Conversion of Cr(VI) to Cr(III) in Water Using Amino-Modified Ordered Mesoporous Silicas: Influence of the Functional Group Architecture

Two nitrogen-modified mesoporous MCM-41-type silicas were synthesized by the sol–gel route and post-grafting surface modification procedure, obtaining an aminopropyl-modified MCM-41 (denoted MCM-41-N) and an aminoethyl-aminopropyl-modified MCM-41 (denoted MCM-41-NN). Hexavalent chromium removal from acidified water by adsorption and reduction to Cr(III) on the solid mesophases was analyzed. The modified silicas were characterized by powder X-ray diffraction (XRD), Fourier transformed infrared spectra (FT-IR), nitrogen adsorption–desorption measurements at −196 °C, X-ray photoelectron spectroscopy (XPS), 29Si solid state Nuclear Magnetic Resonance (29Si-RMN), and thermogravimetric analysis (TGA). Both samples exhibited very high capacities for decreasing Cr(VI) concentrations in water, according to the Langmuir isotherm model: 129.9 mg·g−1 for MCM-41-N and 133.3 mg·g−1 for MCM-41-NN. The chromium speciation in the supernatant after 24 h indicates that MCM-41-N had a higher capacity to reduce Cr(VI) to the less toxic Cr(III) species than MCM-41-NN: 92.9% vs. 72.5% when the initial Cr(VI) concentration was 10 mg·g−1. These differences were related to the different capacity of nitrogen atoms in MCM-41-N and MCM-41-NN to interact with the surrounding surface silanols which are required for the chemical reduction in the hexavalent species to take place, as evidenced by FT-IR and XPS analysis. Also, the Cr(III)/Cr(VI) atomic ratios on the solid’s surfaces were higher for MCM-41-N. These results highlight the characteristics that nitrogen atoms incorporated into silica matrices must possess in order to maximize the transformation of Cr(VI) into the trivalent species, thereby reducing the generation of toxic waste harmful to living organisms.