Electron-Donor Functional Groups, Band Gap Tailoring, and Efficient Charge Separation: Three Keys To Improve the Gaseous Iodine Uptake in MOF Materials - Université de Lille Accéder directement au contenu
Article Dans Une Revue ACS Applied Materials & Interfaces Année : 2023

Electron-Donor Functional Groups, Band Gap Tailoring, and Efficient Charge Separation: Three Keys To Improve the Gaseous Iodine Uptake in MOF Materials

Résumé

Metal–organic frameworks (MOFs) have been largely investigated worldwide for their use in the capture of radioactive iodine due to its potential release during nuclear accident events and reprocessing of nuclear fuel. The present work deals with the capture of gaseous I2 under a continuous flow and its subsequent transformation into I3– within the porous structures of three distinct, yet structurally related, terephthalate-based MOFs: MIL-125(Ti), MIL-125(Ti)_NH2, and CAU-1(Al)_NH2. The synthesized materials exhibited specific surface areas (SSAs) with similar order of magnitude: 1207, 1099, and 1110 m2 g–1 for MIL-125(Ti), MIL-125(Ti)_NH2, and CAU-1(Al)_NH2, respectively. Because of that, it was possible to evaluate the influence of other variables over the iodine uptake capacity─such as band gap energies, functional groups, and charge transfer complexes (CTC). After 72 h of contact with the I2 gas flow, MIL-125(Ti)_NH2 was able to trap 11.0 mol mol–1 of I2, followed by MIL-125(Ti) (8.7 mol mol–1), and by CAU-1(Al)_NH2 (4.2 mol mol–1). The enhanced ability to retain I2 in the MIL-125(Ti)_NH2 was associated with a combined effect between its amino group (which has a great affinity toward iodine), its smaller band gap (2.5 eV against 2.6 and 3.8 eV for CAU-1(Al)_NH2 and MIL-125(Ti), respectively), and its efficient charge separation. In fact, the presence of a linker-to-metal charge transfer (LMCT) mechanism in MIL-125(Ti) compounds separates the photogenerated electrons and holes into the two distinct moieties of the MOF: the organic linker (which stabilizes the holes) and the oxy/hydroxy inorganic cluster (which stabilizes the electrons). This effect was observed using EPR spectroscopy, whereas the reduction of the Ti4+ cations into the paramagnetic Ti3+ species was evidenced after irradiation of the pristine Ti-based MOFs with UV light (<420 nm). In contrast, because CAU-1(Al)_NH2 exhibits a purely linker-based transition (LBT)─with no EPR signals related to Al paramagnetic species─it tends to exhibit faster recombination of the photogenerated charge carriers as, in this case, both electrons and holes are located over the organic linker. Furthermore, the transformation of the gaseous I2 into In– [n = 5, 7, 9, ...] intermediates and then into I3– species was evaluated using Raman spectroscopy by following the evolution of their respective bands at about 198, 180, and 113 cm–1. This conversion─which is favored by an effective charge separation and smaller band gaps─increases the I2 uptake capacity of the compounds by creating specific adsorption sites for these anionic species. In fact, because the −NH2 groups act as an antenna to stabilize the photogenerated holes, both In– and I3– are adsorbed into the organic linker via an electrostatic interaction with these positively charged entities. Finally, changes regarding the EPR spectra before and after the iodine loading were considered to propose a mechanism for the electron transfer from the MOFs structure to the I2 molecules considering their different characteristics.
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Dates et versions

hal-04138757 , version 1 (31-08-2023)

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Citer

Pedro Andrade, Hania Ahouari, Christophe Volkringer, Thierry Loiseau, Herve Vezin, et al.. Electron-Donor Functional Groups, Band Gap Tailoring, and Efficient Charge Separation: Three Keys To Improve the Gaseous Iodine Uptake in MOF Materials. ACS Applied Materials & Interfaces, 2023, ACS Applied Materials & Interfaces, ⟨10.1021/acsami.3c04955⟩. ⟨hal-04138757⟩
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