Maria Celeste Bernini

In heterogeneous oxidation systems, the sequence in which oxidants interact with catalyst surfaces can influence surface chemistry and system response. In this work, the interaction between hydrogen peroxide and the metal–organic framework MIL-100(Fe) is investigated under heterogeneous oxidation conditions associated with Fenton-type reactions, with emphasis on the influence of reactant contact order and oxidant dose.MIL-100(Fe) was thermally activated to generate coordinatively unsaturated iron sites, as confirmed by FTIR and XPS, while preserving the long-range crystalline framework. Controlled contact protocols were used to regulate the interaction sequence between the activated MOF, hydrogen peroxide, and the organic substrate. Experiments using Rhodamine 6G as a model pollutant show that hydrogen peroxide consumption and dye removal strongly depend on the order in which the oxidant and substrate contact the activated material.Structural characterization combining PXRD, SAXD, and vibrational spectroscopy reveals that exposure to hydrogen peroxide induces localized, dose-dependent structural heterogeneities while maintaining framework integrity. Elemental (CHN) analysis and FTIR of recovered solids were used to evaluate dye removal processes.Overall, the results show that the surface response of MIL-100(Fe) to hydrogen peroxide, governed by reactant contact order, plays a key role in pollutant removal behavior.

Defect-inspired amino-functionalization of layered Tb-doped coordination networks generates chemically distinct local environments that control analyte-dependent luminescence attenuation pathways in water.

A deep study on the water induced-phase transition from the 3D MOF-76 structure to the 1D LnBTC coordination polymer is presented. The initial particle size of MOF-76(Y_0.95Eu_0.05) has a lasting impact on the luminescence of the transformed material.

In this work, the influence of degassing temperature and urea functionalization were investigated as ways to improve the CO₂ adsorption performance of CPO-27-Mg. Through post-synthesis modification treatments, four samples with different degrees of urea functionalization were obtained, incorporating 10, 25, 50, and 100% of urea concerning the metal sites of the MOF. Alternatively, the influence of the degassing temperature of the non-functionalized MOF between 70 and 340 °C was also evaluated. The resulting compounds were characterized by N₂ adsorption–desorption isotherms at −196 °C using TGA-MS, FTIR, and PXRD. Finally, the thermally treated and functionalized CPO-27-Mg was evaluated for CO₂ capture.

Coordination networks (CNs) with tailorable multi‐metallic composition were designed and then used as sacrificial materials to obtain promising materials with Up‐conversion (UC) properties. The metal‐organic precursors led to solid solutions of Rare‐Earth Oxides (REO)Y₂O₃:Yb³⁺/Er³⁺or Y₂O₃:Yb³⁺/Er³⁺/Gd³through a calcination process. In order to obtain luminescent UC platforms, spin‐coating technique was implemented to deposit these materials onto glass supports. The synthesized solids and the resulting films were characterized by Scanning Electron Microscopy – Energy Dispersive Spectroscopy (SEM‐EDS), infrared spectroscopy, powder (PXRD), and grazing incidence (GIXRD) X‐ray diffraction techniques. Moreover, the photophysical properties of bulk and deposited Y₂O₃:Ln³⁺doped oxides were evaluated after being irradiated with NIR wavelength (980 nm) laser to excite the Yb³⁺sensitizer ion. Besides, decay emission profiles from each sample were also obtained and lifetime (τ_obs) values were calculated. These results open up the implementation of REO thin films obtained through CN calcination for promising applications such as solar cells and sensor devices.

Water–ethanol suspensions of 2D coordination network (CN) based on rare earth elements and mixed ligands were evaluated as reactive oxygen species (ROS) generators under UV light irradiation, in contact with a biomimetic substrate (tryptophan) or an O₂(¹Δ_g) quencher (1,3-diphenylisobenzofuran; 1,3-DPBF). A combination of bottom-up and top-down strategies was implemented in order to obtain nano-sized CN particles and the subsequent colloidal suspensions were also tested towards photodynamic inactivation of Candida albicans (C. albicans). SEM, TEM, FTIR, and XRD techniques were applied to characterize the solids and ICP-AES was employed to determine the metal content of the colloidal suspensions. Promising results were found indicating that the presence of Tb³⁺ allows an intersystem crossing suitable for singlet oxygen generation, resulting in the antifungal activity of C. albicans culture upon UV-irradiation.

Novel composites were synthesised through a fusion between CPO-27-Mg framework and mesoporous silica KIT-6 and tested in the CO ₂ adsorption.

The intense development that Metal‐Organic Frameworks have experienced along the last two decades, reflects the interest on these compounds as a new generation of multifunctional materials with diverse applications. The first works of Prof. Omar Yaghi devoted to obtain open frameworks by combining rigid aromatic linkers and a variety of metal centers, encouraged the creativity of the scientific community to designcoordination polymers employing aliphatic ligands as multitopic building blocks . Here, a revision of the literature dedicated to rare earth coordination networks mainly based in succinate ligand and derivatives is performed. A structural analysis of 2D and 3D frameworks based on rare earth elements and succinate, was carried out considering their inner connectivities and topologies with focus on those compounds with potential photoluminescent and catalytic technological applications. Thus, a variety of optical behaviours regarding the emission mechanisms, colours, lifetimes, quantum yields as well as chemical/thermal sensing properties are presented and compared with related phases found in literature. The catalytic performance of several rare earth‐succinates in three important reactions is discussed in terms of their acidity, dimensionality and available active centers towards the formation of the desired products analysing parameters such as selectivity, yields and TOFs.