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Luminescent ruthenium diimine complexes have been covalently bound to the surface of a silica polyamine composite (SPC) using peptide coupling agents. The loading of the complexes using this route is quite low (∼0.01-0.04 mmol/g) leaving sufficient surface amines to coordinate added metal ions. When the composite particles containing the Ru complexes are exposed to solutions of Cu2+, Ni2+ or Zn2+, luminescence is quenched with efficiencies that follow concentration dependence and the relative binding affinities of the ions. When heavy metal ions such as mercury or lead are adsorbed onto the same surface, luminescence is enhanced by a factor of ∼3.5. When the complexes are exposed to these metals in solution, no quenching or enhancement is observed. Both phenomena were shown to be the result of adsorption of the cations onto the polyamine surface by using the Stern-Volmer relationship. The mechanism of both quenching and enhancement is discussed and the options for further development of this novel metal sensing technique are presented. [ABSTRACT FROM AUTHOR]

Silica polyamine composites made from silanized amorphous silica gel and a polyamine (polyallylamine (BP-1) and poly(ethyleneimine) (WP-1)) were functionalized with ethylenediamine-N,N,N′,N′-tetraacetic (EDTA) anhydride resulting in the modified composites BP-ED and WP-ED respectively. Successful immobilization of the poly-acetate ligand was confirmed by weight gain, IR and elemental analysis. The modified composites had ligand loading values of 0.78 mmol/g and 0.58 mmol/g respectively. Adsorption characteristics were investigated for BP-ED and WP-ED by pH profiles, time dependent isotherms, concentration dependent isotherms, and the Langmuir and Freundlich adsorption models. Metal ion capacities (mmol of metal adsorbed per gram of adsorbent) were shown to increase with pH for BP-ED and WP-ED, which is in contrast with silica gel modified with EDTA anhydride via amino propyl silane without the use of a polyamine where the opposite trend is observed. The adsorption of Ni(II), Zn(II) and Co(II) onto BP-ED and WP-ED was shown to fit the Langmuir adsorption model, which indicates a monolayer, non-cooperative metal ion uptake. For both composites the divalent metal ion selectivity is as follows: Cu(II)>Ni(II)>> Zn(II), Co(II)>> Mn(II). Also the trivalent metal ion selectivity is as follows: Fe(III)>Ga(III)>> Eu(III)>Al(III). This is in close agreement with reported formation constants for EDTA in solution. Breakthrough and recovery tests were carried out using a 5cc packed column. The separation and recovery of Ni(II) from Co(II) when BP-ED was challenged with a solution containing 1.5 mg/L of both metals resulted in an acidic strip solution of greater than 97% Ni(II) purity. Further, selective separation of Ni(II) from a solution containing low levels of Co(II) and Zn(II) and high level Fe(II) at pH=1 was also achieved. Ni(II) was extracted at a flow rate of 0.1 column volumes per minute (0.5 mL/min) and recovered in greater than 90% purity by an acidic strip. Impurity in the strip was a consequence of Fe(II) oxidation to Fe(III). These tests demonstrate that well resolved separations of one divalent metal ion from one or more other divalent metal ions are possible through the use of EDTA anhydride modified silica polyamine composites with higher capacities than the previously reported amino propyl silane modified silica gel. [ABSTRACT FROM AUTHOR]

A series of core-shell magnetic nanomaterials have been synthesized with the intent of applying them for metal ion capture in a newly designed pipeline reactor. The synthetic chemistry is an extension of a previously developed family of materials based on amorphous silica gel, which has been used in the mining and remediation industries. The nanoparticles were characterized by infrared spectroscopy and TEM and SEM techniques. The size of the starting magnetite core was critical to the behavior of the particles under metal sequestering conditions. The capture kinetics of the resulting nanoagregates is 10 times faster than related micro composites. All of the tests performed point to the future successful development of a technology that circumvents the disadvantages associated with the use of column based microparticles. [ABSTRACT FROM AUTHOR]

A novel silica–polyamine composite material, WP-1, was synthesized according to a new patented procedure for aqueous heavy metal ion removal. The effects of pH and initial concentration of metal ions on adsorption were investigated. Results showed that WP-1 has metal ion capacities in the order Cu(II) > Ni(II) > Fe(II) and generally works best in the 2–4 pH range. Kinetic studies showed the Cu(II) adsorption reaction occurs in a second-order fashion with a rate constant of 4.4 × 10-4 s-1. Two similar silica–polyamine materials, prepared by different procedures cited in the literature, were compared with WP-1 for Cu(II) ion capacity and mechanical durability. These tests showed that capacities were more than twice as high when the new patented procedure was used, indicating much better coverage of the silica gel. During repeated metal loading and unloading tests, WP-1 maintained up to 94% of its initial Cu(II) capacity and its mechanical integrity for 3000 cycles, whereas testing of the other materials had to be stopped prematurely due to degradation of the materials. [ABSTRACT FROM AUTHOR]

Details a study which described two modified silica-polyamine composite materials. Separation of metal ions; Efficiency composite materials in metal ion removal; Discussion and conclusion.