A Silicate/Glycine Switch To Control the Reactivity of Layered Iron(II)–Iron(III) Hydroxides for Dechlorination of Carbon Tetrachloride

Layered FeII–FeIII hydroxide chloride (chloride green rust, GRCl) has high reactivity toward reducible pollutants such as chlorinated solvents. However, this reactive solid is prone to dissolution, and hence loss of reactivity, during storage and handling. In this study, adsorption of silicate (Si) to GRCl was tested for its ability to minimize GRCl dissolution and to inhibit reduction of carbon tetrachloride (CT). Silicate adsorbed with high affinity to GRCl yielding a sorption maximum of 0.026 g of Si/g of GRCl. In the absence of Si, the pseudo-first-order rate constant for CT dehalogenation by GRCl was 2.1 h–1, demonstrating very high reactivity of GRCl but with substantial FeII dissolution up to 2.5 mM. When Si was adsorbed to GRCl, CT dehalogenation was blocked and FeII dissolution extent was reduced by a factor of 28. The addition of glycine (Gly) was tested for reactivation of the Si-blocked GRCl for CT dehalogenation. At 30 mM Gly, partial reactivation of the GRCl was observed with pseudo-first-order rate constant for CT reduction of 0.075 h–1. This blockage and reactivation of GRCl reactivity demonstrates that it is possible to design a switch for GRCl to control its stability and reactivity under anoxic conditions.