clay and pyridine

We investigated the adhesion of two functional groups to α-alumina as a model for the adsorption of organic molecules on clay minerals. Interactions between organic compounds and clay minerals play an important role in processes such as drinking water treatment, remediation of contaminated soil, oil recovery, and fabricating complicated nanomaterials, and there have been claims that organic compound-clay mineral interaction created the ordering that is necessary for the genesis of life. In many organisms, interaction between organic molecules and biominerals makes it possible to control the growth of bones, teeth, and shells. Adhesion of carboxylic acid, -COO(H), and pyridine, -C5H5N(H(+)), on the {0001} plane of α-alumina wafers has been investigated with atomic force microscopy (AFM) in chemical force mapping (CFM) mode. Both functional groups adhered to α-alumina in deionized water at pH < 5, and adhesion decreased as NaCl or CaCl2 concentration increased. X-ray photoelectron spectroscopy (XPS) showed that Na(+) and Ca(2+) adsorbed to the α-alumina surface at pH < 5, decreasing surface interaction with the carboxylic acid and pyridine groups. We interpret the results as evidence that the tips adhere to alumina through hydrogen bonding when only water is present. In solutions containing NaCl and CaCl2, cations are adsorbed but Cl(-) is not. When NaCl solutions are replaced by CaCl2, Ca(2+) replaces Na(+), but rinsing with ultrapure deionized water (pH 5.6) could not restore the original protonated surface. The results demonstrate that the alumina surface at pH 3 has a higher affinity for inorganic cations than for -COO(H) or -C5H5N(H(+)), in spite of the known positive surface charge of α-alumina {0001} wafers. These results demonstrate that solution salinity plays an important role in surface properties, controlling surface tension (i.e., contact angle) and adsorption affinity on α-alumina and, by analogy, on clay minerals.

Topics: Adsorption; Aluminum Oxide; Aluminum Silicates; Calcium Chloride; Carboxylic Acids; Clay; Hydrogen-Ion Concentration; Microscopy, Atomic Force; Pyridines; Salinity; Sodium Chloride; Surface Tension; Thermodynamics; Water

The surface properties and functionality of an illite-containing clay mineral in alkaline solutions containing increasing quantities of calcium hydroxide were investigated using FTIR monitored pyridine adsorption at various temperatures. Results showed that the binding behavior of electron donor pyridine molecules to illite platelets is mostly governed by electron acceptor sites located at the edges of the clay particles. The binding of bulky hydrated calcium ions at the surface of the illite platelets decreases the surface area of illite. Moderate thermal treatments up to 450°C do not affect the structure of the clay mineral but strongly decrease the number of Lewis and Brönsted sites available at the edges of the clay platelets.

Topics: Adsorption; Aluminum Silicates; Binding Sites; Calcium; Calcium Compounds; Calcium Hydroxide; Clay; Electrons; Hot Temperature; Ions; Minerals; Oxides; Pyridines; Spectroscopy, Fourier Transform Infrared; Surface Properties