In situ sensing of metal ion adsorption to a thiolated surface using surface plasmon resonance spectroscopy

The kinetics of the adsorption of metal ions onto a thiolated surface and the selective and quantitative sensing of metal ions were explored using surface plasmon resonance (SPR) spectroscopy. The target metal ion was an aqueous solution of Pt2+ and a thin-gold-film-coated glass substrate was modified with 1,6-hexanedithiol (HDT) as a selective sensing layer. SPR spectroscopy was used to examine the kinetics of metal ion adsorption by means of the change in SPR angle. The selectivity of the thiolated surface for Pt2+ over other divalent metal ions such as Cu2+, Ni2+, and Cd2+ was evident by the time-resolved SPR measurement. SPR angle shift, deltatheta(SPR), was found to increase logarithmically with increasing concentration of Pt2+ in the range of 1.0 x 10(-5)-1.0 mM. The rate of Pt2+ adsorption on HDT observed at both 0.1 and 1 mM Pt2+ accelerates until the surface coverage reaches approximately 17%, after which the adsorption profile follows Langmuirian behavior with the surface coverage. The experimental data indicated that heavy metal ions were adsorbed to the hydrophobic thiolated surface by a cooperative mechanism. A mixed self-assembled monolayer (SAM) composed of HDT and 11-mercaptoundecanoic acid was used to reduce the hydrophobicity of the thiol-functionalized surface. The addition of hydrophilic groups to the surface enhanced the rate of adsorption of Pt2+ onto the surface. The findings show that the adsorption of metal ions is strongly dependent upon the hydrophilicity/hydrophobicity of the surface and that the technique represents an easy method for analyzing the adsorption of metal ions to a functionalized surface by combining SPR spectroscopy with a SAM modification.     

Modifying the surface of TEOS xerogel by metal ion Zn(II)

The removal of 2,4-dichlorophenol from aqueous solution by modified TEOS xerogel has been studied in batch experiments at varying pH (2.0–8.0). Tetraethyl orthosilicate (TEOS) xerogel recently has been considered as an adsorbent which is more active. Surface of the adsorbent due to the outward oxygen atoms in the molecular structure, is negatively charged, so this solid, shows good ability to adsorb metal ions. But because of the negative charge on the surface of the adsorbent, the anions, particularly organic anion compounds are not absorbed. To fix this problem, it can set the metal ions on the surface of the solid. By placing Zn ions on the xerogel, a positive charge on the surface of the adsorbent is made, which increases the ability of the adsorbent to attract 2, 4-dichlorophenol from aqueous solutions. Results show an increase in the adsorption by about 17% on empty xerogel, by about 60% in xerogel modified with metal Zn (II) ion.

     

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane as ligands for Cu(II), Ni(II), Cd(II), Zn(II), and Fe(III) in aqueous solution

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane (ATZ-SSQ) were tested as ligands for transition-metal ions in aqueous solution with a special attention to sorption isotherms, ligand-metal interaction, and determination of metal ions in natural waters. The adsorption potential of the material ATZ-SSQ was compared with related [3(3-amino-1,2,4-triazole)propyl]silica gel (ATZ-SG). The adsorption was performed using a batchwise process and both organofunctionalized surfaces showed the ability to adsorb the metal ions from aqueous solution. The Langmuir model was used to simulate the sorption isotherms. The results suggest that the sorption of these metals on ATZ-SSQ and ATZ-SG occurs mainly by surface complexation. The equilibrium condition is reached at time lower than 3 min for ATZ-SSQ, while for ATZ-SG is only reached at time of 25 min. The maximum metal ion uptake values for ATZ-SSQ were higher than the corresponding values achieved with the ATZ-SG. In order to obtain more information on the ligand-metal interaction of the complexes on the surface of the ATZ-SSQ nanomaterial, ESR study with various degrees of copper loadings was carried out. The ATZ-SSQ was tested for the determination (in flow using a column technique) of the metal ions present in natural waters.     

