Glycine buffered synthesis of layered iron(II)-iron(III) hydroxides (green rusts)

Layered Fe-II-Fe-III hydroxides (green rusts, GRs) are efficient reducing agents against oxidizing contaminants such as chromate, nitrate, selenite, and nitroaromatic compounds and chlorinated solvents. In this study, we adopted a buffered precipitation approach where glycine (GLY) was used in the synthesis of sulfate-interlayered GR (GR(SO4)) by aerial oxidation of Fe-II or co-precipitation by adding Fe-III salt to an aqueous solution of Fe at constant pH. In both the oxidation and the co-precipitation methods pure crystalline GRs04 was precipitated in the presence of 70 mM GLY (pH 8.0), whereas in the absence of GLY, synthesis failed under similar conditions. Gycine functions as both a pH buffer and a ligand; Fen-GLY complexes serve as a source of base (Fe-II-GLY + H2O -> Fe-II + H-GLY + OH-) during GR formation, supplying about 45% of the total base required for the synthesis. The GLY buffer decreases pH fluctuations during base addition and hence allows for fast GRs04 precipitation, minimizing byproduct formation. The use of other pH buffers [4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid and 2-amino-2-(hydroxyme thyl)-1,3-propanediol] was also tested but failed. Mossbauer spectroscopy, X-ray diffraction, Fourier transform infrared, transmission electron microscopy, and Fe-III measurements confirmed the purity, stoichiometry, and pyroaurite-type structure of the obtained GR(SO4). The formula of GR(SO4) was found to be Fe-4.08(II) Fe-1.98(III) (OH)(116)(SO4)(1.00), and the tabular GR crystals had a lateral size of 100-500 nm and a thickness of about 40 nm. Upscaling of the synthesis by either 25 times in volume or 20 times in Fe-II concentration resulted in pure GR(SO4) products. Compared with the conventional unbuffered GR(SO4) synthesis method, the present method can provide pure products with a controllable, fast, and low-cost process. (C) 2016 Elsevier Inc. All rights reserved.