unit can be used to improve the quality of radioactive ion beams. Spectroscopic data obtained at CERN-ISOLDE using a medium-temperature quartz transfer line show the effectivity of selective adsorption for beam purification. New gamma lines of 131Cd have been observed and a tentative decay scheme is presented.

Dressed polyions, counterion condensation, and adsorption excess in polyelectrolyte solutions.

The phenomenon of Manning-Oosawa counterion condensation is given an explicit statistical mechanical and qualitative basis via a dressed polyelectrolyte formalism in connection with the topology of the electrostatic free-energy surface and is derived explicitly in terms of the adsorption excess of ions about the polyion via the nonlinear Poisson-Boltzmann equation. The approach is closely analogous to the theory of ion binding in micelles. Our results not only elucidate a Poisson-Boltzmann analysis, which shows that a fraction of the counterions lie within a finite volume around the polyion even if the volume of the system tends towards infinity, but also provide a direct link between Manning's theta-the number of condensed counterions for each polyion site-and a statistical thermodynamic quantity, namely, the adsorption excess per monomer.

Electrochemical characteristics of ordered mesoporous carbon used as electrode material in Li-ion battery

Ordered mesoporous carbon CMK-5 was comprehensively tested for the first time as electrode materials in lithium ion battery. The surface morphology, pore structure and crystal structure were investigated by Scanning Electronic Microscopy (SEM), N-2 adsorption technique and X-ray diffraction (XRD) respectively. Electrochemical properties of CMK-5 were studied by galvanostatic cycling and cyclic voltammetry, and compared with conventional anode material graphite. Results showed that the reversible capacity of CMK-5 was 525 mAh/g at the third charge-discharge cycle and that CMK-5 was more compatible for quick charge-discharge cycling because of its special mesoporous structure. Of special interest was that the CMK-5 gave no peak on its positive sweep of the cyclic voltammetry, which was different from all the other known anode materials. Besides, X-ray photoelectron spectroscopy (XPS) and XRD were also applied to investigate the charge-discharge characteristics of CMK-5.

Fibronectin/phosphorylcholine coatings on fluorocarboned surfaces: a study upon adsorption and grafting processes

Depuis ces dernières décennies, le domaine des biomatériaux a connu un essor considérable, évoluant de simples prothèses aux dispositifs les plus complexes pouvant détenir une bioactivité spécifique. Outre, le progrès en science des matériaux et une meilleure compréhension des systèmes biologiques a offert la possibilité de créer des matériaux synthétiques pouvant moduler et stimuler une réponse biologique déterminée, tout en améliorant considérablement la performance clinique des biomatériaux. En ce qui concerne les dispositifs cardiovasculaires, divers recouvrements ont été développés et étudiés dans le but de modifier les propriétés de surface et d’améliorer l’efficacité clinique des tuteurs. En effet, lorsqu’un dispositif médical est implanté dans le corps humain, son succès clinique est fortement influencé par les premières interactions que sa surface établit avec les tissus et les fluides biologiques environnants. Le recouvrement à la surface de biomatériaux par diverses molécules ayant des propriétés complémentaires constitue une approche intéressante pour atteindre différentes cibles biologiques et orienter la réponse de l’hôte. De ce fait, l’élucidation de l’interaction entre les différentes molécules composant les recouvrements est pertinente pour prédire la conservation de leurs propriétés biologiques spécifiques. Dans ce travail, des recouvrements pour des applications cardiovasculaires ont été créés, composés de deux molécules ayant des propriétés biologiques complémentaires : la fibronectine (FN) afin de promouvoir l’endothélialisation et la phosphorylcholine (PRC) pour favoriser l’hémocompatibilité. Des techniques d’adsorption et de greffage ont été appliquées pour créer différents recouvrements de ces deux biomolécules sur un polymère fluorocarboné déposé par traitement plasma sur un substrat en acier inoxydable. Dans un premier temps, des films de polytétrafluoroéthylène (PTFE) ont été utilisés en tant que surface modèle afin d’explorer l’interaction de la PRC et de la FN avec les surfaces fluorocarbonées ainsi qu’avec des cellules endothéliales et du sang. La stabilité des recouvrements de FN sur l’acier inoxydable a été étudiée par déformation, mais également par des essais statiques et dynamiques sous-flux. Les recouvrements ont été caractérisés par Spectroscopie Photoéléctronique par Rayons X, immunomarquage, angle de contact, Microscopie Électronique de Balayage, Microscopie de Force Atomique et Spectrométrie de Masse à Ionisation Secondaire à Temps de Vol (imagerie et profilage en profondeur). Des tests d’hémocompatibilité ont été effectués et l’interaction des cellules endothéliales avec les recouvrements a également été évaluée. La FN greffée a présenté des recouvrements plus denses et homogènes alors que la PRC quant à elle, a montré une meilleure homogénéité lorsqu’elle était adsorbée. La caractérisation de la surface des échantillons contenant FN/PRC a été corrélée aux propriétés biologiques et les recouvrements pour lesquels la FN a été greffée suivie de l’adsorption de la PRC ont présenté les meilleurs résultats pour des applications cardiovasculaires : la promotion de l’endothélialisation et des propriétés d’hémocompatibilité. Concernant les tests de stabilité, les recouvrements de FN greffée ont présenté une plus grande stabilité et densité que dans le cas de l’adsorption. En effet, la pertinence de présenter des investigations des essais sous-flux versus des essais statiques ainsi que la comparaison des différentes stratégies pour créer des recouvrements a été mis en évidence. D’autres expériences sont nécessaires pour étudier la stabilité des recouvrements de PRC et de mieux prédire son interaction avec des tissus in vivo.