Solution-phase electronegativity scale: insight into the chemical behaviors of metal ions in solution

By incorporating the solvent effect into the Born effective radius, we have proposed an electronegativity scale of metal ions in aqueous solution with the most common oxidation states and hydration coordination numbers in terms of the effective ionic electrostatic potential. It is found that the metal ions in aqueous solution are poorer electron acceptors compared to those in the gas phase. This solution-phase electronegativity scale shows its efficiency in predicting some important properties of metal ions in aqueous solution such as the aqueous acidities of the metal ions, the stability constants of metal complexes, and the solubility product constants of the metal hydroxides. We have elaborated that the standard reduction potential and the solution-phase electronegativity are two different quantities for describing the processes of metal ions in aqueous solution to soak up electrons with different final states. This work provides a new insight into the chemical behaviors of the metal ions in aqueous solution, indicating a potential application of this electronegativity scale to the design of solution reactions.     

Removal of metal ions from aqueous solution by chelating polymeric microspheres bearing phytic acid derivatives

The aim of this study was to investigate the possibility to synthesize new chelating polymeric microspheres owing immobilized biocompatible agent as chelating functional groups and to evaluate their performance in metal ions removal from aqueous solution.The microparticles were synthesized via precipitation polymerization of 4-O-(4-vinylbenzyl)-myo-inositol 1,3,5-orthoformate with ethylene glycol dimethacrylate (EGDMA) and subsequent exhaustive phosphorylation of myo-inositol groups using phosphoric acid.Spherical geometry with monodisperse nature of the polymeric microparticles was confirmed by scanning electron micrographs (SEM) and dimensional analysis. A large surface area of the microspheres provided a maximum interaction of metal ions and the chelating functional groups on the surface. Absorption capacity of the beads for the selected metal ions, i.e., Cu(II), Ni(II), Fe(III), was investigated in detail in aqueous solution at pH 5.0 utilizing UV/Vis spectroscopy. This study showed that the macromolecular systems are very effective in chelating these metal ions and the affinity order of the microbeads toward metal ions is: Fe(III) > Ni(II) > Cu(II).The chelating beads can be easily regenerated by 1.0 M HNO₃ with high effectiveness. These features make the synthesized beads a potential candidate for metal ions removal at high capacity.     

Analytical application of surface-affinity polymerized vesicular membranes to trace metal analysis by electrothermal atomic absorption spectrometry

The affinity of anionic polymerized vesicular membranes for metal cations in aqueous solutions is explored in terms of metal ion extraction and preconcentration. The method is based on the coordination of metal ions on the surface of charged polymerized vesicles via intra-vesicular complexes. These are causing changes in the selectivity, reactivity and inter-vesicular bridges which facilitate the aggregation of polymerized vesicles promoting phase separation. An analytical demonstration is shown by the optimization of the experimental conditions that enable the determination of antimony (III) in natural waters. The analytical features of the method including detection limits, precision and analytical recoveries from spiked natural water samples suggest that polymerized vesicular membranes can be a promising alternative to surfactant-mediated extractions of metal ions from aqueous matrices.     

Modification of Surface Forces by Metal Ion Adsorption

Abstract

Sorption of ions may lead to variations in interparticle forces and, thus, changes in the stability of colloidal particles. Chemical interactions between metal ions and colloidal particles modify the molecular structure of the surface, the surface charge, and the electrical potential between colloidal particles. These modifications to the surface and to the electrical double layer due to metal ion sorption are reflected in the interaction force between a particle and another surface, which is measured in this study by atomic force microscopy (AFM). Specifically, AFM is used to investigate the sorption of copper ions from aqueous solutions by silica particles. The influence of metal ion concentration and solution ionic strength on surface forces is studied under transient conditions. Results show that as the metal ion concentration is decreased, charge reversal occurs and a longer period of time is required for the system to reach equilibrium. The ionic strength has no significant effect on sorption kinetics. Furthermore, neither metal concentration nor ionic strength exhibits any effect on sorption equilibria, indicating that for the experimental conditions used in this study, the surface sites of the silica particle are fully occupied by copper ions.     

