Iodine Uptake by Zr-/Hf-Based UiO-66 Materials: The Influence of Metal Substitution on Iodine Evolution

Many works reported the encapsulation of iodine in metal-organic frameworks as well as the I₂ → I₃^- chemical conversion. This transformation has been examined by adsorbing gaseous iodine on a series of UiO-66 materials and the different Hf/Zr metal ratios (0-100% Hf) were evaluated during the evolution of I₂ into I₃^-. The influence of the hafnium content on the UiO-66 structure was highlighted by PXRD, SEM images, and gas sorption tests. The UiO-66(Hf) presented smaller lattice parameter (a = 20.7232 Å), higher crystallite size (0.18 ≤ Φ ≤ 3.33 μm), and smaller SSA_BET (818 m²·g^-1) when compared to its parent UiO-66(Zr) ─ a = 20.7696 Å, 100 ≤ Φ ≤ 250 nm, and SSA_BET = 1262 m²·g^-1. The effect of replacing Zr atoms by Hf in the physical properties of the UiO-66 was deeply evaluated by a spectroscopic study using UV-vis, FTIR, and Raman characterizations. In this case, the Hf presence reduced the band gap of the UiO-66, from 4.07 eV in UiO-66(Zr) to 3.98 eV in UiO-66(Hf). Furthermore, the UiO-66(Hf) showed a blue shift for several FTIR and Raman bands, indicating a stiffening on the implied interatomic bonds when comparing to UiO-66(Zr) spectra. Hafnium was found to clearly favor the capture of iodine [285 g·mol^-1, against 230 g·mol^-1 for UiO-66(Zr)] and the kinetic evolution of I₂ into I₃^- after 16 h of I₂ filtration. Three iodine species were typically identified by Raman spectroscopy and chemometric analysis. These species are as follows: "free" I₂ (206 cm^-1), "perturbed" I₂ (173 cm^-1), and I₃^- (115 and 141 cm^-1). It was also verified, by FTIR spectroscopy, that the oxo and hydroxyl groups of the inorganic [M₆O₄(OH)₄] (M = Zr, Hf) cluster were perturbed after the adsorption of I₂ into UiO-66(Hf), which was ascribed to the higher acid character of Hf. Finally, with that in mind and considering that the EPR results discard the possibility of a redox phenomenon involving the tetravalent cations (Hf⁴⁺ or Zr⁴⁺), a mechanism was proposed for the conversion of I₂ into I₃^- in UiO-66─based on an electron donor-acceptor complex between the aromatic ring of the BDC linker and the I₂ molecule.