Effects of Water and pH on the Oxidative Oligomerization of Chloro an Methoxyphenol by a Montmorillonite Clay

This study focussed on the capacity of a montmorillonite clay to oxidize organic contaminants having activating (methoxyphenol) and deactivating (chlorophenol) substituent groups when pH and water conditions are changing. The amount and strength of Lewis and Br?nsted acidity of the clay was measured using organic indicator and titration methods. Water plays two distinct roles in the oxidation of such contaminants by clays: (1) it neutralizes the clay's Lewis acidity, thereby preventing chlorophenol from getting oxidized in significant yields; (2) it does not successfully compete with methoxyphenol for Lewis acid sites because high dimer yields are observed. The high capacity of Na⁺, Ca²⁺, and Fe³⁺ clays to oxidize phenolic compounds at high pH appears to be caused by phenolates being more reactive than the protonated form. The Lewis and Br?nsted acidity measurement of the various homoionic clays tested help explain the high capacity of the clays to oxidize phenolic compounds at low and high pH and their low capacity at near neutral pH. Finally, the results also clarify the effects of exchangeable cations on the capacity of clays to oxidize organic contaminants.