Langmuir-Blodgett composite films for the selective determination of calcium in aqueous solutions

A sensitive membrane of a new type was suggested for the determination of calcium ions in aqueous solutions. Polylayer membranes were formed by the Langmuir-Blodgett method from octadecylamine and 1,2-bis-(2-aminophenoxy)ethane-N,N,N,N-tetraacetic acid. When brought in contact with an aqueous solution of a calcium salt, the ultrathin film sorbs metal ions. The chelator then transports metal ions over the whole membrane volume, and the ions are accumulated in the form of calcium hydroxide crystallites in regions enriched in the diphilic base. The main analytic parameters were determined by piezoquartz weighing, electrochemical impedance spectroscopy, and surface plasmon resonance spectroscopy. The response of sensor elements of this type was shown to be a linear function of the logarithm of the concentration of calcium ions over the concentration range 10^?8–10^?1 mol/l at the contact time between the film and the solution under study no more than 10 s. The conclusion was drawn that the membranes obtained remained highly sensitive with respect to calcium ions in 0.1 M solutions of NaCl and were selective with respect to other biologically relevant cations.     

Complex Formation of d‐Metal Ions at the Interface of TbIII‐Doped Silica Nanoparticles as a Basis of Substrate‐Responsive TbIII‐Centered Luminescence

The complex formation of d‐metal ions at the interface of Tb^III‐doped silica nanoparticles modified by amino groups is introduced as a route to sensing d‐metal ions and some organic molecules. Diverse modes of surface modification (covalent and noncovalent) are used to fix amino groups onto the silica surface. The interfacial binding of d‐metal ions and complexes is the reason for the Tb^III‐centered luminescence quenching. The regularities and mechanisms of quenching are estimated for the series of d‐metal ions and their complexes with chelating ligands. The obtained results reveal the interfacial binding of Cu^II ions as the basis of their quantitative determination in the concentration range 0.1–2.5 μM by means of steady‐state and time‐resolved fluorescence measurements. The variation of chelating ligands results in a significant effect on the quenching regularities due to diverse binding modes (inner or outer sphere) between amino groups at the interface of nanoparticles and Fe^III ions. The applicability of the steady‐state and time‐resolved fluorescence measurements to sense both Fe^III ions and catechols in aqueous solution by means of Tb^III‐doped silica nanoparticles is also introduced.     

Free energy of adsorption of water and metal ions on the [1014] calcite surface

We calculated the free energy profiles of water and three metal ions (magnesium, calcium, and strontium) adsorbing on the [1014] calcite surface in aqueous solution. The approach uses molecular dynamics with parametrized equations to describe the interatomic forces. The potential model is able to reproduce the interactions between water and the metal ions regardless of whether they are at the mineral surface or in bulk water. The simulations predict that the free energy of adsorption of water is relatively small compared to the enthalpy of adsorption calculated in previous papers. This suggests a large change in entropy associated with the water adsorption on the surface. We also demonstrate that the free energy profile of a metal ion adsorbing on the surface correlates with the solvent density and that the rate of formation of an innersphere complex depends on overcoming a large free energy barrier, which is mainly electrostatic in nature. Furthermore, comparison among the rates of desorption of magnesium, calcium, and strontium from the calcite surface suggests that magnesium has a much lower rate of desorption due to its strong interactions with both water and the surface.     

Catalytic Activity of Alkali Metal Cations for the Chemical Oxygen Reduction Reaction in a Biphasic Liquid System Probed by Scanning Electrochemical Microscopy

Chemical reduction of dioxygen in organic solvents for the production of reactive oxygen species or the concomitant oxidation of organic substrates can be enhanced by the separation of products and educts in biphasic liquid systems. Here, the coupled electron and ion transfer processes is studied as well as reagent fluxes across the liquid|liquid interface for the chemical reduction of dioxygen by decamethylferrocene (DMFc) in a dichloroethane-based organic electrolyte forming an interface with an aqueous electrolyte containing alkali metal ions. This interface is stabilized at the orifice of a pipette, across which a Galvani potential difference is externally applied and precisely adjusted to enforce the transfer of different alkali metal ions from the aqueous to the organic electrolyte. The oxygen reduction is followed by H₂O₂ detection in the aqueous phase close to the interface by a microelectrode of a scanning electrochemical microscope (SECM). The results prove a strong catalytic effect of hydrated alkali metal ions on the formation rate of H₂O₂, which varies systematically with the acidity of the transferred alkali metal ions in the organic phase.     

