Insight into the Mechanism of Arsenic(III/V) Uptake on Mesoporous Zerovalent Iron-Magnetite Nanocomposites: Adsorption and Microscopic Studies.

Mesoporous zerovalent iron-magnetite nanocomposites (ZVI-MNCs) were developed to circumvent the limitations of magnetite, such as its susceptibility to phase transition in air-water interfaces. High-resolution transmission electron microscopy images revealed the presence of Fe0 and Fe3O4 in the as-prepared adsorbent. High-resolution X-ray photoelectron spectroscopy (HR-XPS) Fe 2p deconvoluted spectra showed that electron transfer between Fe0 and Fe3O4 controlled the magnetite transformation. The isotherm equilibrium data for As(III) and As(V) are described by the Sips model, which suggests single- and multilayer formation onto a heterogeneous surface with different binding sites, whereas adsorption is controlled by a pseudo-second-order kinetic model, which indicates chemisorption. The maximum sorption capacities (qm) for As(III) and As(V) are 632.6 and 1000 μmol g-1, respectively, which are larger than the qm of similar adsorbents. The greater qm for As(V) is attributed to a higher multilayer formation and a stronger bonding force compared with As(III). The arsenic uptake capacity showed that the as-prepared adsorbent was effective over a wide pH range, and an optimal uptake capacity was recorded between pH 5.0 and 9.0 for As(III) and 3.0 and 7.0 for As(V). The adsorbent exhibited a remarkable regeneration performance for As(III) and As(V) uptake. Several microscopic analytical tools, including Fourier transform infrared spectroscopy, HR-XPS, and X-ray absorption near-edge structure together with zeta potential, confirmed that the binding mode of As(III) and As(V) on ZVI-MNCs was predominantly inner-sphere coordination. Partial redox transformation occurred for As(III) and As(V) on nearly 10 nm of the adsorbent, which indicates that a surface redox mechanism contributed partially to arsenic uptake on the near surface of the ZVI-MNCs. Extended X-ray absorption fine structure spectral analysis proposed that a corner-sharing monodentate mononuclear (1V) complex occurred for As(III) with a small portion of a corner-sharing bidentate binuclear (2C) complex, whereas As(V) formed a corner-sharing bidentate binuclear (2C) complex with octahedral Fe bonding.