Metal ligand complexes, adsorption

Several approaches to immobilize transition metal catalysts on polymer supports have been reported in the literature. The most representative ones are (1) immobilization of ligands as well as ligand-metal complexes by covalent and/or coordination bonds (2) adsorption of catalysts on the supports (3) formation of ionic pairs between, for example, the surface of the support bearing anionic functional groups and cationic metal species and (4) entrapment of catalysts... 

In metal chelate adsorption chromatography a metal is immobilised by partial chelation on a column which contains bi- or tri- dentate ligands. Its application is in the separation of substances which can complex with the bound metals and depends on the stability constants of the various ligands (Porath, Carlsson, Olsson and Belfrage Nature 258 598 I975 Loennerdal, Carlsson and Porath FEES Lett 75 89 1977). 

Molecular simulation methods can be a complement to surface complexation modeling on metal-bacteria adsorption reactions, which provides a more detailed and atomistic information of how metal cations interact with specific functional groups within bacterial cell wall. Johnson et al., (2006) applied molecular dynamics (MD) simulations to analyze equilibrium structures, coordination bond distances of metal-ligand complexes. 

Instead of electrostatic (or physical) adsorption, metal uptake onto oxides might be considered chemical in nature. In chemical mechanisms, the metal precursor is envisioned to react with the oxide surface, involving as surface-ligand exchange [13,14] in which OH groups from the surface replace ligands in the adsorbing metal complex. In this section it will be shown that a relatively simple electrostatic interpretation of the adsorption of a number of catalyst precursors is the most reasonable one for a number of noble metal/oxide systems. 

The retention of hydration sheaths upon adsorption is more consistent with an electrostatic view of adsorption than a chemical one, since by remaining a relatively large distance away from the surface, the metal complexes are less likely to participate in surface-ligand exchange. 

Organic material can strongly adsorb metal ions the functional groups on their surfaces act as ligands (carboxyl, amino groups etc.) for metal ions. All these functional groups favor the surface complex formation with metals the adsorption reactions are favored at higher pH (Fig. 11.11). 

Metal Ion Adsorption in Mixtures of Multiple Solid Phases. One of the arguments put forth for extending the concepts of solution coordination chemistry to heterogeneous systems is the hypothesis that the mineral components of soils or sediments can be considered as ligands which compete for complexation of adsorbates. To this end, it is important to know the relative ability of different mineral surfaces to complex solutes. 

Speciation is a dynamic process that depends not only on the ligand-metal concentration but on the properties of the aqueous solution in chemical equilibrium with the surrounding solid phase. As a consequence, the estimation of aqueous speciation of contaminant metals should take into account the ion association, pH, redox status, formation-dissolution of the solid phase, adsorption, and ion-exchange reactions. From the environmental point of view, a complexed metal in the subsurface behaves differently than the original compound, in terms of its solubility, retention, persistence, and transport. In general, a complexed metal is more soluble in a water solution, less retained on the solid phase, and more easily transported through the porous medium. 

The presence of anions in solution may enhance cation adsorption by formation of mixed metal/ligand surface complexes (Schindler, 1990). This effect is termed ternary adsorption. Two forms of ternary adsorption have been identified ... 

Selective and reversible adsorption of gaseous molecules such as dioxygen, carbon monoxide, ethylene, acetylene, and dinitrogen have been performed by the use of suitable macromolecule-metal complexes. Selective adsorption of metal ions such as UO has also been studied using polymeric ligands. 

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