Competitive sorption of Cu(II) and Eu(III) ions on olive-cake carbon in aqueous solutions—a potentiometric study

The competitive sorption of Cu(II) and Eu(III) ions from aqueous solutions by olive-cake carbon, has been investigated by potentiometry at pH 6, I=0.1 M NaClO₄, 25°C and under normal atmospheric conditions. Evaluation of the experimental data supports the formation of inner-sphere surface complexes and results in the calculation of the formation constant of the surface complexes ((=S–O)₂Cu), which is found to amount log β _Cu=5.3±0.3. Addition of competing Eu(III) ions in the aqueous system leads to replacement of the Cu(II) by the competitor metal ion. Evaluation of the potentiometric data obtained from competition experiments indicates an ion-exchange mechanism. The formation constant of the Eu(III) species sorbed on olive cake carbon is found to be log β _Eu=5.1±0.5. Comparison of the complex formation constants of the olive-cake carbon with the corresponding complex formation constants for of olive cake and humic acid with the two metal ions, indicates that the same type of active sites is responsible for the metal ion complexation on the surface of the different types natural organic matter (e.g. olive-cake carbon, olive-cake and humic acid).     

Breakdown of hydration repulsion between charged surfaces in aqueous Cs+ solutions

Using a surface force balance, we have measured the normal and shear forces between mica surfaces across aqueous caesium salt solutions (CsNO(3) and CsCl) up to 100 mM concentrations. In contrast to all other alkali metal ions at these concentrations, we find no evidence of hydration repulsion between the mica surfaces on close approach: the surfaces appear to be largely neutralized by condensation of the Cs ions onto the charged lattice sites, and are attracted on approach into adhesive contact. The contact separation at adhesion indicates that the condensed Cs ions protrude by 0.3 +/- 0.2 nm from each surface, an observation supported both by the relatively weak adhesion energies between the surfaces, and the relatively weak frictional yield stress when they are made to slide past each other. These observations show directly that the hydration shells about the Cs(+) ions are removed as the ions condense into the charged surface lattice. This effect is attributed to the low energies-resulting from their large ionic radius-required for dehydration of these ions.     

金属离子的光催化去除研究进展

利用光催化剂表面的光生电子或空穴等活性物种，通过还原或氧化反应去除水相中的金属离子，是与环境保护、贵金属回收或金属担载催化剂制备相关的重要过程。笔者结合半导体的结构特征，综述了利用光催化还原反应或氧化反应，对铬、汞、铜、镍、银及铂、钯等贵金属和锰、铀等的光催化去除效果，介绍了该技术在处理金属离子混合体系实现金属分离过程的应用。结合有关实验数据，对一些可能反应机制进行了探讨。对与环境保护及其它相关工艺过程的应用进行了介绍。     

A rhodamine-based fluorescent and colorimetric chemodosimeter for the rapid detection of Hg2+ ions in aqueous media

A rhodamine-based fluorescent and colorimetric chemodosimeter for the rapid detection of Hg2+ ions in aqueous media was developed. The system, which utilizes an irreversible Hg2+-promoted oxadiazole forming reaction, responds instantaneously at room temperature in a 1:1 stoichiometric manner to the amount of Hg2+. The selectivity of this system for Hg2+ over other metal ions is remarkably high, and its sensitivity is below 2 ppb in aqueous solutions.     

Simple electrochemical method for deposition and voltammetric inspection of silver particles at the liquid-liquid interface of a thin-film electrode

