Coordination nature of aluminum (oxy)hydroxides formed under the influence of tannic acid studied by X-ray absorption spectroscopy

The effect of biomolecules on the mechanisms of the formation and nature of the transformation products of Al (oxy)hydroxides at the atomic and molecular levels and the impact on their nano-scale surface chemistry remain to be uncovered. In this article, the coordination structure of Al in Al (oxy)hydroxides formed under the influence of tannic acid was studied with X-ray absorption near edge structure (XANES) spectroscopy. Al K-edge and L-edge spectra show that as the tannate/Al molar ratio (MR) was increased from 0, 0.001, 0.01 to 0.1, the coordination number of Al changed from the sixfold coordination to mixed six-, five-, and/or fourfold coordination in the structural network of the Al (oxy)hydroxides formed under the increasing perturbation of tannic acid. In O K-edge spectra, the intensity of the peak assigned to the π^∗ at 532.1 eV increased as the tannate/Al MR increased, with the spectrum of the Al precipitate formed at a tannate/Al MR of 0.1 being almost identical to that of tannic acid. These results indicate that tannate ligands are incorporated into the structural network of short-range ordered Al (oxy)hydroxides to perturb their structural configuration during the formation of Al precipitates under the influence of tannic acid. With increasing tannate/Al MR, the Al (oxy)hydroxides decreased in amount and developed structural defects and the Al-tannate precipitates increased in amount. The decrease in the coordination number of Al in the Al (oxy)hydroxides is attributed to steric and electronic factors which cause the change in Al-O bonding, because Al is complexed with tannate which has different functional groups and is much larger in size compared with OH and H₂O ligands. The surface reactivity of a metal-O bond is related to its covalency and coordination geometry. The findings obtained in the present study are, thus, of fundamental significance in understanding the structural and surface chemistry of Al (oxy)hydroxides and their impact on the transformation, transport, and fate of nutrients and pollutions in the environment.