Wastewater treatment by novel hybrid biological – ion exchange processes

This study presents two novel methods for treating important environmental contaminants from two different wastewater streams. One process utilizes the kinetic advantages and reliability of ion exchanging clinoptilolite in combination with biological treatment to remove ammonium from municipal sewage. A second process, HAMBgR (Hybrid Adsorption Membrane Biological Reactor), combines both ion exchange resin and bacteria into a single reactor to treat perchlorate contaminated waters. Combining physicochemical adsorptive treatment with biological treatment can provide synergistic benefits to the overall removal processes. Ion exchange removal solves some of the common operational reliability limitations of biological treatment, like slow response to environmental changes and leaching. Biological activity can in turn help reduce the economic and environmental challenges of ion exchange processes, like regenerant cost and brine disposal. The second section of this study presents continuous flow column experiments, used to demonstrate the ability of clinoptilolite to remove wastewater ammonium, as well as the effectiveness of salt regeneration using highly concentrated sea salt solutions. The working capacity of clinoptilolite more than doubled over the first few loading cycles, while regeneration recovered more than 98% of ammonium. Using the regenerant brine for subsequent halotolerant algae growth allowed for its repeated use, which could lead to cost savings and production of valuable algal biomass. The algae were able to uptake all ammonium in solution, and the brine was able to be used again with no loss in regeneration efficiency. This process has significant advantages over conventional biological nitrification; shorter retention times, wider range of operational conditions, and higher quality effluent free of nitrate. Also, since the clinoptilolite is continually regenerated and the regenerant is rejuvenated by algae, overall input costs are expected to be low. The third section of this study introduces the HAMBgR process for the elimination of perchlorate and presents batch isotherm experiments and pilot reactor tests. Results showed that a variety of ion-exchange resins can be effectively and repeatedly regenerated biologically, and maintain an acceptable working capacity. The presence of an adsorbent in the HAMBgR process improved bioreactor performance during operational fluctuations by providing a physicochemical backup to the biological process. Pilot reactor tests showed that the HAMBgR process reduced effluent perchlorate spikes by up to 97% in comparison to a conventional membrane bio-reactor (MBR) that was subject to sudden changes in influent conditions. Also, the HAMBgR process stimulated biological activity and lead to higher biomass concentrations during increased contaminant loading conditions. Conventional MBR systems can be converted into HAMBgR’s at a low cost, easily justifiable by the realized benefits. The concepts employed in the HAMBgR process can be adapted to treat other target contaminants, not just perchlorate.

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.

DEVELOPMENT OF ION EXCHANGE MODELS FOR WATER TREATMENT AND APPLICATION TO THE INTERNATIONAL SPACE STATION WATER PROCESSOR

The International Space Station (ISS) requires a substantial amount of potable water for use by the crew. The economic and logistic limitations of transporting the vast amount of water required onboard the ISS necessitate onboard recovery and reuse of the aqueous waste streams. Various treatment technologies are employed within the ISS water processor to render the waste water potable, including filtration, ion exchange, adsorption, and catalytic wet oxidation. The ion exchange resins and adsorption media are combined in multifiltration beds for removal of ionic and organic compounds. A mathematical model (MFBMODEL™) designed to predict the performance of a multifiltration (MF) bed was developed. MFBMODEL consists of ion exchange models for describing the behavior of the different resin types in a MF bed (e.g., mixed bed, strong acid cation, strong base anion, and weak base anion exchange resins) and an adsorption model capable of predicting the performance of the adsorbents in a MF bed. Multicomponent ion exchange ii equilibrium models that incorporate the water formation reaction, electroneutrality condition, and degree of ionization of weak acids and bases for mixed bed, strong acid cation, strong base anion, and weak base anion exchange resins were developed and verified. The equilibrium models developed use a tanks-inseries approach that allows for consideration of variable influent concentrations. The adsorption modeling approach was developed in related studies and application within the MFBMODEL framework was demonstrated in the Appendix to this study. MFBMODEL consists of a graphical user interface programmed in Visual Basic and Fortran computational routines. This dissertation shows MF bed modeling results in which the model is verified for a surrogate of the ISS waste shower and handwash stream. In addition, a multicomponent ion exchange model that incorporates mass transfer effects was developed, which is capable of describing the performance of strong acid cation (SAC) and strong base anion (SBA) exchange resins, but not including reaction effects. This dissertation presents results showing the mass transfer model's capability to predict the performance of binary and multicomponent column data for SAC and SBA exchange resins. The ion exchange equilibrium and mass transfer models developed in this study are also applicable to terrestrial water treatment systems. They could be applied for removal of cations and anions from groundwater (e.g., hardness, nitrate, perchlorate) and from industrial process waters (e.g. boiler water, ultrapure water in the semiconductor industry).