A novel experimental methodology for depositing and voltammetric study of Ag nanoparticles at the water-nitrobenzene (W-NB) interface is proposed by means of thin-film electrodes. The electrode assembly consists of a graphite electrode modified with a thin NB film containing decamethylferrocene (DMFC) as a redox probe. In contact with an aqueous electrolyte containing Ag(+) ions, a heterogeneous electron-transfer reaction between DMFC((NB)) and Ag(+)((W)) takes place to form DMFC(+)((NB)) and Ag deposit at the W-NB interface. Based on this interfacial reaction, two different deposition strategies have been applied. In the uncontrolled potential deposition protocol, the electrode is immersed into an AgNO(3) aqueous solution for a certain period under open circuit conditions. Following the deposition step, the Ag-modified thin-film electrode is transferred into an aqueous electrolyte free of Ag(+) ions and voltammetrically inspected. In the second protocol the deposition was carried out under controlled potential conditions, i.e., in an aqueous electrolyte solution containing Ag(+) ions by permanent cycling of the electrode potential. In this procedure, DMFC((NB)) is electrochemically regenerated at the electrode surface, hence enabling continuation and voltammetric control of the Ag deposition. Hence, the overall electrochemical process can be regarded as an electrochemical reduction of Ag(+)((W)) at the W-NB interface, where the redox couple DMFC(+)/DMFC acts as a mediator for shuttling electrons from the electrode to the W-NB interface. Ag-particles deposited at the W-NB interface affect the ion transfer across the interface, which provides the basis for voltammetric inspection of the metal deposit at the liquid-liquid interface with thin-film electrodes. Voltammetric properties of thin-film electrodes are particularly sensitive to the deposition procedure, reflecting differences in the properties of the Ag deposit. Moreover, this methodology is particularly suited to inspect catalytic activities of metal particles deposited at the liquid-liquid interface toward heterogeneous electron-transfer reactions occurring at the at the liquid-liquid interface.     

Zinc Porphyrin Metal‐Center Exchange at the Solid–Liquid Interface

Demetalation of zinc 5,10,15,20‐tetraphenylporphyrin (ZnTPP) under acidic conditions and ion exchange with Cu²⁺ ions at neutral pH are both rapid reactions in the liquid medium. However, for ZnTPP monolayers adsorbed on a Au(111) surface exposed to aqueous solution, we find that, although ion exchange takes place rapidly as expected, demetalation does not occur, even at pH values as low as 0. Based on this, we conclude that metal center exchange on the surface does not proceed through a free‐base porphyrin as an intermediate. Furthermore, once formed, CuTPP is stable on the surface and the reverse exchange from CuTPP to ZnTPP in the presence of Zn²⁺ ions could not be achieved. The preference for copper is so strong that even an attempt to exchange adsorbed ZnTPP with Ni²⁺ ions in the presence of traces of Cu²⁺ yielded CuTPP rather than NiTPP.     

The influence of ionic strength, nutrients and pH on bacterial adhesion to metals

Bacteria-metal interactions in aqueous solutions are important in biofilm formation, biofouling and biocorrosion problems in the natural environment and engineered systems. In this study, the adhesion forces of two anaerobes (Desulfovibrio desulfuricans and Desulfovibrio singaporenus) and an aerobe (Pseudomonas sp.) to stainless steel 316 in various aqueous systems were quantified using atomic force microscopy (AFM) with a cell probe. Results show that the nutrient and ionic strength of the solutions influence the bacteria-metal interactions. The bacteria-metal adhesion force was reduced in the presence of the nutrients in the solution, because a trace organic film was formed and thus decreased the metal surface wettability. Stronger ionic strength in the solution results in a larger bacteria-metal adhesion force, which is due to the stronger electrostatic attraction force between the positively charged metal surface and negatively charged bacterial surface. Solution pH also influences the interaction between the bacterial cells and the metal surface; the bacteria-metal adhesion force reached its highest value when the pH of the solution was near the isoelectric point of the bacteria, i.e. at the zero point charge. The adhesion forces at pH 9 were higher than at pH 7 due to the increase in the attraction between Fe ions and negative carboxylate groups.     

Self-motion of a phenanthroline disk on divalent metal ion aqueous solutions coupled with complex formation

The self-motion of a 1,10-phenanthroline disk on divalent metal ion aqueous solutions was investigated as a simple autonomous motor coupled with complex formation. The characteristic features of motion (continuous and oscillatory motion) and their concentration regions differed among metal ions, and the frequency of oscillatory motion depended on the temperature of the aqueous solution. The nature of the characteristic motion is discussed in relation to the stability constant of complex formation between phenanthroline and a metal ion, and the difference in surface tension between phenanthroline and its metal complex as the driving force.     

纳米零价铁去除水中重金属离子的研究进展

重金属离子危害严重.本文综述了近几年纳米零价铁去除水中重金属离子的研究,总结了纳米零价铁去除水中重金属离子的机理,主要包括:纳米零价铁的表面吸附-配合、还原、吸附-还原,并对纳米零价铁在这一领域的应用进行了展望.